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  • 1. Achenbach, Bastian
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Wahiduzzaman, Mohammad
    Pappler, Sandra K.
    Meinhart, Marcel
    Siegel, Renée
    Maurin, Guillaume
    Senker, Jürgen
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Porous Salts Containing Cationic Al24-Hydroxide-Acetate Clusters from Scalable, Green and Aqueous Synthesis Routes2023In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 62, no 29, article id e202218679Article in journal (Refereed)
    Abstract [en]

    The solution chemistry of aluminum is highly complex and various polyoxocations are known. Here we report on the facile synthesis of a cationic Al24 cluster that forms porous salts of composition [Al24(OH)56(CH3COO)12]X4, denoted CAU-55-X, with X=Cl, Br, I, HSO4. Three-dimensional electron diffraction was employed to determine the crystal structures. Various robust and mild synthesis routes for the chloride salt [Al24(OH)56(CH3COO)12]Cl4 in water were established resulting in high yields (>95 %, 215 g per batch) within minutes. Specific surface areas and H2O capacities with maximum values of up to 930 m2 g−1 and 430 mg g−1 are observed. The particle size of CAU-55-X can be tuned between 140 nm and 1250 nm, permitting its synthesis as stable dispersions or as highly crystalline powders. The positive surface charge of the particles, allow fast and effective adsorption of anionic dye molecules and adsorption of poly- and perfluoroalkyl substances (PFAS). 

  • 2. Albat, Martin
    et al.
    Inge, Andrew Kentaro
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Synthesis and crystal structure of three new bismuth(III) arylsulfonatocarboxylates2017In: Zeitschrift für Kristallographie - Crystalline Materials, ISSN 2194-4946, Vol. 232, no 1-3, p. 245-253Article in journal (Refereed)
    Abstract [en]

    Three new bismuth arylsulfonatocarboxylates [Bi(OH)(SB)] (1), [Bi-4(ST)(2)(HST)O-2(H2O)(2)]center dot H2O (2) and [Bi-4(ST)(2)O-3(H2O)(2)] (3) were synthesized under solvothermal reaction conditions at 180 degrees C using the potassium or sodium salt of 4-sulfobenzoic acid (H2SB) and 2-sulfoterephthalic acid (H3ST), respectively. The compounds were characterized in detail and the crystal structures were determined from single crystal X-ray diffraction data. Phase purity was confirmed by powder X-ray diffraction and elemental analysis. Structural comparisons to the only three other known bismuth sulfonatocarboxylates are presented. Due to the higher reaction temperatures employed for the synthesis of the title compounds a higher degree of condensation of the BiOx polyhedra (X = 7 or 8) to tetrameric units, 1D chains or a 2D layer is observed. Connection through the organic linker molecules leads to the formation of 3D coordination polymers in all three title compounds.

  • 3. Amombo Noa, Francoise M.
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Åhlén, Michelle
    Reinholdsson, William E.
    Göb, Christian R.
    Coudert, François-Xavier
    Cheung, Ocean
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Öhrström, Lars
    Chiral Lanthanum Metal–Organic Framework with Gated CO2 Sorption and Concerted Framework Flexibility2022In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 144, no 19, p. 8725-8733Article in journal (Refereed)
    Abstract [en]

    A metal–organic framework (MOF) CTH-17 based on lanthanum(III) and the conformationally chiral linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)benzene, cpb6–: [La2(cpb)]·1.5dmf was prepared by the solvothermal method in dimethylformamide (dmf) and characterized by variable-temperature X-ray powder diffraction (VTPXRD), variable-temperature X-ray single-crystal diffraction (SCXRD), and thermogravimetric analysis (TGA). CTH-17 is a rod-MOF with new topology och. It has high-temperature stability with Sohncke space groups P6122/P6522 at 90 K and P622 at 300 and 500 K, all phases characterized with SCXRD and at 293 K also with three-dimensional (3D) electron diffraction. VTPXRD indicates a third phase appearing after 620 K and stable up to 770 K. Gas sorption isotherms with N2 indicate a modest surface area of 231 m2 g–1 for CTH-17, roughly in agreement with the crystal structure. Carbon dioxide sorption reveals a gate-opening effect of CTH-17 where the structure opens up when the loading of CO2 reaches approximately ∼0.45 mmol g–1 or 1 molecule per unit cell. Based on the SCXRD data, this is interpreted as flexibility based on the concerted movements of the propeller-like hexatopic cpb linkers, the movement intramolecularly transmitted by the π–π stacking of the cpb linkers and helped by the fluidity of the LaO6 coordination sphere. This was corroborated by density functional theory (DFT) calculations yielding the chiral phase (P622) as the energy minimum and a completely racemic phase (P6/mmm), with symmetric cpb linkers representing a saddle point in a racemization process.

  • 4.
    Bartoszewicz, Agnieszka
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Marcos, Rocio
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sahoo, Suman
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols2012In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 45, p. 14510-14519Article, review/survey (Refereed)
    Abstract [en]

    A series of new iridium(III) complexes containing bidentate N-heterocyclic carbenes (NHC) functionalized with an alcohol or ether group (NHC?OR, R=H, Me) were prepared. The complexes catalyzed the alkylation of anilines with alcohols as latent electrophiles. In particular, biscationic IrIII complexes of the type [Cp*(NHC-OH)Ir(MeCN)]2+2[BF4-] afforded higher-order amine products with very high efficiency; up to >99?% yield using a 1:1 ratio of reactants and 12.5 mol?% of Ir, in short reaction times (216 h) and under base-free conditions. Quantitative yields were also obtained at 50?degrees C, although longer reaction times (4860 h) were needed. A large variety of aromatic amines have been alkylated with primary and secondary alcohols. The reactivity of structurally related iridium(III) complexes was also compared to obtain insights into the mechanism and into the structure of possible catalytic intermediates. The IrIII complexes were stable towards oxygen and moisture, and were characterized by NMR, HRMS, single-crystal X-ray diffraction, and elemental analyses.

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  • 5. Benecke, Jannik
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Engesser, Tobias A.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Reinsch, Helge
    Observation of three different linker conformers in a scandium ferrocenedicarboxylate coordination polymer2020In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 22, no 34, p. 5569-5572Article in journal (Refereed)
    Abstract [en]

    Electron and powder diffraction were combined to elucidate the structure of the new coordination polymer [Sc-2(FcDC)(3)] based on 1,1'-ferrocenedicarboxylate (FcDC(2-)), denoted as CAU-50. Remarkably, three different conformers of the very same linker molecule are observed, two of which serve as connectors for the scandium cations while one conformer acts as capping agent.

  • 6. Benecke, Jannik
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fuß, Alexander
    Wöhlbrandt, Stephan
    Engesser, Tobias A.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Reinsch, Helge
    Polymorphous Indium Metal-Organic Frameworks Based on a Ferrocene Linker: Redox Activity, Porosity, and Structural Diversity2020In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 59, no 14, p. 9969-9978Article in journal (Refereed)
    Abstract [en]

    The metallocene-based linker molecule 1,1'-ferrocenedicarboxylic acid (H(2)FcDC) was used to synthesize four different polymorphs of composition [In(OH)(FeC12H8O4)]. Using conventional solvent-based synthesis methods and varying the synthetic parameters such as metal source, reaction temperature, and solvent, two different MOFs and one ID-coordination polymer denoted as CAU-43 (1), In-MIL-53-FcDC_a (2), and InFcDC (3) were obtained. Furthermore, thermal treatment of CAU-43 (1) at 190 degrees C under vacuum yielded a new polymorph of 2, In-MIL-53-FcDC_b (4). Both MOFs 2 and 4 crystallize in a MIL-53 type structure, but in different space groups C2/m for 2 and P (1) over bar for 4. The structures of the four title compounds were determined by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), or a combination of three-dimensional electron diffraction measurements (3D ED) and PXRD. N-2 sorption experiments of 1, 2, and 4 showed specific surface areas of 355 m(2) g(-)(1), 110 m(2) g(-1), and 140 m(2) g(-)(1), respectively. Furthermore, the electronic properties of the title compounds were characterized via Mossbauer and EPR spectroscopy. All Mossbauer spectra showed the characteristic doublet, proving the persistence of the ferrocene moiety. In the cases of 1, 3, and 4, appreciable impurities of ferrocenium ions could be detected by electron paramagnetic resonance spectroscopy. Cyclovoltammetric experiments were performed to demonstrate the accessible redox activity of the linker molecule of the title compounds. A redox process of FcDC(2-) with oxidation (between 0.86 and 0.97 V) and reduction wave (between 0.69 and 0.80 V) was observed.

  • 7.
    Bonneau, Charlotte
    et al.
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Sanchez-Smith, Rebeca
    Guo, Bing
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Zhang, Daliang
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Inge, Andrew Kentaro
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Edén, Mattias
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
    Open-Framework Germanate Built from the Hexagonal Packing of Rigid Cylinders2009In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 48, no 21, p. 9962-9964Article in journal (Refereed)
    Abstract [en]

    We present a novel open-framework oxide material constructed from Ge10(O,OH)28 (Ge10) oxide clusters prepared via a nonsurfactant route. The material shows two distinct pore windows of 9.43 and 4.65 Å and a low framework density structure of 12.7 Ge atoms per 1000 Å3. The topological study leads to the recognition of a newly observed trinodal 6,7-heterocoordinated net related to the 7-coordinated swh net. The structure displays large rigid cylinders showing features indicating a growth mechanism by hard-sphere packing of the inorganic moiety similar to that observed in mesoporous materials.

  • 8. Castner, Ashleigh T.
    et al.
    Su, Hao
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Johnson, Ben A.
    Ahlquist, Mårten S. G.
    Ott, Sascha
    Microscopic Insights into Cation-Coupled Electron Hopping Transport in a Metal–Organic Framework2022In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 144, no 13, p. 5910-5920Article in journal (Refereed)
    Abstract [en]

    Electron transport through metal–organic frameworks by a hopping mechanism between discrete redox active sites is coupled to diffusion-migration of charge-balancing counter cations. Experimentally determined apparent diffusion coefficients, Deapp, that characterize this form of charge transport thus contain contributions from both processes. While this is well established for MOFs, microscopic descriptions of this process are largely lacking. Herein, we systematically lay out different scenarios for cation-coupled electron transfer processes that are at the heart of charge diffusion through MOFs. Through systematic variations of solvents and electrolyte cations, it is shown that the Deapp for charge migration through a PIZOF-type MOF, Zr(dcphOH-NDI) that is composed of redox-active naphthalenediimide (NDI) linkers, spans over 2 orders of magnitude. More importantly, however, the microscopic mechanisms for cation-coupled electron propagation are contingent on differing factors depending on the size of the cation and its propensity to engage in ion pairs with reduced linkers, either non-specifically or in defined structural arrangements. Based on computations and in agreement with experimental results, we show that ion pairing generally has an adverse effect on cation transport, thereby slowing down charge transport. In Zr(dcphOH-NDI), however, specific cation–linker interactions can open pathways for concerted cation-coupled electron transfer processes that can outcompete limitations from reduced cation flux. 

  • 9. Chang, Ribooga
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Clairefond, Teva
    Tikhomirov, Evgenii
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Cheung, Ocean
    Synthesis and characterization of sodium hafnium oxide (Na2HfO3) and its high-temperature CO2 sorption properties2023In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 11, no 14, p. 7617-7628Article in journal (Refereed)
    Abstract [en]

    The CO2 sorption properties of sodium hafnium oxide (Na2HfO3) were investigated in this study. Na2HfO3 was synthesized by solid-state synthesis using Na2CO3 and HfO2 as starting materials. The solid-state synthesized Na2HfO3 appeared structurally similar to other mixed metal oxides such as Na2ZrO3, but stacking disorder appeared to be common in Na2HfO3. The synthesis conditions, including the Na : Hf ratio (between 0.5 and 1.5 : 1), synthesis temperature, time and heating rate, were investigated to optimize CO2 sorption properties of Na2HfO3. The Na2HfO3 sorbent showed comparable CO2 uptake capacity, reaction rate and excellent cycling stability compared to other metal oxide sorbents. Na2HfO3 with Na : Hf = 1 : 1 and 1.25 : 1 showed the highest CO2 uptake among all Na2HfO3 samples obtained, with a CO2 uptake capacity of around 15 wt% (at 650–800 °C). The CO2 uptake rate of NHO-1 and NHO-1.25 was fast with over 80% of the equilibrium uptake reached within 250 s. Na2HfO3 remained stable even after 100 cycles with less than 3% difference in the CO2 uptake capacity between the 1st and 100th cycles. We performed kinetic analysis on the CO2 sorption data and found that the Avrami–Erofeev model fitted the kinetic data best among the kinetic models used. Apart from sorbent optimization, we showed that 3D-printing of Na2HfO3 : HfO2 mixtures can be used to produce structured Na2HfO3 sorbents with a slightly improved CO2 uptake rate and the same CO2 uptake capacity as the powder-based solid-state synthesized Na2HfO3 sorbent.

  • 10. Cui, Peng
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Spackman, Peter R.
    Wu, Yue
    Clowes, Rob
    Day, Graeme M.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Little, Marc A.
    Cooper, Andrew
    An Expandable Hydrogen-Bonded Organic Framework Characterized by Three-Dimensional Electron Diffraction2020In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 142, no 29, p. 12743-12750Article in journal (Refereed)
    Abstract [en]

    A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA, adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2, has robust dynamic porosity (SA(BET) = 1 183 m(2) g(-1)) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.

  • 11. Dazem, Cyrielle L. F.
    et al.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Luneau, Dominique
    Öhrstrom, Lars
    Nenwa, Justin
    Synthesis, structure and magnetic properties of two bis(oxalato)cuprate(ıı) salts with pyridinium type counter ions2023In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 25, no 10, p. 1479-1485Article in journal (Refereed)
    Abstract [en]

    Mono- and a di-protonated pyridine type cations have been used for the synthesis of two bis(oxalato)cuprate(ıı) salts, namely, (C5H7N2O)2[Cu(C2O4)2] (C5H7N2O = 2-amino-3-hydroxypyridinium) 1 and C13H16N2[Cu(C2O4)2] (C13H16N2 = 4,4′-trimethylenedipyridinium) 2. In the crystal structures, C2O42− adopts different coordination modes: the common bidentate chelating oxalate in 1 and the relatively scarce μ-oxalato-κ3O1,O2:O1′ in 2. X-ray diffraction also revealed that [Cu(C2O4)2]2− anions do not polymerize in 1 (a phenomenon hardly observed in such salts), while in 2, the polymerization of [Cu(C2O4)2]2− units occurs via the Cu–Oaxial contact forming a zigzag Cu(ıı) chain. In complex 1, the emerging building blocks are linked into 2D supramolecular layers via N–H⋯O and O–H⋯O hydrogen bonds and weaker C–H⋯O interaction to form a 3D net. In contrast to 2, the emerging building blocks are linked into 1D chains via N–H⋯O hydrogen bonds, which further extend to form a 3D supramolecular framework through Cu–Oaxial and other C–H⋯O interactions. The structural diversities show that iminium counterions play key roles in the construction of various architectures. Thermal analyses showed no weight loss for either system in the temperature range of 20–180 °C, which indicates that none of these complexes possess solvation water molecules. Magnetic studies indicate the presence of antiferromagnetic coupling between the spin centres in 1 and 2.

  • 12. Duan, Lele
    et al.
    Wang, Lei
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fischer, Andreas
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Licheng
    Insights into Ru-Based Molecular Water Oxidation Catalysts: Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities2013In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 52, no 14, p. 7844-7852Article in journal (Refereed)
    Abstract [en]

    A series of Ru-bda water oxidation catalysts [Ru(bda)L-2] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; L = [HNEt3][3-SO3-pyridine], 1; 4-(EtOOC)-pyridine, 2; 4-bromopyridine, 3; pyridine, 4; 4-methoxypyridine, 5; 4-(Me2N)-pyridine, 6; 4-[Ph(CH2)(3)]-pyridine, 7) were synthesized with election-donating/-withdrawing groups and hydro-philic/hydrophobic groups in the axial ligands. These complexes were characterized by H-1 NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and electrochemistry. In addition, complexes 1 and 6 were further identified by single crystal X-ray crystallography, revealing a highly distorted octahedral configuration of the Ru coordination sphere. All of these complexes are highly active toward Ce-IV-driven (Ce-IV = Ce(NH4)(2)(NO3)(6)) water oxidation with oxygen evolution rates up to 119 mols of O-2 per mole of catalyst per second. Their structure-activity relationship was investigated. Electron-withdrawing and noncovalent interactions (attraction) exhibit positive effect on the catalytic activity of Ru-bda catalysts.

  • 13.
    Etman, Ahmed S.
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Alexandria University, Egypt.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Xu, Jiaru
    Younesi, Reza
    Edström, Kristina
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Peking University, China.
    A Water Based Synthesis of Ultrathin Hydrated Vanadium Pentoxide Nanosheets for Lithium Battery Application: Free Standing Electrodes or Conventionally Casted Electrodes?2017In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 252, p. 254-260Article in journal (Refereed)
    Abstract [en]

    Ultrathin hydrated vanadium pentoxide (V2O5 center dot nH(2)O) nanosheets are fabricated via a water based exfoliation technique. The exfoliation process involves reflux of the precursor, 1:4 mixture of VO2 and V2O5, in water at 80 degrees C for 24 h. Operando and ex situ X-ray diffraction (XRD) studies are conducted to follow the structural changes during the exfoliation process. The chemical and thermal analyses suggest that the molecular formula of the nanosheet is (H0.2V1.8V0.2O5)-V-V-O-IV center dot 0.5H(2)O. The V2O5 center dot nH(2)O nanosheets are mixed with 10% of multi-walled carbon nanotube (MW-CNT) to form a composite material assigned as (VOx-CNT). Free standing electrodes (FSE) and conventionally casted electrodes (CCE) of VOx-CNT are fabricated and then tested as a positive electrode material for lithium batteries. The FSE shows reversible capacities of 300 and 97 mAhg(-1) at current densities of 10 and 200 mAhg(-1), respectively. This is better than earlier reports for free-standing electrodes. The CCE delivers discharge capacities of 175 and 93 mAhg(-1) at current densities of 10 and 200 mAhg(-1), respectively.

  • 14. Fan, Ke
    et al.
    He, Min
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Kuang, Panyong
    Jia, Yufei
    Fan, Lizhou
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zhang, Biaobiao
    Sun, Licheng
    Yu, Jiaguo
    Amorphous WO3 induced lattice distortion for a low-cost and high-efficient electrocatalyst for overall water splitting in acid2020In: Sustainable Energy & Fuels, E-ISSN 2398-4902, Vol. 4, no 4, p. 1712-1722Article in journal (Refereed)
    Abstract [en]

    The development of highly active and durable catalysts for water oxidation under acidic conditions is necessary but challenging for renewable energy conversion. Ir-based catalysts are highly efficient for water oxidation in acid, but their large scale application is hindered by the high cost and scarcity of iridium. Herein, we use an amorphous WO3 induced lattice distortion (AWILD) strategy to reduce the Ir content to only 2 wt% in the final material. The optimized hybrid nitrogen-doped carbon (NC)/WO3/IrO2 can efficiently catalyze water oxidation with a low overpotential of 270 mV at 10 mA cm(-2) current density (eta (10)) and a high turnover frequency of over 2 s(-1) at 300 mV overpotential in 0.5 M H2SO4, a performance that surpasses that of commercial IrO2 significantly. Introducing the layer of amorphous WO3 between IrO2 nanoparticles and NC can distort the lattice of IrO2, exposing more highly active sites for water oxidation. The AWILD effect compensates for the lower Ir content and dramatically reduces the cost of the catalyst without sacrificing the catalytic activity. Additionally, this catalyst also exhibits high activity in acid for hydrogen evolution with only 65 mV of eta (10) attributed to the AWILD effect, exhibiting efficient bifunctionality as a Janus catalyst for overall water splitting. The AWILD approach provides a novel and efficient strategy for low-cost and highly efficient electrocatalysts for acidic overall water splitting with an extremely low content of noble metals.

  • 15. Fan, Ke
    et al.
    Zou, Haiyuan
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fan, Lizhou
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Duan, Lele
    Zhang, Biaobiao
    Sun, Licheng
    Surface and bulk reconstruction of CoW sulfides during pH-universal electrocatalytic hydrogen evolution2021In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 9, no 18, p. 11359-11369Article in journal (Refereed)
    Abstract [en]

    Electrocatalytic water splitting is an efficient means of producing energy carriers, such as H-2. The hydrogen evolution reaction (HER) requires high-efficiency electrocatalysts. Understanding the active site structures of the HER electrocatalysts is essential for the rational design and development of water splitting devices. In this study, porous CoW sulfides were employed as model electrocatalysts for pH-universal HER. Multiple characterization studies, such as X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and operando X-ray diffraction, were systematically used to investigate the reconstruction of the active species at the surface and in the bulk. The results show that during the HER, the structural transformation of the species CoW sulfides is strongly dependent on the pH of the electrolyte. Electrolytes of varying pH lead to varied reconstruction and influence the true catalytically active species responsible for the HER. The surface and the bulk of the electrocatalysts transform to different oxides/hydroxides when subjected to the HER. This is the first time that the pH-dependent bulk and surface structural evolution in the HER has been revealed. This study reveals the reconstruction and potential active site evolution of mixed-metal sulfides for the HER. We believe that the present study not only provides an idealized pre-catalyst for pH-universal highly-efficient HER, but also provides a thorough understanding about the identification of the real active sites and the mechanism of the structural evolution of the electrocatalysts during hydrogen evolution.

  • 16. Fan, Ke
    et al.
    Zou, Haiyuan
    Ding, Yunxuan
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fan, Lizhou
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Duan, Lele
    Zhang, Biaobiao
    Sun, Licheng
    Sacrificial W Facilitates Self-Reconstruction with Abundant Active Sites for Water Oxidation2022In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 18, no 13, article id 2107249Article in journal (Refereed)
    Abstract [en]

    Water oxidation is an important reaction for multiple renewable energy conversion and storage-related devices and technologies. High-performance and stable electrocatalysts for the oxygen evolution reaction (OER) are urgently required. Bimetallic (oxy)hydroxides have been widely used in alkaline OER as electrocatalysts, but their activity is still not satisfactory due to insufficient active sites. In this research, A unique and efficient approach of sacrificial W to prepare CoFe (oxy)hydroxides with abundant active species for OER is presented. Multiple ex situ and operando/in situ characterizations have validated the self-reconstruction of the as-prepared CoFeW sulfides to CoFe (oxy)hydroxides in alkaline OER with synchronous W etching. Experiments and theoretical calculations show that the sacrificial W in this process induces metal cation vacancies, which facilitates the in situ transformation of the intermediate metal hydroxide to CoFe-OOH with more high-valence Co(III), thus creating abundant active species for OER. The Co(III)-rich environment endows the in situ formed CoFe oxyhydroxide with high catalytic activity for OER on a simple flat glassy carbon electrode, outperforming those not treated by the sacrificial W procedure. This research demonstrates the influence of etching W on the electrocatalytic performance, and provides a low-cost means to improve the active sites of the in situ self-reconstructed bimetallic oxyhydroxides for OER.

  • 17. Fan, Lizhou
    et al.
    Zhang, Biaobiao
    Qiu, Zhen
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Timmer, Brian J. J.
    Zhang, Fuguo
    Sheng, Xia
    Liu, Tianqi
    Meng, Qijun
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Edvinsson, Tomas
    Sun, Licheng
    Molecular Functionalization of NiO Nanocatalyst for Enhanced Water Oxidation by Electronic Structure Engineering2020In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 13, no 22, p. 5901-5909Article in journal (Refereed)
    Abstract [en]

    Tuning the local environment of nanomaterial-based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure-activity relationship was discovered: the increasing electron-withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron-withdrawing modification facilitates the charge-transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high-valent gamma-NiOOH reactive species generation. The NiO-C(6)F(5)catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well-designed and effective approach for heterogeneous catalyst fabrication under the molecular level.

  • 18. Fan, Lizhou
    et al.
    Zhang, Biaobiao
    Timmer, Brian J. J.
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sheng, Xia
    Tai, Cheuk-Wai
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zhang, Fuguo
    Liu, Tianqi
    Meng, Qijun
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Licheng
    Promoting the Fe(VI) active species generation by structural and electronic modulation of efficient iron oxide based water oxidation catalyst without Ni or Co2020In: Nano Energy, ISSN 2211-2855, E-ISSN 2211-3282, Vol. 72, article id 104656Article in journal (Refereed)
    Abstract [en]

    Fe is considered as a promising alternative for OER catalysts owing to its high natural abundance and low cost. Due to the low conductivity and sluggish catalytic kinetics, the catalytic efficiency of Fe-rich catalysts is far from less abundant Ni, Co-rich alternatives and has been hardly improved without the involvement of Ni or Co. The lower activity of Fe-rich catalysts renders the real active center of state-of-the-art NiFe, CoFe catalyst in long-term scientific debate, despite of detection of Fe-based active intermediates in these catalysts during catalytic process. In the present work, we fabricated a series of sub-5 nm Fe1-yCryOx nanocatalysts via a simple solvothermal method, achieving systematically promoted high-valent Fe(VI) species generation by structural and electronic modulation, displaying highly active OER performance without involvement of Ni or Co. Detailed investigation revealed that the high OER activity is related to the ultrasmall nanoparticle size that promotes abundant edge- and corner-site exposure at catalyst surface, which involves in OER as highly reactive site; and the incorporated Cr ions that remarkably accelerate the charge transfer kinetics, providing an effective conduit as well as suitable host for high-valent active intermediate. This work reveals the structural prerequisites for efficient Fe-rich OER catalyst fabrication, inspiring deeper understanding of the structure-activity relationship as well as OER mechanism of Fe-based catalysts.

  • 19.
    Fang, Liang
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Liu, Leifeng
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Yun, Yifeng
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Wan, Wei
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Geo, Feifei
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    SU-77: An Open-Framework Germanate Containing 12 × 10 × 10-Ring Channels Solved by Combining Rotation Electron Diffraction and Powder X-ray Diffraction2014In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 14, no 10, p. 5072-5078Article in journal (Refereed)
    Abstract [en]

    A novel open-framework germanate, denoted as SU-77, was prepared by hydrothermal synthesis using ethylenediamine as the structure directing agent. The as-synthesized SU-77 is monoclinic with space group P21/a and a = 13.52427(5) Å, b = 12.64862(5) Å, c = 9.60578(3) Å, β = 92.8599(4)°. The structure of SU-77 is built from a novel Ge6O17(C2H8N2)F (Ge6) cluster building unit. The Ge6 clusters are connected to form chains along the c-axis. These chains are further connected in the [110] and [1–10] directions to form a three-dimensional framework with 12 × 10 × 10-ring channels. The as-synthesized monoclinic SU-77 became orthorhombic while being observed in a transmission electron microscope (TEM) or when heated to 200 °C in air. The orthorhombic structure of SU-77 was solved from micrometer-sized crystals by rotation electron diffraction (RED). The monoclinic structure was built from the orthorhombic structure and subsequently refined against synchrotron powder X-ray diffraction data. SU-77 is the first example of an open-framework germanate with mixed coordination polyhedra solved by electron diffraction.

  • 20.
    Fijoł, Natalia
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Wallenberg Wood Science Center, Sweden.
    Mautner, Andreas
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bacsik, Zoltán
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Mathew, Aji P.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Wallenberg Wood Science Center, Sweden.
    MOF@Cell: 3D printed biobased filters anchored with a green metal–organic framework for effluent treatment2023In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 11, no 23, p. 12384-12394Article in journal (Refereed)
    Abstract [en]

    Multifunctional, biobased materials processed by means of additive manufacturing technology can behighly applicable within the water treatment industry. This work summarizes a scalable and sustainablemethod of anchoring a green metal–organic framework (MOF) SU-101 onto the surface of 3D printed,biobased matrices built of polylactic acid (PLA)-based composites reinforced with TEMPO-oxidizedcellulose nanofibers (TCNFs). The two tested anchoring methods were hydrolysis via either concentratedhydrochloric acid treatment or via a photooxidation reaction using UV–ozone treatment. Stabledeposition of SU-101 distributed homogenously over the filter surface was achieved and confirmed byFT-IR, XPS and SEM measurements. The obtained 3D printed and functionalized MOF@PLA andMOF@TCNF/PLA (aka MOF@Cell) filters exhibit high efficiency in removing heavy metal ions from mineeffluent and methylene blue from contaminated water, as demonstrated through batch adsorptionexperiments. In addition to their potential for removal of contaminants from water, the MOF@Cell filtersalso exhibit excellent mechanical properties with a Young's modulus value of about 1200 MPa,demonstrating their potential for use in practical water treatment applications. The MOF@Cell filterswere able to maintain their structural integrity and filtration performance even after multiple cycles ofuse and regeneration. This study highlights the potential of multifunctional, biobased materials processedby additive manufacturing technology as a cost-effective alternative to traditional water treatmentmethods. The MOF@Cell filters presented in this study demonstrate high efficiency, durability, andreusability, making them promising candidates for practical applications in the modern water treatmentindustry.

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  • 21. Frank, Sara
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Drath Bøjesen, Espen
    Larsen, Rasmus
    Lamagni, Paolo
    Catalano, Jacopo
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Lock, Nina
    Exploring the influence of atomic level structure, porosity, and stability of bismuth(iii) coordination polymers on electrocatalytic CO2 reduction2021In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 9, no 46, p. 26298-26310Article in journal (Refereed)
    Abstract [en]

    Bismuth-based coordination polymers (CPs) have recently attracted attention as catalyst precursors for the electrocatalytic CO2 reduction reaction (eCO(2)RR). We present a comparative study by investigating six bismuth-based compounds in-depth to elucidate the correlation between their structures and their catalytic CO2-to-formate conversion. Thereby, we identify structural indicators of the pristine CPs resulting in optimized catalytic performance, paving the way for future design of CP derived catalysts. The structural properties of the six pristine materials vary in terms of porosity (from non-porous to 495 m(2) g(-1)), linker type (carboxylate- or phenolate-based), thermal- and chemical stability, and metal content. Herein, electrochemical studies are combined with comprehensive structural investigations using electron microscopy, powder X-ray diffraction, and X-ray absorption spectroscopy. Our study reveals that low chemical stability of the pristine CPs is crucial for the conversion of the precursors into active Bi2O2CO3 and of paramount importance for the eCO(2)RR activity, while the nature of the pristine material mostly influence the catalyst morphology and transport properties. Of the six investigated CPs, the best performing compounds selectively convert CO2 to formate with faradaic efficiencies in the range 80(3)-95(3)% and current densities of 5(1)-8(1) mA cm(-2) at -0.97 V-RHE.

  • 22.
    García-Vázquez, Víctor
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martínez-Pardo, Pablo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Postole, Alexandru
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Martín‐Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis of α,γ-Chiral Trifluoromethylated Amines through the Stereospecific Isomerization of α-Chiral Allylic Amines2022In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 24, no 21, p. 3867-3871Article in journal (Refereed)
    Abstract [en]

    Chiral γ-branched aliphatic amines are present in a large number of pharmaceuticals and natural products. However, enantioselective methods to access these compounds are scarce and mainly rely on the use of designed chiral transition-metal complexes. Herein, we combined an organocatalytic method for the stereospecific isomerization of chiral allylic amines with a diastereoselective reduction of the chiral imine/enamine intermediates, leading to γ-trifluoromethylated aliphatic amines with two noncontiguous stereogenic centers, in excellent yields and high diastereo- and enantioselectivities. This approach has been used with primary amine substrates. This approach also provides a new synthetic pathway to chiral trifluoromethylated scaffolds, of importance in medicinal chemistry. Additionally, a gram-scale reaction demonstrates the applicability of this synthetic procedure. 

  • 23. Gosch, Jonas
    et al.
    Guiotto, Virginia
    Steinke, Felix
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Atzori, Cesare
    Mertin, Kalle
    Otto, Tobias
    Ruser, Niklas
    Meier, Christoph
    Morelli Venturi, Diletta
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Lomachenko, Kirill A.
    Crocellà, Valentina
    Stock, Norbert
    Discovery and In Situ Crystallization Studies of Cerium-Based Metal–Organic Frameworks with V-Shaped Linker Molecules2023In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 62, no 51, p. 20929-20939Article in journal (Refereed)
    Abstract [en]

    We report the discovery and characterization of two porous Ce(III)-based metal–organic frameworks (MOFs) with the V-shaped linker molecules 4,4′-sulfonyldibenzoate (SDB2–) and 4,4′-(hexafluoroisopropylidene)bis(benzoate) (hfipbb2–). The compounds of framework composition [Ce2(H2O)(SDB)3] (1) and [Ce2(hfipbb)3] (2) were obtained by using a synthetic approach in acetonitrile that we recently established. Structure determination of 1 was accomplished from 3D electron diffraction (3D ED) data, while 2 could be refined against powder X-ray diffraction (PXRD) data using the crystal structure of an isostructural La-MOF as the starting model. Their framework structures consist of chain-like inorganic building units (IBUs) or hybrid-BUs that are interconnected by the V-shaped linker molecules to form framework structures with channel-type pores. The composition of both compounds was confirmed by PXRD, elemental analysis, as well as NMR and IR spectroscopy. Interestingly, despite the use of (NH4)2[CeIV(NO3)6] in the synthesis, cerium ions in both MOFs occur exclusively in the + III oxidation state as determined by X-ray absorption near edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). Thermal analyses reveal remarkably high thermal stabilities of ≥400 °C for the MOFs. Initial N2 sorption measurements revealed the peculiar sorption behavior of 2 which prompted a deeper investigation by Ar and CO2 sorption experiments. The combination with nonlocal density functional theory (NL-DFT) calculations adds to the understanding of the nature of the different pore diameters in 2. An extensive quasi-simultaneous in situ XANES/XRD investigation was carried out to unveil the formation of Ce-MOFs during the solvothermal syntheses in acetonitrile. The crystallization of the two Ce(III)-MOFs presented herein as well as two previously reported Ce(IV)-MOFs, all obtained by a similar synthetic approach, were studied. While the XRD patterns show time-dependent MOF crystallization, the XANES data reveal the presence of Ce(III) intermediates and their subsequent conversion to the MOFs. The addition of acetic acid in combination with the V-shaped linker molecule was identified as the crucial factor for the formation of the crystalline Ce(III/IV)-MOFs. 

  • 24. Gosch, Jonas
    et al.
    Morelli Venturi, Diletta
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Atzori, Cesare
    Donà, Lorenzo
    Steinke, Felix
    Otto, Tobias
    Tjardts, Tim
    Civalleri, Bartolomeo
    Lomachenko, Kirill A.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Costantino, Ferdinando
    Stock, Norbert
    Synthesis, Crystal Structure, and Photocatalytic Properties of Two Isoreticular Ce(IV)-MOFs with an Infinite Rod-Shaped Inorganic Building Unit2023In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 62, no 13, p. 5176-5185Article in journal (Refereed)
    Abstract [en]

    The use of the V-shaped linker molecules 4,4′-oxydibenzoic acid (H2ODB) and 4,4′-carbonyldibenzoic acid (H2CDB) led to the discovery of two isoreticular Ce(IV)-based metal–organic frameworks (MOFs) of composition [CeO(H2O)(L)], L = ODB2–, CDB2–, denoted CAU-58 (CAU = Christian-Albrechts-University). The recently developed Ce-MOF synthesis approach in acetonitrile as the solvent proved effective in accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units (IBUs) and circumventing the formation of the predominantly observed hexanuclear [Ce6O8] cluster. For the structure determination of the isoreticular MOFs, three-dimensional electron diffraction (3D ED) and powder X-ray diffraction (PXRD) data were used in combination with density functional theory (DFT) calculations. [CeO(H2O)(CDB)] shows reversible H2O adsorption by stirring in water and thermal treatment at 190 °C, which leads to a unit cell volume change of 11%. The MOFs feature high thermal stabilities (T > 290 °C), which exceed those of most Ce(IV)-MOFs and can be attributed to the infinite rod-shaped IBU. Surface and bulk oxidation states of the cerium ions were analyzed via X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). While Ce(III) ions are observed by the highly surface-sensitive XPS method, the bulk material contains predominantly Ce(IV) ions according to XANES. Application of the MOFs as catalysts for the catalytic degradation of methyl orange in aqueous solutions was also studied. While degradation activity for both MOFs was observed, only CAU-58-ODB revealed enhanced photocatalytic activity under ultraviolet (UV) light. The photocatalytic mechanism likely involves a ligand-to-metal charge transfer (LMCT) from the linkers to the Ce(IV) centers. Analyses by XANES and inductively coupled plasma-optical emission spectroscopy (ICP-OES) demonstrate that leaching of Cerium ions as well as partial reduction of Ce(IV) to Ce(III) takes place during catalysis. At the same time, PXRD data confirm the structural stability of the remaining MOF catalysts. 

  • 25. Gosch, Jonas
    et al.
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Atzori, Cesare
    Steinke, Felix
    Lomachenko, Kirill A.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Solubility and Stability of Hexanuclear Ce(IV)-O Clusters2023In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 35, no 15, p. 5876-5885Article in journal (Refereed)
    Abstract [en]

    Stable molecular clusters are of interest for targeted deposition in porous materials. In this work, we report the discovery of two new molecular Ce–O clusters of composition [Ce6O4(OH)4(NO3)4(DMF)4(C7H4O2X)8]·(DMF)4(H2O)2 (1-X) and [Ce6O4(OH)4(H2O)6(NO3)6(C7H4O2X)6] (2-X) (X = −Cl, −CHO, and −Br). Both cluster types contain a similar hexanuclear building unit, and crystal structures were determined from single-crystal X-ray diffraction or 3D electron diffraction data and subsequent Rietveld refinements against powder X-ray diffraction (PXRD) data. The crystal structure data is complemented by results from the local structure around the cerium ions, determined by extended X-ray absorption fine structure (EXAFS) measurements in the solid state. The composition of all Ce–O clusters was confirmed by elemental analysis, NMR and IR spectroscopy. The Ce–O clusters are highly soluble, up to 101 and 136 g/L for 1-Cl and 2-Cl, respectively, in organic solvents, which strongly depends on the type of cluster and functionalization of the benzoate ligands. Moreover, the structural and compositional integrity of dissolved clusters in different solvents was established. Recrystallization of 1-Cl from dichloromethane (DCM) and Raman spectroscopy confirm the integrity of both cluster types in solution. Further examination by EXAFS measurements on the Ce K-edge of clusters containing 4-chlorobenzoate reveals that only minor changes in the cerium environment of 1-Cl are observed upon dissolution in THF, DCM, and dioxane, while the results for 2-Cl indicate a partial degradation upon dissolution. After proving the stability, a cluster solution of 1-Cl was used to impregnate the mesoporous metal–organic framework Cr-MIL-101. Extensive characterization by PXRD, inductively coupled plasma-optical emission spectroscopy, and energy-dispersive X-ray spectroscopy, as well as thermogravimetry and N2-sorption measurements, confirm the successful insertion of Ce–O clusters into the large mesoporous cages of the framework. Due to the combination of high surface area and potential catalytic activity, the Cluster@MOF materials could be of high interest for application in heterogeneous catalysis.

  • 26.
    Guo, Bing
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, Andrew K.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bonneau, Charlotte
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Christensen, Kirsten E.
    Yuan, Zhong-Yong
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Investigation of the GeO2-1,6-Diaminohexane-Water-Pyridine-HF Phase Diagram Leading to the Discovery of Two Novel Layered Germanates with Extra-Large Rings2011In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 1, p. 201-207Article in journal (Refereed)
    Abstract [en]

    The systematic exploration of the phase diagram of the GeO2-1,6-diaminohexane-water-pyridine-HF system has allowed the identification of specific roles of the HF, H2O contents, and HF/H2O ratio in the formation of Ge7X19 (Ge7), Ge9X25−26 (Ge9), and Ge10X28 (Ge10) clusters (X = O, OH, F). This work has led to the discovery of two novel structures with extra-large 18-membered rings accommodating 1,6-diaminohexane (DAH): SU-63, |1.5H2DAH|[Ge7O14X3]·2H2O, a layered germanate constructed from Ge7 clusters with the Kagom topology, and SU-64, |11H2DAH|[Ge9O18X4][Ge7O14X3]6·16H2O, a germanate built of two-dimensional slabs containing both Ge7 and Ge9 clusters (X = OH or F). We also put SU-64 in context with previously reported cluster germanate compounds with related topologies by means of a simple crystal deconstruction study.

  • 27. Halis, Seida
    et al.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Dehning, Niklas
    Weyrich, Thomas
    Reinsch, Helge
    Stock, Norbert
    Dihydroxybenzoquinone as Linker for the Synthesis of Permanently Porous Aluminum Metal-Organic Frameworks2016In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 15, p. 7425-7431Article in journal (Refereed)
    Abstract [en]

    Two new dihydroxybenzoquinone-based metal-organic frameworks, ((CH3)(2)NH2)(3)[Al-4(L1)(3)(L1(center dot))(3)]center dot 3DMF (1, denoted CAU - 20) and ((CH3)(2)NH2)(3)[Al-4(L2)(3)(L2 center dot)(3)]center dot 9DMF (2, denoted CAU-20-Cl-2), were synthesized at 120 degrees C in PAU using 2,5-dihydroxy-p-benzoquinone ((C6H2(OH)(2)(O)(2)), H(2)L1) and 2,5-dichloro-3,6-dihydroxy-p-benzoquinone ((C6Cl2(OH)(2)(O)(2)), H(2)L2), respectively. Compared to other Al-MOFs, which contain carboxylate or phosphonate groups that connect the metal sites, in 1 and 2 the Al3+ are coordinated by oxido groups. The metal ions are octahedrally surrounded by oxygen atoms Of the deprotonated linker molecules to generate honeycomb layers with a metal to linker ratio of Al: L1/L2 = 2:3. The layers contain L1(2-) and L2(2-) ions as well as linker radical ions L1(center dot 3-) and L2(center dot 3-) in a molar ratio of 1 to 1. The presence of radical ions was confirmed by EPR and UV-vis-spectroscopic Measurements, and the composition was determined from a combination of PXRD, H-1, NMR, TG, and elemental analyses. Charge balance is accomplished through intercalation of (CH3)(2)NH2+ ions which are formed by partial hydrolysis of DMF. In the structures of 1 and 2 the eclipsed layers are AA and ABAB stacked, respectively, and one-dimensional hexagonal channels with diameters of ca. 9 and 6 angstrom are formed. Both compounds exhibit permanent porosity and have specific surface areas of 1440 and 1430 m(2) g(-1), respectively.

  • 28. Heidenreich, N.
    et al.
    Rütt, U.
    Köppen, M.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Beier, S.
    Dippel, A. -C.
    Suren, R.
    Stock, N.
    A multi-purpose reaction cell for the investigation of reactions under solvothermal conditions2017In: Review of Scientific Instruments, ISSN 0034-6748, E-ISSN 1089-7623, Vol. 88, no 10, article id 104102Article in journal (Refereed)
    Abstract [en]

    A new versatile and easy-to-use remote-controlled reactor setup aimed at the analysis of chemical reactions under solvothermal conditions has been constructed. The reactor includes a heating system that can precisely control the temperature inside the reaction vessels in a range between ambient temperature and 180 degrees C. As reaction vessels, two sizes of commercially available borosilicate vessels (V-max = 5 and 11 ml) can be used. The setup furthermore includes the option of stirring and injecting of up to two liquid additives or one solid during the reaction to initiate very fast reactions, quench reactions, or alter chemical parameters. In addition to a detailed description of the general setup and its functionality, three examples of studies conducted using this setup are presented.

  • 29. Huang, Jin
    et al.
    Olsén, Peter
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Odelius, Karin
    Simple Approach to Macrocyclic Carbonates with Fast Polymerization Rates and Their Polymer-to-Monomer Regeneration2022In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 55, no 2, p. 608-614Article in journal (Refereed)
    Abstract [en]

    Designing polymeric materials for closed-loop material streams is the key to achieving a circular society. Here, a library of macrocyclic carbonates (MCs) was designed by a facile and direct one-pot, two-step synthesis approach without the use of a solvent at a 10 g scale. We demonstrate that anionic polymerization with tert-butoxide enables the ultrafast ring-opening polymerization (ROP) of MCs with high conversion (>97%) within seconds (3–10 s) at ambient temperature. The polymerization rate depends on the odd or even number of methylene groups between the carbonate linkages in the MCs, and not the overall ring size, yielding an “odd–even” effect. This polymerization rate is related to the difference in molecular conformation of the MCs, as determined by X-ray crystallography. The polymers (polypenta-, hexa-, heptamethylene carbonate) were subsequently regenerated back to their original MCs at a high selectivity (95–99 mol %) and good yields (70–85%), hence taking a step toward closing the loop on these long alkyl chain polycarbonates. 

  • 30.
    Huang, Shiliang
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Yang, Sihai
    Christensen, Kirsten E.
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    SU-75: a disordered Ge-10 germanate with pcu topology2012In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 41, no 40, p. 12358-12364Article in journal (Refereed)
    Abstract [en]

    A disordered open-framework germanate, denoted as SU-75, was synthesized under hydrothermal conditions using diethylenetriamine (dien) or alternatively 1,4-diaminobutane (dab) as the structure directing agent (SDA). SU-75 crystallizes in a tetragonal space group I-42d(No. 122) with a= 18.145(3) Å and c= 41.701(9) Å. The three-dimensional (3D) framework is built from Ge10(O,OH)28(Ge10) clusters that are connected following the pcu ( primitive cubic) net topology. SU-75 has 10-, 11- and 12-ring channels along the a- and b-axes and channels with alternating 8-, 10-, 12-, 10-ring openings along the c-axis. The framework exhibits a serious disorder, resulted from two possible connectivities between the units of four Ge 10clusters (4Ge10 unit). The chemical formula of SU-75 is |(H2SDA)2(H2O)n|[Ge10O21(OH)2] (SDA = dien or dab,n= 5–6), determined by combining single crystalsynchrotron X-ray diffraction, thermogravimetric analysis (TGA) and CHN elemental analysis. A superoctahedron is introduced to simplify the description of the connectivity of the Ge10 clusters and to illustrate the disorder. This is also used to compare the structure of SU-75 with those of related Ge10 germanates.

  • 31.
    Huang, Zhehao
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Svensson Grape, Erik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Li, Jian
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    3D electron diffraction as an important technique for structure elucidation of metal-organic frameworks and covalent organic frameworks2021In: Coordination chemistry reviews, ISSN 0010-8545, E-ISSN 1873-3840, Vol. 427, article id 213583Article, review/survey (Refereed)
    Abstract [en]

    Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have emerged as the most widely investigated classes of porous materials during the past two decades. The almost unlimited combination of building units (metal clusters and organic molecules) endows highly tuneable porosities and functionalities that are appealing for a wide scope of applications. The applications of MOFs and COFs depend on their physical and chemical properties, which in turn are determined by the arrangement of atoms - the crystal structures. Therefore, structure determination is arguably the most important characterization step for MOFs and COFs. While single crystal X-ray diffraction (SCXRD) is the most widely used method for structure determination, many MOFs and COFs are synthesized in too small sizes or their crystal qualities are too low for SCXRD. During recent years, three-dimensional electron diffraction (3DED) methods has undergone rapid developments and can be used for structure determination of nano- and submicro-sized crystals to overcome this fundamental drawback. In this review, we summarize the development of 3DED methods and their applications for structure elucidation of MOFs and COFs. Advances of 3DED data collection techniques are described, from step-wise rotation to continuous rotation of the crystal. The latter allows fast data collection which is crucial for beam sensitive materials including MOFs and COFs. Examples of ab initio structure determination of various MOFs and COFs by using 3DED are presented, with highlighted examples for solving the structures of mesoporous MOFs, mixed-metal MOFs, flexible MOFs, and for studying host-guest interactions. Finally, the accuracy and reproducibility of structure determination by 3DED are presented. We show the structure information obtained from 3DED provides crucial insights into structure-property relationships, which could further accelerate the development of new functional materials.

  • 32. Huo, Meiling
    et al.
    Sun, Tu
    Wang, Yanzhi
    Sun, Pengfei
    Dang, Jingshuang
    Wang, Bin
    Dharanipragada, N. V. R. Aditya
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zhang, Wei
    Cao, Rui
    Ma, Yanhang
    Zheng, Haoquan
    A heteroepitaxially grown two-dimensional metal-organic framework and its derivative for the electrocatalytic oxygen reduction reaction2022In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 10, no 19, p. 10408-10416Article in journal (Refereed)
    Abstract [en]

    Two-dimensional (2D) metal–organic frameworks (MOFs) have become a hot topic recently due to their high surface area, larger number of exposed active sites, and improved conductivity. Combining different 2D MOFs could introduce new physical and chemical properties. Here, we have synthesized a heteroepitaxially grown 2D zeolitic imidazolate framework with a leaf-like morphology (ZIF-L). ZIF-L has a layer-by-layer dense structure, which possesses a high content of N and metal ions as active sites. ZIF-L-Co is heteroepitaxially grown on ZIF-L-Zn, while ZIF-L-Zn@ZIF-Co has been successfully prepared. After pyrolysis, the heteroepitaxially grown MOF derived ultra-small Co nanoparticle immobilized nitrogen doped carbon (NC) material (HM-Co@NC) exhibits superior oxygen reduction reaction (ORR) activity (Eonset = 0.998 V, E1/2 = 0.905 V) and better stability than Pt/C, achieving well-qualified assemblies for use in rechargeable Zn–air batteries.

  • 33.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Christensen, Kirsten E.
    Willhammar, Tom
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    A Germanate with a Collapsible Open-Framework2016In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 16, no 12, p. 6967-6973Article in journal (Refereed)
    Abstract [en]

    A novel open-framework germanate, vertical bar NC2H8 vertical bar vertical bar N2C6H18 vertical bar, [Ge7O14.5F2].4H(2)O denoted SU-65 (SU = Stockholm University), with 24-ring channels and a very low framework density of 8.9 Ge atoms per 1000 angstrom(3) was synthesized under hydro-solvothermal conditions. The framework of SU-65 is built of 5-connected Ge-7 clusters decorating the fee net and is a framework orientation isomer to ASU-16. Half of the 8- and 12-rings in ASU-16 are instead 10-rings in SU-65 due to the different orientations of half of the clusters in the crystal structure. Flexibility of the frameworks is also influenced by the orientation of the clusters. The unique unit cell angle in SU-65 changes upon heating, unlike ASU-16 which only undergoes changes in unit cell lengths. SU-65 undergoes significant structural changes at 180 degrees C in a vacuum, forming SU-65ht. The crystal structure of SU-65ht was investigated by rotation electron diffraction, X-ray powder diffraction, and infrared spectroscopy. Through these techniques it was deduced that SU-65ht has similar clusters, symmetry, and topology as SU-65, but one of the unit cell lengths is shortened by approximately 5 A. This corresponds to a 22% decrease in unit cell volume.

  • 34.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Christensen, Kirsten
    Guo, Bing
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    SU-65: The Orientation of Five-connected Ge7X19(X = O, OH, F) Clusters in the fee NetManuscript (preprint) (Other academic)
  • 35.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fahlquist, Henrik
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Willhammar, Tom
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Huang, Yining
    McCusker, Lynne B.
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Solving complex open-framework structures from X-ray powder diffraction by direct-space methods using composite building units2013In: Journal of applied crystallography, ISSN 0021-8898, E-ISSN 1600-5767, Vol. 46, p. 1094-1104Article in journal (Refereed)
    Abstract [en]

    The crystal structure of a novel open-framework gallogermanate, SU-66 {|(C6H18N2)(18)(H2O)(32)|[Ga4.8Ge87.2O208]}, has been solved from laboratory X-ray powder diffraction (XPD) data by using a direct-space structure solution algorithm and local structural information obtained from infrared (IR) spectroscopy. IR studies on 18 known germanates revealed that the bands in their IR spectra were characteristic of the different composite building units (CBUs) present in the structures. By comparing the bands corresponding to Ge-O vibrations in the IR spectra of SU-66 with those of the 18 known structures with different CBUs, the CBU of SU-66 could be identified empirically as the Ge-10(O,OH)(27) cluster (Ge-10). The unit cell and space group (extinction symbol P--a; a = 14.963, b = 31.593, c = 18.759 angstrom) were determined initially from the XPD pattern and then confirmed by selected-area electron diffraction. The structure of SU-66 was solved from the XPD data using parallel tempering as implemented in FOX [Favre-Nicolin & Cerny (2002). J. Appl. Cryst. 35, 734-743] by assuming P2(1)ma symmetry and two Ge-10 clusters in the asymmetric unit. Rietveld refinement of the resulting structure using synchrotron XPD data showed the framework structure to be correct and the space group to be Pmma. The framework has extra-large (26-ring) onedimensional channels and a very low framework density of 10.1 Ge/Ga atoms per 1000 angstrom(3). SU-66, with 55 framework atoms in the asymmetric unit, is one of the more complicated framework structures solved from XPD data. Indeed, 98% of the reflections were overlapping in the XPD pattern used for structure solution. Tests on other open-framework germanates (SU-62, SU-65, SU-74, PKU-12 and ITQ-37) for which the XPD data, unit cell, space group and IR spectra were available proved to be equally successful. In a more complex case (SU-72) the combination of FOX and powder charge flipping was required for structure solution.

  • 36.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Huang, Shiliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Chen, Hong
    Moraga, Francisca
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    The Structure of a Complex Open-framework Germanate Obtained by Combining Powder Charge-Flipping and Simulated Annealing2012In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 12, no 10, p. 4853-4860Article in journal (Refereed)
    Abstract [en]

    A novel open-framework germanate SU-74 containing intersecting 10- and 12-ring channels was prepared by hydrothermal synthesis using 2-methylpentamethylenediamine (MPMD) or 1-(2-aminoethyl)piperazine (AEP) as the organic structure directing agent (SDA). The framework structure of SU-74-MPMD was solved from X-ray powder diffraction (XRPD) data using powder charge-flipping (pCF). The guest species H2MPMD2+, NH4+ cations and water molecules were located in the voids using real-space simulated annealing. SU-74-MPMD contains 51 non-hydrogen atoms in its asymmetric unit and is one of the most complex framework structures solved by XRPD. The structure of SU-74-AEP was solved by single crystal synchrotron X-ray diffraction. SU-74-MPMD and SU-74-AEP have the same framework structure. The location of the NH4+ cations in both structures is similar, while the positions of the SDAs in the pores are different. SU-74 follows the fcu-11-P21/c net. The underlying topology of SU-74 is compared to those of other Ge10 structures containing additional GeO4 tetrahedra. The presence of additional tetrahedra can significantly affect the framework topology through the addition of edges between the Ge10 nodes.

  • 37.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Christian-Albrechts-Universität zu Kiel, Germany.
    Köppen, Milan
    Su, Jie
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Feyand, Mark
    Xu, Hongyi
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    O'Keeffe, Michael
    Stock, Norbert
    Unprecedented Topological Complexity in a Metal-Organic Framework Constructed from Simple Building Units2016In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 6, p. 1970-1976Article in journal (Refereed)
    Abstract [en]

    A bismuth-based metal-organic framework (MOP), [Bi(BTC)(H2O)]center dot 2H(2)O center dot MeOH denoted CAU-17, was synthesized and found to have an exceptionally complicated structure with helical Bi-O rods cross-linked by 1,3,5-benzenetricarboxylate (BTC3-) ligands. Five crystallographically independent 1D channels including two hexagonal channels, two rectangular channels, and one triangular channel have accessible diameters of 9.6, 9.6, 3.6, 3.6, and 3.4 angstrom, respectively. The structure is further complicated by twinning. Rod-incorporated MOF structures typically have underlying nets with only one unique node and three or four unique edges. In contrast, topological analysis of CAU-17 revealed unprecedented complexity for a MOF structure with 54 unique nodes and 135 edges. The complexity originates from the rod packing and the rods themselves, which are related to aperiodic helices.

  • 38.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Peskov, Maxim V.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    SU-62: Synthesis and Structure Investigation of a Germanate with a Novel Three-Dimensional Net and Interconnected 10- and 14-Ring Channels2012In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 12, no 1, p. 369-375Article in journal (Refereed)
    Abstract [en]

    A novel 3D open-framework germanate, vertical bar N(2)C(4)H(14)vertical bar(4) [Ge(20)O(41)(OH)(6)]center dot 3H(2)O (SU-62), was prepared from hydrothermal synthesis using 1,4-diaminobutane as the organic structure directing agent (SDA). The crystal structure was solved by single crystal X-ray diffraction. The framework is built from Ge(10)(O,OH)(27) (Ge(10)) secondary building units and exhibits an irregular three-dimensional channel system encircled by 10- and 14-rings. The framework of SU-62 has an underlying topology that follows a novel five-coordinated svh-5-I4(1)/amd net, while the pores follow the tsi net. The thermal behavior of SU-62 was studied by thermogravimetric (TG) analysis and in situ X-ray diffraction (XRPD). Crystallographic data: orthorhombic, space group Fdd2, unit cell parameters a = 15.297(3) angstrom, b = 53.58(1) angstrom, c = 14.422(3) angstrom, V = 11821(4) angstrom(3), Z = 8.

  • 39.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Moraga, Francisca
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Guo, Bing
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Three low dimensional open germanates based on the 4(4) net2012In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 14, no 17, p. 5465-5471Article in journal (Refereed)
    Abstract [en]

    Three novel low-dimensional open-germanates, denoted as SU-71, SU-72 and SU-73, were synthesized by solvothermal methods and their structures were determined by single crystal X-ray diffraction. The structures of SU-71, SU-72 and SU-73 are all built from Ge7X19 (X = O, OH or F) clusters that are connected according to the topologies related to the 4(4) net. SU-71 has a layered structure following the 4(4) net, SU-72 contains 2D slabs with unprecedented crescent-shaped 23-ring channels and SU-73 consists of zero-dimensional (0D) open nanoballs. SU-71 and SU-72 were both synthesized using 1-(2-aminoethyl)piperazine (AEP) as the organic structure directing agent, while pentaethylenehexamine (PEHA) was used for the synthesis of SU-73. All three phases form in the presence of HF, which promotes the formation of the Ge7X19 cluster. A comparison of the related structures reveals a relationship between the orientation of the Ge7X19 building units and the curvature of the 4(4) net layer.

  • 40.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Moraga, Francisca
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Guo, Bing
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Three Low-Dimensional Open-Germanates Derived from the 4^4 NetIn: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033Article in journal (Refereed)
  • 41.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Willhammar, Tom
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    McCusker, Lynne
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    SU-66: An Open-framework Gallogermanate with 26-ringchannels Solved by Combining Infrared Spectroscopy, ElectronDiffraction and X-ray Powder DiffractionManuscript (preprint) (Other academic)
  • 42.
    Inge, A. Ken
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Open-Framework Germanates and Related Materials2013In: Nanoporous Materials: Synthesis and Applications / [ed] Qiang Xu, London: Taylor & Francis Group, 2013, p. 319-349Chapter in book (Other academic)
  • 43.
    Inge, Andrew Kentaro
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Open-Framework Germanates: Synthesis, Structure, and Characterization2012Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Novel open-framework germanates and open low-dimensional structures were synthesized and characterized. Their crystal structures were solved by single crystal X-ray diffraction or X-ray powder diffraction combined with other techniques. Although related open-framework materials, such as zeolites, are of interest for the ability to selectively accommodate guest species in their rings, pores and channels, germanates are primarily of interest for their unique structural properties. Compared to aluminosilicate-based zeolites, germanium oxides readily form frameworks with extra-large rings and low framework density. The formation of elegant germanate architectures is attributed to the unique Ge-O bond geometries compared to Si-O, and the tendency to form large clusters.

    This thesis is to serve as an introduction to germanate synthesis, structures and characterization. Structures are categorized in accordance to their building units; the Ge7X19 (Ge7), Ge9X25-26 (Ge9) and Ge10X28 (Ge10) (X = O, OH, or F) clusters. Structure determination techniques as well as the characterization techniques used to examine the properties of the materials are presented. While most of the discussed techniques have routinely been used to study crystalline open-frameworks, we introduce the use of infrared spectroscopy for the identification of cluster types, valuable for structure determination by X-ray powder diffraction. Structures and properties of the novel materials ASU-21, SU-62, SU-63, SU-64, SU-65, SU-66, SU-71, SU-72, SU-73, SU-74, SU-75 and SU-JU-14 are described and put into context with previously known structures. The novel structures are all built of the Ge7, Ge9 or Ge10 clusters, and vary from a framework with novel topology to the first open zero-dimensional germanate cavities built of such clusters.

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  • 44. Koeppen, Milan
    et al.
    Meyer, Vanessa
    Ångström, Jonas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Solvent-Dependent Formation of Three New Bi-Metal-Organic Frameworks Using a Tetracarboxylic Acid2018In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 18, no 7, p. 4060-4067Article in journal (Refereed)
    Abstract [en]

    Systematic solvent screening using high-throughput solvothermal syntheses with bismuth nitrate pentahydrate and 1,2,4,5-tetrakis-(4-carboxyphenyl)benzene (H4TCPB) led to three new porous Bi-metal-organic frameworks [Bi-2(H2TCPB)(TCPB)(H2O)(2)]center dot xH(2)O (CAU-31), (NH2(CH3)(2) [Bi(TCPB)(H2O)]center dot xH(2)O (CAU-32), and [Bi-4(O)(2)(OH)(2)(H2TCPB)(TCPB)(H2O)(2)]center dot xH(2)O (CAU-33). Compounds CAU-31, -32, and -33 were synthesized in CH3OH, CH3OH/DMF, and DMF/toluene, respectively. The crystal structures were determined using electron diffraction and single-crystal X-ray diffraction in combination with the Rietveld method. The structures of CAU-31 and CAU-32 are composed of isolated Bi3+ ions as the inorganic building unit (IBU), which are connected by the linker ions to form a layered structure with inclined interpenetration and a three-dimensional anionic network, respectively. The IBU of CAU-33 consists of infinite bismuth-oxo rods forming a three-dimensional network by connection of the organic linkers. For CAU-33 structural flexibility was observed, and two phases denoted alpha- and beta-CAU-33 could be isolated.

  • 45. Krüger, Martin
    et al.
    Albat, Martin
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Investigation of the effect of polar functional groups on the crystal structures of indium MOFs2017In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 19, no 31, p. 4622-4628Article in journal (Refereed)
    Abstract [en]

    Three new In-MOFs with -NH2 and/or -NO2 functionalities are reported using 2-amino-(H2BDC-NH2), 2-nitro-(H2BDC-NO2) and 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2). Their structures were determined from single crystal X-ray diffraction data. The structure of the first In-MOF of composition [In(BDC-NH3)(BDC-NH2)] center dot 1.6DMF center dot 1.9H(2)O (In-BDC-NH2;DMF is dimethylformamide; the space group is P6(2)22, a = b = 14.738(2) angstrom and c = 12.257(3) angstrom) is built up by two interpenetrating nets of InOB polyhedra interconnected by BDC-NH2 2-ions to form a framework with qtz topology. Charge balance is accomplished by partial protonation of the amino group, which was confirmed by IR spectroscopy. The interpenetration leads to a decrease of the pore dimension (4.4 angstrom in diameter). Thermogravimetric analysis revealed stability up to 300 degrees C. Replacement of H2BDC-NH2 by H2BDC-NO2 in the reaction mixture led to the iso-reticular MOF containing no -NO2 groups but exclusively un- and amino-functionalized linkers. Hence an indium mediated reduction of the H2BDC-NO2 linker molecule during solvothermal synthesis has occurred. The use of H2BDC-NH2/NO2 under exactly the same reaction conditions did not result in the formation of a MOF, but by changing the synthesis parameters, a new -NH2/-NO2 bifunctionalised In-MOF of composition (DMA)(2).In-3.mu(3)-O)(BDC-NH2/NO2) 4.5] center dot DMF (DMA is dimethylammonium), denoted In-BDC-NH2/NO2, was obtained. The crystal morphology can be altered from cubic to truncated octahedral crystals by varying the DMF/ethanol volume ratio during synthesis. The compound crystallises in the cubic space group I43m, a = 24.8947(1) angstrom, and the framework contains trinuclear {In-3.mu(3)-O)} clusters which are interlinked by the BDC-NH2/NO2 2-ions to form super-tetrahedra. Four face-sharing super-tetrahedra form ultra-tetrahedra which are connected to form the final cubic framework with an ncb topology and isolated inaccessible pores.

  • 46. Krüger, Martin
    et al.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Reinsch, Helge
    Li, Yuan-Han
    Wahiduzzaman, Mohammad
    Lin, Chia-Her
    Wang, Sue-Lein
    Maurin, Guillaume
    Stock, Norbert
    Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization2017In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 56, no 10, p. 5851-5862Article in journal (Refereed)
    Abstract [en]

    The in situ and systematic high-throughput investigation of the system Al3+/4,4'-benzophenonedicarboxylic acid (H2BPDC)/DMF/H2O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) angstrom, c = 23.864(1) angstrom). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8O8} IBUs are arranged in a bcu packing and connected via BPDC2(-) ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 angstrom are formed. In addition, tetrahedral cavities are formed by the BPDC2(-) linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2(-) ions. Replacing H2BPDC by 4,4'-oxydibenzoic acid (H2ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 degrees C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N-2 and CO2, while the latter only adsorb CO2.

  • 47. Krüger, Martin
    et al.
    Reinsch, Helge
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Stock, Norbert
    Effect of partial linker fluorination and linker extension on structure and properties of the Al-MOF CAU-102017In: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 249, p. 128-136Article in journal (Refereed)
    Abstract [en]

    The systematic investigation of the solvothermal system Al3+/5-fluoroisophthalic acid (H(2)mBDC-5F)/isophthalic acid (H(2)mBDC)/DMF/H2O through a mixed-linker approach led to new mixed-linker CAU-10 derivatives containing 11, 28 and 44% of fluorinated linker molecules (denoted as CAU-10-H/F-11, CAU-10-H/F-28 and CAU-10-H/F-44, respectively), as determined by NMR spectroscopy. The crystal structure of CAU-10-H/F-28 was determined using the Rietveld method (space group 14(1)md, a = b = 21.3075(5), c = 10.7101(3) angstrom). The structure is built up by helical chains composed of cis corner-sharing AlO6 polyhedra. Each of these helices is interconnected to four adjacent helices with alternating rotational orientation through the carboxylate groups of mBDC(2-) linker molecules. Thus, accessible, square-shaped channels are formed. Sorption measurements revealed a high dependency of the adsorbed amount of gas on the degree of fluorination. With increasing fluorination, the total uptake decreases in N-2, H-2 and H2O sorption experiments and the hydrophobic character of the pores increases. In addition, an extended CAU-10 derivative, CAU-10-HTATB, was discovered using the tricarboxylic acid 4,4',4-s-triazine-2,4,6-triyl-tribenzoic acid (H(3)TATB) during the high-throughput investigation of the system Al3+/H(3)TATB/DMF/H2O. This new MOF, which was denoted CAU-10-HTATB, was thoroughly characterized using IR spectroscopy, thermogravimetric and elemental analysis, temperature dependent powder X-ray diffraction (PXRD) and sorption measurements. Although the compound is thermally stable up to 400 degrees C according to temperature-dependent PXRD measurements, it is not porous towards N2 molecules. The structure of CAU-10-HTATB could be also refined from PXRD data using the Rietveld method (space group l4(1)/a, a = b = 36.438 (1), c = 10.9373 (9) angstrom).

  • 48. Kumar, Amol
    et al.
    Li, Jingguo
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Ott, Sascha
    Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency2023In: ACS Nano, ISSN 1936-0851, E-ISSN 1936-086X, Vol. 17, no 21, p. 21595-21603Article in journal (Refereed)
    Abstract [en]

    The power of isoreticular chemistry has been widely exploited to engineer metal–organic frameworks (MOFs) with fascinating molecular sieving and storage properties but is underexplored for designing MOFs with tunable optoelectronic properties. Herein, three dipyrazole-terminated XDIs (X = PM (pyromellitic), N (naphthalene), or P (perylene); DI = diimide) with different lengths and electronic properties are prepared and employed as linkers for the construction of an isoreticular series of Zn-XDI MOFs with distinct electrochromism. The MOFs are grown on fluorine-doped tin oxide (FTO) as high-quality crystalline thin films and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Due to the constituting electronically isolated XDI linkers, each member of the isoreticular thin film series exhibits two reversible one-electron redox events, each at a distinct electrochemical potential. The orientation of the MOFs as thin films as well as their isoreticular nature results in identical cation-coupled electron hopping transport rates in all three materials, as demonstrated by comparable apparent electron diffusion coefficients, Deapp. Upon electrochemical reduction to either the [XDI]•– or [XDI]2– state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm2 C–1 at 746 nm, which is attributed to the maximized Faradaic transformations at each electronically isolated PDI unit. The electrochromic response of the thin film is retained to more than 99% over 100 reduction–oxidation cycles, demonstrating the applicability of the presented materials.

  • 49.
    Kumar, Bhaskar Pal
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Di Tommaso, Ester Maria
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Olofsson, Berit
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Photoredox-Catalyzed Stereoselective Vinylation Reactions with Vinylbenziodoxol(on)esManuscript (preprint) (Other academic)
    Abstract [en]

    We have disclosed an efficient transition-metal-free radical-mediated C-C cross-coupling reaction of 4-alkyl-1,4-DHPs and VBXs through photo-redox catalysis to afford vinylated products in good yields with retention of configuration from parent VBXs. This mild photocatalysis system featured excellent functional group tolerance, a wide range of substrate scope and unique stereoselectivities. The utility of this new protocol has been demonstrated via the syntheses of diastereoselective C-vinyl glycosides. Preliminary mechanistic studies signify the involvement of radicals and the formation of ligand coupled TS in the reaction pathway.

  • 50. Köppen, Milan
    et al.
    Dhakshinamoorthy, Amarajothi
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Christian‐Albrechts‐Universität zu Kiel, Germany.
    Cheung, Ocean
    Ångström, Jonas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Mayer, Peter
    Stock, Norbert
    Synthesis, Transformation, Catalysis, and Gas Sorption Investigations on the Bismuth Metal-Organic Framework CAU-172018In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 30, p. 3496-3503Article in journal (Refereed)
    Abstract [en]

    Very few microporous bismuth metal-organic frameworks have been discovered to date. Of these, no detailed experimental characterization of the synthesis and properties have been reported until now for the only one which can be prepared from inexpensive starting materials: CAU-17 [Bi(BTC)(H2O)], with H3BTC = trimesic acid. In-situ powder X-ray diffraction during solvothermal synthesis of CAU-17 revealed that it crystallizes rapidly within 2 minutes, and if the reaction is not stopped, the MOF transforms into a nonporous dense purely inorganic material within one hour, revealing that CAU-17 is a crystalline intermediate phase. Synthesis scale-up employing more concentrated reaction mixtures resulted in another Bi trimesate of composition [Bi(HBTC)(NO3)(MeOH)]MeOH, which structurally decomposes upon storage under ambient conditions. Sorption experiments showed that CAU-17 is microporous with a BET surface area of 530 m(2)/g. As a potential greenhouse gas sorbent, CAU-17 showed high SF6/N-2 and CO2/N-2 selectivity > 31 and 29, respectively. Furthermore, the catalytic activity of CAU-17 was studied in the regioselective ring-opening of styrene oxide by methanol to obtain 2-methoxy-2-phenylethanol, thus demonstrating the existence of coordinatively unsaturated sites in the crystal structure of CAU-17.

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