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Characterization of crystalline materials by rotation electron diffraction: Phase identification and structure determination
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Electron crystallography is powerful for determination of complex structures. The newly-developed 3D electron diffraction (ED) methods make structure determination from nano- and micron-sized crystals much easier than using other methods, for example X-ray diffraction. Almost complete 3D ED data can be collected easily and fast from crystals at any arbitrary orientations. Dynamical effects are largely reduced compared to zonal ED patterns. 3D ED is powerful for phase identification and structure solution from individual nano- and micron-sized crystals, while powder X-ray diffraction (PXRD) provides information from all phases present in the samples. 3D ED methods and PXRD are complementary and their combinations are promising for studying multiphasic samples and complicated crystal structures.

In this thesis, the feasibility and capability of 3D ED methods, specifically rotation electron diffraction (RED), in phase identification and structure determination of different kinds of crystalline materials with nano- or submicrometer-sized crystals are investigated. Experimental conditions for RED data collection and data processing in relation to data quality, as well as the challenges in the applications of RED are discussed.

RED was combined with PXRD to identify phases from as-synthesized samples and to characterize atomic structures of eleven crystalline compounds. It was shown to be possible to identify as many as four distinct compounds within one sample containing submicron-sized crystals in a Ni-Se-O-Cl system. RED was also used to determine unit cell and symmetry of isoreticular metal-organic frameworks (SUMOF-7) and solve five zeolite structures with new frameworks, ITQ-51, ITQ-53, ITQ-54, EMM-23 and EMM-25 and that of a metal-organic framework (MOF), SUMOF-7I. The structure of an open-framework germanate SU-77 was solved by combining RED with PXRD. The structures of the zeolites and SU-77 were confirmed by Rietveld refinement against PXRD. High-resolution transmission electron microscopy was used to confirm the structure models of ITQ-51, EMM-25 and SUMOF-7I.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University , 2014. , 102 p.
Keyword [en]
electron microscopy, phase identification, rotation electron diffraction, structure determination, three-dimensional electron diffraction
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-108930ISBN: 978-91-7649-017-4 (print)OAI: oai:DiVA.org:su-108930DiVA: diva2:761516
Public defence
2014-12-17, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Submitted. Paper 4: Accepted. Paper 6: Manuscript. Paper 7: Epub ahead of print. Paper 9: Manuscript. Paper 11: Manuscript.

Available from: 2014-11-25 Created: 2014-11-06 Last updated: 2015-10-27Bibliographically approved
List of papers
1. Structural Determination of Ordered Porous Solids by Electron Crystallography
Open this publication in new window or tab >>Structural Determination of Ordered Porous Solids by Electron Crystallography
2014 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 24, no 2 (SI), 182-199 p.Article, review/survey (Refereed) Published
Abstract [en]

Knowing the structure of porous materials is essential for understanding their properties and exploiting them for applications. Electron crystallography has two main advantages compared to X-ray diffraction for structure determination. Crystals too small or too complicated to be studied by X-ray diffraction can be studied by electron crystallography. The crystallographic structure factor phase information, which is lost in X-ray diffraction, can be obtained from high-resolution transmission electron microscopy (HRTEM) images. Here, different electron microscopic techniques and their applications for structure determination of porous materials are reviewed. The recently developed automated diffraction tomography (ADT), the rotation electron diffraction (RED), and the through-focus structure projection reconstruction (QFcous) methods make the structure determination by electron crystallography more feasible for non-TEM experts and as efficient as that by X-ray diffraction. How the various electron crystallographic methods are chosen are demonstrated and these methods used for solving different structural problems in porous materials. The benefits of combining electron crystallography and X-ray diffraction for studying complex zeolite structures are also shown. A large number of examples are given to demonstrate the use of various electron crystallographic techniques for structure determination of zeolites, metal-organic frameworks and ordered mesoporous materials. These electron crystallographic methods are general and can also be used for structural studies of other functional materials.

National Category
Nano Technology Materials Engineering Materials Chemistry
Identifiers
urn:nbn:se:su:diva-95866 (URN)10.1002/adfm.201301949 (DOI)000330963000002 ()
Funder
Knut and Alice Wallenberg FoundationVinnovaSwedish Research Council
Note

AuthorCount: 3;

Available from: 2013-11-05 Created: 2013-11-05 Last updated: 2017-12-06Bibliographically approved
2. Three-dimensional electron diffraction as a complementary technique to powder X-ray diffraction for phase identification and structure solution of powders
Open this publication in new window or tab >>Three-dimensional electron diffraction as a complementary technique to powder X-ray diffraction for phase identification and structure solution of powders
2015 (English)In: IUCrJ, ISSN 2052-2525, Vol. 2, 267-282 p.Article in journal (Refereed) Published
Abstract [en]

Phase identification and structure determination are important and widely used techniques in chemistry, physics and materials science. Recently, two methods for automated three-dimensional electron diffraction (ED) data collection, namely automated diffraction tomography (ADT) and rotation electron diffraction (RED), have been developed. Compared with X-ray diffraction (XRD) and two-dimensional zonal ED, three-dimensional ED methods have many advantages in identifying phases and determining unknown structures. Almost complete three-dimensional ED data can be collected using the ADT and RED methods. Since each ED pattern is usually measured off the zone axes by three-dimensional ED methods, dynamic effects are much reduced compared with zonal ED patterns. Data collection is easy and fast, and can start at any arbitrary orientation of the crystal, which facilitates automation. Threedimensional ED is a powerful technique for structure identification and structure solution from individual nano-or micron-sized particles, while powder X-ray diffraction (PXRD) provides information from all phases present in a sample. ED suffers from dynamic scattering, while PXRD data are kinematic. Three-dimensional ED methods and PXRD are complementary and their combinations are promising for studying multiphase samples and complicated crystal structures. Here, two three-dimensional ED methods, ADTand RED, are described. Examples are given of combinations of three-dimensional ED methods and PXRD for phase identification and structure determination over a large number of different materials, from Ni-Se-O-Cl crystals, zeolites, germanates, metal-organic frameworks and organic compounds to intermetallics with modulated structures. It is shown that three-dimensional ED is now as feasible as X-ray diffraction for phase identification and structure solution, but still needs further development in order to be as accurate as X-ray diffraction. It is expected that three-dimensional ED methods will become crucially important in the near future.

Keyword
three-dimensional electron diffraction, powder X-ray diffraction, phase identification, structure determination
National Category
Chemical Sciences Materials Engineering
Identifiers
urn:nbn:se:su:diva-119011 (URN)10.1107/S2052252514028188 (DOI)000356866400016 ()
Available from: 2015-07-28 Created: 2015-07-24 Last updated: 2015-10-27Bibliographically approved
3. A complex pseudo-decagonal quasicrystal approximant, Al-37(Co,Ni)(15.5), solved by rotation electron diffraction
Open this publication in new window or tab >>A complex pseudo-decagonal quasicrystal approximant, Al-37(Co,Ni)(15.5), solved by rotation electron diffraction
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2014 (English)In: Journal of applied crystallography, ISSN 0021-8898, E-ISSN 1600-5767, Vol. 47, no 1, 215-221 p.Article in journal (Refereed) Published
Abstract [en]

Electron diffraction is a complementary technique to single-crystal X-ray diffraction and powder X-ray diffraction for structure solution of unknown crystals. Crystals too small to be studied by single-crystal X-ray diffraction or too complex to be solved by powder X-ray diffraction can be studied by electron diffraction. The main drawbacks of electron diffraction have been the difficulties in collecting complete three-dimensional electron diffraction data by conventional electron diffraction methods and the very time-consuming data collection. In addition, the intensities of electron diffraction suffer from dynamical scattering. Recently, a new electron diffraction method, rotation electron diffraction (RED), was developed, which can overcome the drawbacks and reduce dynamical effects. A complete three-dimensional electron diffraction data set can be collected from a sub-micrometre-sized single crystal in less than 2 h. Here the RED method is applied for ab initio structure determination of an unknown complex intermetallic phase, the pseudo-decagonal (PD) quasicrystal approximant Al-37.0(Co,Ni)(15.5), denoted as PD2. RED shows that the crystal is F-centered, with a = 46.4, b = 64.6, c = 8.2 angstrom. However, as with other approximants in the PD series, the reflections with odd l indices are much weaker than those with l even, so it was decided to first solve the PD2 structure in the smaller, primitive unit cell. The basic structure of PD2 with unit-cell parameters a = 23.2, b = 32.3, c = 4.1 angstrom and space group Pnmm has been solved in the present study. The structure with c = 8.2 angstrom will be taken up in the near future. The basic structure contains 55 unique atoms (17 Co/Ni and 38 Al) and is one of the most complex structures solved by electron diffraction. PD2 is built of characteristic 2 nm wheel clusters with fivefold rotational symmetry, which agrees with results from high-resolution electron microscopy images. Simulated electron diffraction patterns for the structure model are in good agreement with the experimental electron diffraction patterns obtained by RED.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-101248 (URN)10.1107/S1600576713029294 (DOI)000330485100029 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation, 3DEM-NATUR
Note

AuthorCount:6;

Available from: 2014-03-04 Created: 2014-03-03 Last updated: 2017-12-05Bibliographically approved
4. Phase identification and structure determination from multiphasic crystalline powder samples by rotation electron diffraction
Open this publication in new window or tab >>Phase identification and structure determination from multiphasic crystalline powder samples by rotation electron diffraction
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(English)In: Journal of applied crystallography, ISSN 0021-8898, E-ISSN 1600-5767Article in journal (Refereed) Accepted
Abstract [en]

Phase identification and structure characterisation are important in synthetic and material science. It is difficult to characterise the individual phases from multiphasic crystalline powder samples, especially if some of the phases are unknown. Here we describe how this problem can be solved by combining rotation electron diffraction (RED) and powder X-ray diffraction (PXRD). Four phases were identified on the same transmission electron microscopy (TEM) grid from a multiphasic sample in the Ni-Se-O-Cl system and their structures were solved from the RED data. Phase 1 (NiSeO3) was found in the Inorganic Crystal Structure Data (ICSD) database using the information from RED. Phase 2 (Ni3Se4O10Cl2) is an unknown compound but it is iso-structural to Co3Se4O10Cl2, which was recently solved by single crystal X-ray diffraction. Phase 3 (Ni5Se6O16Cl4H2) and Phase 4 (Ni5Se4O12Cl2) are new compounds. The fact that there are at least four different compounds in the as-synthesised material explains why the phase identification and structure determination could not be done only by PXRD. The RED method makes phase identification from such multiphasic powder samples much easier compared to powder X-ray diffraction. The RED method also makes structure determination of submicron-sized crystals from multiphasic samples possible.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108925 (URN)
Available from: 2014-11-06 Created: 2014-11-06 Last updated: 2017-12-05
5. Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents
Open this publication in new window or tab >>Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents
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2013 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 110, no 10, 3749-3754 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis of crystalline microporous materials containing large pores is in high demand by industry, especially for the use of these materials as catalysts in chemical processes involving bulky molecules. An extra-large-pore silicoaluminophosphate with 16-ring openings, ITQ-51, has been synthesized by the use of bulky aromatic proton sponges as organic structure-directing agents. Proton sponges show exceptional properties for directing extra-large zeolites because of their unusually high basicity combined with their large size and rigidity. This extra-large-pore material is stable after calcination, being one of the very few examples of hydrothermally stable molecular sieves containing extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals using the rotation electron diffraction method. Finally, several hypothetical zeolites related to ITQ-51 have been proposed.

Keyword
aluminophosphate, extra-large microporous materials, zeolite synthesis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-89553 (URN)10.1073/pnas.1220733110 (DOI)000316377400028 ()
Funder
Swedish Research CouncilVINNOVAKnut and Alice Wallenberg Foundation
Note

AuthorCount:7;

Available from: 2013-05-02 Created: 2013-04-29 Last updated: 2017-11-16Bibliographically approved
6. The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule
Open this publication in new window or tab >>The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

A new germanosilicate zeolite (denoted as ITQ-53) with extra-large 14-ring pores has been synthesized using tri-tertbutylmethylphosphonium cation as the organic structure directing agent (OSDA). The new rotation electron diffraction (RED) method was used to both identify and solve the structure of ITQ-53 from an initially synthesized sample containing impurities, which facilitated the synthesis optimization that led to pure ITQ-53. The structure was refined against PXRD data. ITQ-53 is the first example of extra-large pore zeolites with tri-directional interconnected 14 × 14 × 14-ring channels. It is built from double 3-rings (D3Rs), double 4-rings (D4Rs), and a new composite building unit [42.54.63]. D3Rs are very rare, previously only found in two zeolitic silicogermanates. ITQ-53 is stable up to at least 450 °C. The structure of ITQ-53 was changed from monoclinic to orthorhombic up on calcination.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108927 (URN)
Available from: 2014-11-06 Created: 2014-11-06 Last updated: 2014-11-07
7. ITQ-54: a multi-dimensional extra-large pore zeolite with 20 [times] 14 [times] 12-ring channels
Open this publication in new window or tab >>ITQ-54: a multi-dimensional extra-large pore zeolite with 20 [times] 14 [times] 12-ring channels
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2015 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 6, 480-485 p.Article in journal (Refereed) Published
Abstract [en]

A multi-dimensional extra-large pore silicogermanate zeolite, named ITQ-54, has been synthesised by in situ decomposition of the N,N-dicyclohexylisoindolinium cation into the N-cyclohexylisoindolinium cation. Its structure was solved by 3D rotation electron diffraction (RED) from crystals of ca. 1 [small mu ]m in size. The structure of ITQ-54 contains straight intersecting 20 [times] 14 [times] 12-ring channels along the three crystallographic axes and it is one of the few zeolites with extra-large channels in more than one direction. ITQ-54 has a framework density of 11.1 T atoms per 1000 A3, which is one of the lowest among the known zeolites. ITQ-54 was obtained together with GeO2 as an impurity. A heavy liquid separation method was developed and successfully applied to remove this impurity from the zeolite. ITQ-54 is stable up to 600 [degree]C and exhibits permanent porosity. The structure was further refined using powder X-ray diffraction (PXRD) data for both as-made and calcined samples.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108918 (URN)10.1039/C4SC02577F (DOI)000345901600055 ()
Available from: 2014-11-06 Created: 2014-11-06 Last updated: 2017-12-05Bibliographically approved
8. EMM-23: A Stable High-Silica Multidimensional Zeolite with Extra-Large Trilobe-Shaped Channels.
Open this publication in new window or tab >>EMM-23: A Stable High-Silica Multidimensional Zeolite with Extra-Large Trilobe-Shaped Channels.
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2014 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 136, no 39, 13570-3 p.Article in journal (Refereed) Published
Abstract [en]

Stable, multidimensional, and extra-large pore zeolites are desirable by industry for catalysis and separation of bulky molecules. Here we report EMM-23, the first stable, three-dimensional extra-large pore aluminosilicate zeolite. The structure of EMM-23 was determined from submicron-sized crystals by combining electron crystallography, solid-state nuclear magnetic resonance (NMR), and powder X-ray diffraction. The framework contains highly unusual trilobe-shaped pores that are bound by 21-24 tetrahedral atoms. These extra-large pores are intersected perpendicularly by a two-dimensional 10-ring channel system. Unlike most ideal zeolite frameworks that have tetrahedral sites with four next-nearest tetrahedral neighbors (Q(4) species), this unusual zeolite possesses a high density of Q(2) and Q(3) silicon species. It is the first zeolite prepared directly with Q(2) species that are intrinsic to the framework. EMM-23 is stable after calcination at 540 °C. The formation of this highly interrupted structure is facilitated by the high density of extra framework positive charge introduced by the dicationic structure directing agent.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108916 (URN)10.1021/ja507615b (DOI)000342608800026 ()25198917 (PubMedID)
Available from: 2014-11-06 Created: 2014-11-06 Last updated: 2017-12-05Bibliographically approved
9. Rational synthesis and structure of a borosilicate zeolite with intersecting 10- and 11-ring channels
Open this publication in new window or tab >>Rational synthesis and structure of a borosilicate zeolite with intersecting 10- and 11-ring channels
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(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-95867 (URN)
Available from: 2013-11-05 Created: 2013-11-05 Last updated: 2014-11-10
10. SU-77: An Open-Framework Germanate Containing 12 × 10 × 10-Ring Channels Solved by Combining Rotation Electron Diffraction and Powder X-ray Diffraction
Open this publication in new window or tab >>SU-77: An Open-Framework Germanate Containing 12 × 10 × 10-Ring Channels Solved by Combining Rotation Electron Diffraction and Powder X-ray Diffraction
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2014 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 14, no 10, 5072-5078 p.Article in journal (Refereed) Published
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.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-102757 (URN)10.1021/cg500681k (DOI)000342609300027 ()
Available from: 2014-04-22 Created: 2014-04-22 Last updated: 2017-12-05Bibliographically approved
11. Highly porous isoreticular lanthanide metal-organic frameworks
Open this publication in new window or tab >>Highly porous isoreticular lanthanide metal-organic frameworks
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

As an emerging type of porous materials, metal–organic frameworks (MOFs) have the advantages over conventional inorganic porous materials in that their structures and functions are systematically and predictably designable. Isoreticular expansion is an efficient way for systematic design and control of pore size and shape for MOFs. By using our proposed strategy, a series of highly porous isoreticular lanthanide-based metal-organic frameworks with systematic pore apertures has been obtained, which afford an isoreticular series of MIL-103 structures (termed SUMOF-7I to IV) with pore apertures ranging from 7.2 Å to 23 Å. These materials demonstrated exhibit robust architectures with permanent porosity, and exceptional thermal stability and chemical stability in various solvents. The combination of luminescence property and significant porosity of these MOFs enable them as a potential platform for multifunctional purpose.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108928 (URN)
Available from: 2014-11-06 Created: 2014-11-06 Last updated: 2016-01-29Bibliographically approved

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