Herein, Zn plating-stripping onto metallic Zn using a couple of acetonitrile (AN)-based electrolytes (0.5 mZn(TFSI)(2)/AN and 0.5 mZn(CF3SO3)(2)/AN) is studied. Both electrolytes show a reversible Zn plating/stripping over 1000 cycles at different applied current densities varying from 1.25 to 10 mA cm(-2). The overpotentials of Zn plating-stripping over 500 cycles at constant current of 1.25 and 10 mA cm(-2)are +/- 0.05 and +/- 0.2 V, respectively. X-ray photoelectron spectroscopy analysis reveals that no decomposition product is formed on the Zn surface. The anodic stability of four different current collectors of aluminum foil (Al), carbon-coated aluminum foil (C/Al), TiN-coated titanium foil (TiN/Ti), and multiwalled carbon nanotube paper (MWCNT-paper) is tested in both electrolytes. As a general trend, the current collectors have a higher anodic stability in Zn(TFSI)(2)/AN compared with Zn(CF3SO3)(2)/AN. The Al foil displays the highest anodic stability of approximate to 2.25 V versus Zn2+/Zn in Zn(TFSI)(2)/AN electrolyte. The TiN/Ti shows a comparable anodic stability with that of Al foil, but its anodic current density is higher than Al. The promising reversibility of the Zn plating/stripping combined with the anodic stability of Al and TiN/Ti current collectors paves the way for establishing highly reversible Zn-ion batteries.

Microscopic pathways of structural phase transitions inmetal halide perovskites are difficult to probe because they occur over disparate time and length scales and because electron-based microscopies typically used to directly probe nanoscale dynamics of phase transitions often damage metal halide perovskite materials. Using in situ nanoscale cathodoluminescence microscopy with low electron beam exposure, we visualize nucleation and growth in the thermally driven transition to the perovskite phase in hundreds of non-perovskite phase nanowires. In combination with molecular dynamics simulations, we reveal that the transformation does not follow a simple martensitic mechanism, but proceeds despite a substantial energy barrier via ion diffusion through a liquid-like interface between the two structures. While cations are disordered in this liquid-like region, the halide ions retain substantial spatial correlations. This detailed picture not only reveals how phase transitions between disparate structures can proceed, but also opens the possibility to control such processes.

Heavy metal-free CuInS2 quantum dots (QDs) were employed as a photosensitizer on a NiO photocathode to drive an immobilized molecular Re catalyst for photoelectrochemical CO2 reduction for the first time. A photocurrent of 25 mu A cm(-2) at -0.87 V vs. NHE was obtained, providing a faradaic efficiency of 32% for CO production.

Two-dimensional (2D) transition metal oxides (TMOs) are a category of materials which have unique physical and chemical properties compared to their bulk counterparts. However, the synthesis of 2D TMOs commonly includes the use of environmental threats such as organic solvents. In this thesis, we developed environmentally friendly strategies to fabricate TMO nanosheets from the commercially available bulk oxides. In particular, hydrated vanadium pentoxide (V₂O₅∙nH₂O) nanosheets and oxygen deficient molybdenum trioxide (MoO_3-x) nanosheets were prepared.  The V₂O₅∙nH₂O nanosheets were drop-cast onto multi-walled carbon nanotube (MWCNT) paper and applied as a free-standing electrode (FSE) for a lithium battery. The accessible capacity of the FSE was dependent on the electrode thickness; the thickest electrode delivered the lowest accessible capacity.  Alternatively, a composite material of V₂O₅∙nH₂O nanosheets with 10% MWCNT (VO_x-CNT composite) was prepared and two types of electrodes, FSE and conventionally cast electrode (CCE), were employed as cathode materials for lithium batteries. A detailed comparison between these electrodes was presented. In addition, the VO_x-CNT composite was applied as a negative electrode for a sodium-ion battery and showed a reversible capacity of about 140 mAh g^-1. On the other hand, the MoO_3-x nanosheets were employed as binder-free electrodes for supercapacitor application in an acidified Na₂SO₄ electrolyte. Furthermore, the MoO_3-x nanosheets were used as photocatalysts for organic dye degradation. The simple eco-friendly synthesis methods coupled with the potential application of the TMO nanosheets reflect the significance of this thesis in both the synthesis and the energy-related applications of 2D materials.

Nanostructured hydrated vanadium oxides (V2O5 center dot nH(2)O) are actively being researched for applications in energy storage, catalysis, and gas sensors. Recently, a one-step exfoliation technique for fabricating V2O5 center dot nH(2)O nano-sheets in aqueous media was reported; however, the underlying mechanism of exfoliation has been challenging to study. Herein, we followed the synthesis of V2O5 center dot nH(2)O nanosheets from the V2O5 and VO2 precursors in real using solution- and solid-state V-51 NMR. Solution-state V-51 NMR showed that the aqueous solution contained mostly the decavanadate anion [H2V10O28](4-) and the hydrated dioxova-nadate cation [VO2 center dot 4H(2)O](+), and during the exfoliation process, decavanadate was formed, while the amount of [VO2 center dot 4H(2)O](+) remained constant. The conversion of the solid precursor V2O5, which was monitored with solid-state V-51 NMR, was initiated when VO2 was in its monoclinic forms. The dried V2O5 center dot nH(2)O nanosheets were weakly paramagnetic because of a minor content of isolated V4+. Its solid-state V-51 signal was less than 20% of V2O5 and arose from diamagnetic V4+ or V5+.This study demonstrates the use of real-time NMR techniques as a powerful analysis tool for the exfoliation of bulk materials into nanosheets. A deeper understanding of this process will pave the way to tailor these important materials.

Herein, a simple aqueous‐exfoliation strategy is introduced for the fabrication of a series of MoO_3−x nanosheets (where x stands for oxygen vacancies) using two commercial molybdenum oxide precursors, MoO₂ and MoO₃. The nanosheets offer a localized surface plasmon resonance (LSPR) effect which is dependent on the structure and local environment of the nanosheets. The LSPR can be efficiently tuned by changing the weight ratio between the molybdenum oxide precursor(s) and/or by solar light irradiation using a low‐energy UV lamp (36 W). For the pristine MoO_3−x nanosheets, the highest LSPR signal is obtained for nanosheets prepared using 80% MoO₂. On the contrary, after solar light irradiation, the nanosheets prepared using pure MoO₃ offer the highest LSPR response. The nanosheets also show an outstanding rate capability when used as binder‐free supercapacitor electrodes in an acidified Na₂SO₄ electrolyte. The electrodes exhibit discharge capacities of 110 and 75 C g⁻¹ at a scan rate of 20 and 1000 mV s⁻¹, respectively. The MoO_3−x nanosheets can likewise be used as a negative electrode material for lithium‐ion batteries. The efficient eco‐friendly synthesis and the ability to tune the photochemical and electrochemical properties of the nanosheets make this approach interesting to many energy‐related research fields.

Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In+/In3+) inorganic halide perovskite with the composition of Cs2In(I)In(III)Cl-6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I4/m with a = 17.2604(12) angstrom, c = 11.0113(16) angstrom if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications.

A solution-processed NiO-dye-ZnO photocathode was developed for applications in both solid-state p-type dye-sensitized solar cells (p-ssDSCs) and p-type dye-sensitized photoelectrosynthesis cells (p-DSPECs). In p-ssDSCs, the solar cell using ZnO as electron transport material showed a short circuit current, up to 680 mu A cm(-2), which is 60-fold larger than that previously reported device using TiO2 as electron transport material with similar architecture. In the p-DSPECs, a remarkable photocurrent of 100 mu A cm(-2) was achieved in a pH = 5.0 acetate buffer solution under a bias potential at 0.05 V vs RHE with platinum as the proton reduction catalyst. A Faradaic efficiency approaching 100% for the H-2 evolution reaction was obtained after photoelectrolysis for 9 h. Importantly, the solution-processed NiO-dye-ZnO photocathode exhibited excellent long-term stability in both p-ssDSCs and p-DSPECs. To the best of our knowledge, this is the first study where a solution-processable, nanoporous NiO-dye-ZnO photocathode is used for both p-ssDSCs and p-DSPECs having both excellent device performance and stability.

Two dimensional (2D) transition metal oxides and chalcogenides demonstrate a promising performance in sodium-ion batteries (SIBs) application. In this study, we investigated the use of a composite of freeze dried V₂O₅·nH₂O nanosheets and multi-walled carbon nanotube (MWCNT) as a negative electrode material for SIBs. Cyclic voltammetry (CV) results indicated that a reversible sodium-ion insertion/deinsertion into the composite electrode can be obtained in the potential window of 0.1–2.5 V vs. Na⁺/Na. The composite electrodes delivered sodium storage capacities of 140 and 45 mAh g⁻¹ under applied current densities of 20 and 100 mA g⁻¹, respectively. The pause test during constant current measurement showed a raise in the open circuit potential (OCP) of about 0.46 V, and a charge capacity loss of ∼10%. These values are comparable with those reported for hard carbon electrodes. For comparison, electrodes of freeze dried V₂O₅·nH₂O nanosheets were prepared and tested for SIBs application. The results showed that the MWCNT plays a significant role in the electrochemical performance of the composite material.

Covalently linking photosensitizers and catalysts in an inorganic-organic hybrid photocatalytic system is beneficial for efficient electron transfer between these components. However, general and straightforward methods to covalently attach molecular catalysts on the surface of inorganic semiconductors are rare. In this work, a classic rhenium bipyridine complex (Re catalyst) has been successfully covalently linked to the low toxicity CuInS2 quantum dots (QDs) by click reaction for photocatalytic CO2 reduction. Covalent bonding between the CuInS2 QDs and the Re catalyst in the QD-Re hybrid system is confirmed by UV-visible absorption spectroscopy, Fourier-transform infrared spectroscopy and energy-dispersive X-ray measurements. Time-correlated single photon counting and ultrafast time-resolved infrared spectroscopy provide evidence for rapid photo-induced electron transfer from the QDs to the Re catalyst. Upon photo-excitation of the QDs, the singly reduced Re catalyst is formed within 300 fs. Notably, the amount of reduced Re in the linked hybrid system is more than that in a sample where the QDs and the Re catalyst are simply mixed, suggesting that the covalent linkage between the CuInS2 QDs and the Re catalyst indeed facilitates electron transfer from the QDs to the Re catalyst. Such an ultrafast electron transfer in the covalently linked CuInS2 QD-Re hybrid system leads to enhanced photocatalytic activity for CO2 reduction, as compared to the conventional mixture of the QDs and the Re catalyst.