Photoelectrocatalytic Hydrogen Generation: Current Advances in Materials and Operando Characterization.

Photoelectrochemical (PEC) hydrogen generation is a promising technology for green hydrogen production yet faces difficulties in achieving stability and efficiency. The scientific community is pushing toward the development of new electrode materials and a better understanding of the underlying reactions and degradation mechanisms. Advances in photocatalytic materials are being pursued through the development of heterojunctions, tailored crystal nanostructures, doping, and modification of solid-solid and solid-electrolyte interfaces. Operando and in situ techniques are utilized to deconvolute the charge transfer mechanisms and degradation pathways. In this review, both materials development and Operando characterization are covered for advancing PEC technologies. The recent advances made in the PEC materials are first reviewed including the applied improvement strategies for transition metal oxides, nitrites, chalcogenides, Si, and group III-V semiconductor materials. The efficiency, stability, scalability, and electrical conductivity of the aforementioned materials along with the improvement strategies are compared. Next, the Operando characterization methods and cite selected studies applied for PEC electrodes are described. Operando studies are very successful in elucidating the reaction mechanisms, degradation pathways, and charge transfer phenomena in PEC electrodes. Finally, the standing challenges and the potential opportunities are discussed by providing recommendations for designing more efficient and electrochemically stable PEC electrodes.

Tailoring p-Type Behavior in ZnO Quantum Dots through Enhanced Sol-Gel Synthesis: Mechanistic Insights into Zinc Vacancies.

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol-gel process that effectively eliminates the residual intermediate reaction molecules, which would otherwise weaken the excitonic emission. This process supports the creation of ZnO with p-type properties or compensation of inherited n-type defects, primarily due to zinc vacancies under oxygen-rich conditions. The in-depth analysis of carrier recombination in the midgap across several time scales reveals microsecond carrier lifetimes at room temperature which are expected to occur via zinc vacancy defects, supporting the promoted p-type character of the synthesized ZnO QDs.

Boron Carbide as an Electrode Material: Tailoring Particle Morphology to Control Capacitive Behaviour.

In this study, boron carbide powders consisting mainly of nano/micro fibers or polyhedral-equiaxed particles were synthesized via the sol-gel technique, and the influence of particle morphology on electrochemical performance of boron carbide electrodes was investigated. Thermal decomposition duration of the precursors played a determinant role in the final morphology of the synthesized boron carbide powders. The morphology of boron carbide powders successfully tuned from polyhedral-equiaxed (with ~3 µm average particle size) to nano/micro fibers by adjusting the thermal decomposition duration of precursors. The length and thickness of fibers were in the range of 30 to 200 µm and sub-micron to 5 µm, respectively. The electrochemical performance analysis of boron carbide powders has shown that the particle morphology has a considerable impact on the boron carbide electrodes electrochemical performance. It was found that the synergetic effects of polyhedral-equiaxed and nano/micro fiber morphologies exhibited the best electrochemical performance in supercapacitor devices, resulting in the power and energy density of 34.9 W/kg and 0.016 Wh/kg, respectively.

All-in-One Electric Double Layer Supercapacitors Based on CH3NH3PbI3 Perovskite Electrodes.

Supercapacitors (SCs) are widely used energy storage devices in various applications that require instantaneous power supply and fast response times; however, the challenge for achieving high performance demands the continuous development and tailoring of electrode materials. Organic-inorganic halide perovskites (OIHPs) have recently received significant attention in electrochemical energy storage and conversion applications due to their unique properties including high charge carrier mobility, high mixed (electronic-ionic) conductivity, and presence of large oxygen vacancies. This study presents the fabrication and use of OIHPs based on methyl-ammonium lead iodide (CH3NH3PbI3) and its Co2+- and Bi3+-substituted derivatives (CH3NH3Pb1-x Co x I3 and CH3NH3Pb1-x Bi x I3, respectively, where x = 0.1) as electrodes for SCs. SC devices were constructed symmetrically by sandwiching the synthesized electrode materials in a quasi-solid-state electrolyte between two TiO2-coated FTO glasses. We discussed the optimization parameters (i.e., A-site doping, B-site doping, and controlling the stoichiometry of the anion and cation) to improve the electrochemical performance of the fabricated SCs. Furthermore, the effects of substitution ions (Co2+ and Bi3+) on the charge-discharge performance, energy and power density, defects, crystallinity, and microstructure were demonstrated. Electrochemical performances of the electrodes were analyzed by using CV, EIS, and GCPL techniques. The highest power density of 934.6 W/kg was obtained for Bi-substituted perovskite electrodes. Fabricated SC devices show good cyclability with 97.2, 96.3, and 86.6% retention of the initial capacitances after 50 cycles for pure, Co2+-substituted, and Bi3+-substituted perovskite electrodes, respectively.

ZnO and reduced graphene oxide electrodes for all-in-one supercapacitor devices.

Reduced graphene oxide/zinc oxide (rGO/ZnO) hybrid nanocomposites were prepared from synthesized GO and high energy ball milled (HEBM) ZnO for supercapacitor electrodes. Evolution of intrinsic point defects and defect-induced morphological, structural and size-dependent properties of rGO/ZnO hybrid nanocomposites were investigated using electron paramagnetic resonance (EPR) spectroscopy. CV, PEIS and GCPL techniques were employed to investigate the electrochemical behavior of the electrode materials and the effects of defects on the electrochemical performance of the electrodes by using the standard two-electrode cell in a 6 M KOH electrolyte. Analyses of the obtained CV and impedance profiles have shown the pseudocapacitive and EDLC-type contributions in the supercapacitors. Cycling stabilities were evaluated using galvanostatic charge-discharge curves at current densities between 0.10 and 2.40 A g-1. The capacitance retention of all electrodes was found to be 100% after 30 cycles at 0.30 A g-1. The electrochemical analyses revealed that the incorporation of ZnO that is rich in core defects improved the charge transfer performance and ion diffusion of the rGO electrode.