Amine???Rich Hydrogels Enhance Solar Water Oxidation via Boosting Proton???Coupled Electron Transfer

Photoelectrochemical (PEC) water oxidation is a highly challenging task that acts as a bottleneck for efficient solar hydrogen production. It is because each cycle of water oxidation is composed of four proton-coupled electron transfer (PCET) processes and conventional photoanodes and cocatalysts have limited roles in enhancing the charge separation and storage rather than in enhancing catalytic activity. In this study, a simple and generally applicable strategy to improve the PEC performance of water oxidation photoanodes through their modification with polyethyleneimine (PEI) hydrogel is reported. The rich amine groups of PEI not only allow the facile and stable modification of photoanodes by crosslinking but also contribute to improving the kinetics of PEC water oxidation by boosting the PCET. Consequently, the PEC performance of various photoanodes, such as BiVO4, Fe2O3, and TiO2, is significantly enhanced in terms of photocurrent densities and onset potentials even in the presence of notable cocatalyst, cobalt phosphate. The present study provides new insights into and strategies for the design of efficient photoelectrodes and PEC devices

Superaerophobic hydrogels for enhanced electrochemical and photoelectrochemical hydrogen production

The efficient removal of gas bubbles in (photo)electrochemical gas evolution reactions is an important but underexplored issue. Conventionally, researchers have attempted to impart bubble-repellent properties (so-called superaerophobicity) to electrodes by controlling their microstructures. However, conventional approaches have limitations, as they are material specific, difficult to scale up, possibly detrimental to the electrodes' catalytic activity and stability, and incompatible with photoelectrochemical applications. To address these issues, we report a simple strategy for the realization of superaerophobic (photo)electrodes via the deposition of hydrogels on a desired electrode surface. For a proof-of-concept demonstration, we deposited a transparent hydrogel assembled from M13 virus onto (photo)electrodes for a hydrogen evolution reaction. The hydrogel overlayer facilitated the elimination of hydrogen bubbles and substantially improved the (photo)electrodes' performances by maintaining high catalytic activity and minimizing the concentration overpotential. This study can contribute to the practical application of various types of (photo)electrochemical gas evolution reactions

Modular Flow Reactors for Valorization of Kraft Lignin and Low???Voltage Hydrogen Production

Recent studies have found that green hydrogen production and biomass utilization technologies can be combined to efficiently produce both hydrogen and value-added chemicals using biomass as an electron and proton source. However, the majority of them have been limited to proof-of-concept demonstrations based on batch systems. Here the authors report the design of modular flow systems for the continuous depolymerization and valorization of lignin and low-voltage hydrogen production. A redox-active phosphomolybdic acid is used as a catalyst to depolymerize lignin with the production of aromatic compounds and extraction of electrons for hydrogen production. Individual processes for lignin depolymerization, byproduct separation, and hydrogen production with catalyst reactivation are modularized and integrated to perform the entire process in the serial flow. Consequently, this work enabled a one-flow process from biomass conversion to hydrogen gas generation under a cyclic loop. In addition, the unique advantages of the fluidic system (i.e., effective mass and heat transfer) substantially improved the yield and efficiency, leading to hydrogen production at a higher current density (20.5 mA cm???2) at a lower voltage (1.5 V) without oxygen evolution. This sustainable eco-chemical platform envisages scalable co-production of valuable chemicals and green hydrogen for industrial purposes in an energy-saving and safe manner

Bias-free solar hydrogen production at 19.8???mA???cm???2 using perovskite photocathode and lignocellulosic biomass

Solar hydrogen production is one of the ultimate technologies needed to realize a carbon-neutral, sustainable society. However, an energy-intensive water oxidation half-reaction together with the poor performance of conventional inorganic photocatalysts have been big hurdles for practical solar hydrogen production. Here we present a photoelectrochemical cell with a record high photocurrent density of 19.8???mA???cm???2 for hydrogen production by utilizing a high-performance organic???inorganic halide perovskite as a panchromatic absorber and lignocellulosic biomass as an alternative source of electrons working at lower potentials. In addition, value-added chemicals such as vanillin and acetovanillone are produced via the selective depolymerization of lignin in lignocellulosic biomass while cellulose remains close to intact for further utilization. This study paves the way to improve solar hydrogen productivity and simultaneously realize the effective use of lignocellulosic biomass

Water oxidation for electrochemical and photoelectrochemical hydrogen production

Water oxidation is simple but considered one of the most important electrochemical reactions; it can provide a clean and cheap source of electrons for various (photo)electrochemical reactions [1]. For example, high-purity hydrogen can be produced in an environmentally friendly manner via electrolysis of water in conjunction with the use of renewable energy sources. However, the oxidation of water is a challenging task and often acts as a rate-determining step for the overall reactions, necessitating the development of efficient water oxidation catalyst (WOC). In this presentation, recent efforts on the development of homogeneous and heterogeneous WOCs will be reviewed with a specific focus on cheap and stable WOCs consisting of earth-abundant transition metals. Then, I will present our progress over the past few years in the development of efficient heterogeneous WOCs through defect engineering of transition metal oxides [2,3]. [1] S. Bae et al. ???Tailored assembly of molecular water oxidation catalysts on photoelectrodes for artificial photosynthesis??? Eur. J. Inorg. Chen. 2019, 2019, 2040-2057. [2] Y. Han et al. ???Cobalt polyoxometalate-derived CoWO4 oxygen-evolving catalysts for efficient electrochemical and photoelectrochemical water oxidation??? J. Catal. 2018, 367, 212-220. [3] C. Kim, et al., In preparation of manuscript