Boron modification promoting electrochemical surface reconstruction of NiFe-LDH for efficient and stable freshwater/seawater oxidation catalysis.

Transition metal-based electrocatalysts generally take place surface reconstruction in alkaline conditions, but little is known about how to improve the reconstruction to a highly active oxyhydroxide surface for an efficient and stable oxygen evolution reaction (OER). Herein, we develop a strategy to accelerate surface reconstruction by combining boron modification and cyclic voltammetry (CV) activation. Density functional theory calculations and in-situ/ex-situ characterizations indicate that both B-doping and electrochemical activation can reduce the energy barrier and contribute to the surface evolution into highly active oxyhydroxides. The formed oxyhydroxide active phase can tune the electronic configuration and boost the OER process. The reconstructed catalyst of CV-B-NiFe-LDH displays excellent alkaline OER performance in freshwater, simulated seawater, and natural seawater with low overpotentials at 100 mA cm-2 (η100: 219, 236, and 255 mV, respectively) and good durability. This catalyst also presents outstanding Cl- corrosion resistance in alkalized seawater electrolytes. The CV-B-NiFe-LDH||Pt/C electrolyzer reveals prominent performance for alkalized freshwater/seawater splitting. This study provides a guideline for developing advanced OER electrocatalysts by promoting surface reconstruction.

Unraveling the crucial contribution of additive chromate to efficient and stable alkaline seawater oxidation on Ni-based layered double hydroxides.

Seawater electrolysis to generate hydrogen offers a clean, green, and sustainable solution for new energy. However, the catalytic activity and durability of anodic catalysts are plagued by the corrosion and competitive oxidation reactions of chloride in high concentrations. In this study, we find that the additive CrO42- anions in the electrolyte can not only promote the formation and stabilization of the metal oxyhydroxide active phase but also greatly mitigate the adverse effect of Cl- on the anode. Linear sweep voltammetry, accelerated corrosion experiments, corrosion polarization curves, and charge transfer resistance results indicate that the addition of CrO42- distinctly improves oxygen evolution reaction (OER) kinetics and corrosion resistance in alkaline seawater electrolytes. Especially, the introduction of CrO42- even in the highly concentrated NaCl (2.5 M) electrolyte prolongs the durability of NiFe-LDH to almost five times the case without CrO42-. Density functional theory calculations also reveal that the adsorption of CrO42- can tune the electronic configuration of active sites of metal oxyhydroxides, enhance conductivity, and optimize the intermediate adsorption energies. This anionic additive strategy can give a better enlightenment for the development of efficient and stable oxygen evolution reactions for seawater electrolysis.

Enhanced Hydroxyl Adsorption in Ultrathin NiO/Cr2 O3 In-Plane Heterostructures for Efficient Alkaline Methanol Oxidation Reaction.

The exploration of advanced nickel-based electrocatalysts for alkaline methanol oxidation reaction (MOR) holds immense promise for value-added organic products coupled with hydrogen production, but still remain challenging. Herein, we construct ultrathin NiO/Cr2 O3 in-plane heterostructures to promote the alkaline MOR process. Experimental and theoretical studies reveal that NiO/Cr2 O3 in-plane heterostructures enable a favorable upshift of the d-band center and enhanced adsorption of hydroxyl species, leading to accelerated generation of active NiO(OH)ads species. Furthermore, ultrathin in-plane heterostructures endow the catalyst with good charge transfer ability and adsorption behavior of methanol molecules onto catalytic sites, contributing to the improvement of alkaline MOR kinetics. As a result, ultrathin NiO/Cr2 O3 in-plane heterostructures exhibit a remarkable MOR activity with a high current density of 221 mA cm-2 at 0.6 V vs Ag/AgCl, which is 7.1-fold larger than that of pure NiO nanosheets and comparable with other highly active catalysts reported so far. This work provides an effectual strategy to optimize the activity of nickel-based catalysts and highlights the dominate efficacy of ultrathin in-plane heterostructures in alkaline MOR.

Inhibiting Ion Migration Through Chemical Polymerization and Chemical Chelation Toward Stable Perovskite Solar Cells.

The migration of ions is known to be associated with various detrimental phenomena, including current density-voltage hysteresis, phase segregation, etc., which significantly limit the stability and performance of perovskite solar cells, impeding their progress toward commercial applications. To address these challenges, we propose incorporating a polymerizable organic small molecule monomer, N-carbamoyl-2-propan-2-ylpent-4-enamide (Apronal), into the perovskite film to form a crosslinked polymer (P-Apronal) through thermal crosslinking. The carbonyl and amino groups in Apronal effectively interact with shallow defects, such as uncoordinated Pb2+ and iodide vacancies, leading to the formation of high-quality films with enhanced crystallinity and reduced lattice strain. Furthermore, the introduction of P-Apronal improves energy level alignment, and facilitates charge carrier extraction and transport, resulting in a champion efficiency of 25.09 %. Importantly, P-Apronal can effectively suppress the migration of I- ions and improve the long-term stability of the devices. The present strategy sets forth a path to attain long-term stability and enhanced efficiency in perovskite solar cells.