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Efficient and durable electrocatalysts toward alkaline hydrogen evolution reaction (HER) are of great significance for the widespread application of anion‐exchange membrane water electrolyzer (AEMWE). Numerous single‐phase catalysts, such as Ru2P, have been explored as efficient HER catalysts; however, many have failed to overcome the inherent sluggish kinetics of the two separate steps involved in the alkaline HER: water dissociation and hydrogen production. In this study, density functional theory calculations are conducted to identify promising combinations of Ir2P and Ru2P materials that promote fast cascade water dissociation and H2 production via kinetically favorable hydrogen spillover from the Ru2P surface to the adjacent Ir2P. An unprecedented construction of Ir2P cluster‐decorated Ru2P hollow nanotubes (c‐RP/IP HNTs), which feature a cooperative heterostructural synergy are developed. This configuration shows greater performance than commercial Pt/C, achieving an overpotential of 23.2 mV at 10 mA cm−2 and maintaining long‐term stability for 55 h in half‐cell tests. Furthermore, the practical AEMWE test, incorporating c‐RP/IP HNTs, demonstrated a remarkable single‐cell performance of 12.23 A cm−2 at 2.0 V and operated stably under 1.0 A cm−2 for over 250 h. This surpasses that of the state‐of‐the‐art proton‐exchange membrane WE. [ABSTRACT FROM AUTHOR]

While anion exchange membrane (AEM) water electrolysis has many advantages, its commercialization is impeded by the low alkaline stability of most AEM, due to the fragility of quaternary ammonium groups. Ion solvating membranes (ISM) can be an alternative, but so far require high alkaline concentrations. Here, it is shown that sulfonation of polybenzimidazole results in ISM which swell strongly in 1 m KOH. Crosslinking with dibromoxylene controls the swelling, and after activation conductivities of >100 mS cm−1 can be reached in 1 m KOH. Stability in 1 m KOH at 80 °C is excellent: Conductivity remains unchanged and tensile strength and Young's modulus remains high over the test period of a half year. In an electrolyzer operating with 1 m KOH feed solution at 80 °C, a stable performance is achieved for over 500 h test without failure, suggesting that the high alkaline stability observed in ex situ tests is also achieved in the electrolyzer. [ABSTRACT FROM AUTHOR]

Bifunctional catalysts based on noble metals have achieved practical‐level performances in round‐trip energy conversion systems. However, the required amount of noble metals should be substantially reduced via a new catalyst design that can pursue the synergy of the constituent materials' intrinsic properties and architectural maneuver over reactant/product transport. In this study, cross‐stacked Ir and Pt nanowires resolved the bottlenecks of two reactions essential for the hydrogen‐based energy system: i) hydrogen spillover phenomenon between Pt and Ir nanowires to expedite the hydrogen oxidation reaction and ii) spacing Ir nanowires sufficiently to enhance the mass transport of the oxygen evolution reaction. Simultaneously accommodating the different strategies within the single catalyst layer, a new horizon to design a bifunctional electrode is proposed with the high performance of polymer electrolyte membrane unitized regenerative fuel cells: 47% of round‐trip efficiency at 0.5 A cm−2 with total noble metal loading < 0.3 mg cm−2. [ABSTRACT FROM AUTHOR]

The ability to capture, store, and use CO2 is important for remediating greenhouse‐gas emissions and combatting global warming. Herein, Au nanoparticles (Au‐NPs) are synthesized for effective electrochemical CO2 reduction and syngas production, using polyethylenimine (PEI) as a ligand molecule. The PEI‐assisted synthesis provides uniformly sized 3‐nm Au NPs, whereas larger irregularly shaped NPs are formed in the absence of PEI in the synthesis solution. The Au‐NPs synthesized with PEI (PEI−Au/C, average PEI Mw=2000) exhibit improved CO2 reduction activities compared to Au‐NPs formed in the absence of PEI (bare Au NPs/C). PEI−Au/C displays a 34 % higher activity toward CO2 reduction than bare Au NPs/C; for example, PEI−Au/C exhibits a CO partial current density (jCO) of 28.6 mA cm−2 at −1.13 VRHE, while the value for bare Au NPs/C is 21.7 mA cm−2; the enhanced jCO is mainly due to the larger surface area of PEI−Au/C. Furthermore, the PEI−Au/C electrode exhibits stable performance over 64 h, with an hourly current degradation rate of 0.25 %. The developed PEI−Au/C is employed in a CO2‐reduction device coupled with an IrO2 water‐oxidation catalyst and a proton‐conducting perfluorinated membrane to form a PEI−Au/C|Nafion|IrO2 membrane‐electrode assembly. The device using PEI−Au/C as the CO2‐reduction catalyst exhibits a jCO of 4.47 mA/cm2 at 2.0 Vcell. Importantly, the resulted PEI−Au/C is appropriate for efficient syngas production with a CO ratio of around 30–50 %. [ABSTRACT FROM AUTHOR]

Abstract: Demands for sustainable production of hydrogen are rapidly increasing because of environmental considerations for fossil fuel consumption and development of fuel cell technologies. Thus, the development of high‐performance and economical catalysts has been extensively investigated. In this study, a nanoporous Mo carbide electrode is prepared using a top‐down electrochemical process and it is applied as an electrocatalyst for the hydrogen evolution reaction (HER). Anodic oxidation of Mo foil followed by heat treatment in a carbon monoxide (CO) atmosphere forms a nanostructured Mo carbide with excellent interconnections, and these structural characteristics lead to high activity and durability when applied to the HER. Additionally, characteristic behavior of Mo is observed; metallic Mo nanosheets form during electrochemical anodization by exfoliation along the (110) planes. These nanosheets are viable for chemical modification, indicating their feasibility in various applications. Moreover, the role of carbon shells is investigated on the surface of the electrocatalysts, whereby it is suggested that carbon shells serve as a mechanical barrier against the oxidative degradation of catalysts that accompanies unavoidable volume expansion. [ABSTRACT FROM AUTHOR]

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO2-coated p-Si photocathode for the photo-reduction of protons to H2. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO2 layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO2|hydrogenase photocathode displays visible-light driven production of H2 at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme-materials interface. [ABSTRACT FROM AUTHOR]

An efficient, stable and scalable hybrid photoelectrode for visible-light-driven H2 generation in an aqueous pH 9.2 electrolyte solution is reported. The photocathode consists of a p-type Si substrate layered with a Ti and Ni-containing composite film, which acts as both a protection and electrocatalyst layer on the Si substrate. The film is prepared by the simple drop casting of the molecular single-source precursor, [{Ti2(OEt)9(NiCl)}2] (TiNipre), onto the p-Si surface at room temperature, followed by cathodic in situ activation to form the catalytically active TiNi film (TiNicat). The p-Si ∣ TiNicat photocathode exhibits prolonged hydrogen generation with a stable photocurrent of approximately -5 mA cm-2 at 0 V vs. RHE in an aqueous pH 9.2 borate solution for several hours, and serves as a benchmark non-noble photocathode for solar H2 evolution that operates efficiently under neutral-alkaline conditions. [ABSTRACT FROM AUTHOR]