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Water electrolysis is a promising method for efficiently producing hydrogen and oxygen, crucial for renewable energy conversion and fuel cell technologies. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are two key electrocatalytic reactions occurring during water splitting, necessitating the development of active, stable, and low-cost electrocatalysts. Transition metal (TM)-based electrocatalysts, spanning noble metals and TM oxides, phosphides, nitrides, carbides, borides, chalcogenides, and dichalcogenides, have garnered significant attention due to their outstanding characteristics, including high electronic conductivity, tunable valence electron configuration, high stability, and cost-effectiveness. This timely review discusses developments in TM-based electrocatalysts for the HER and OER in alkaline media in the last 10 years, revealing that the exposure of more accessible surface-active sites, specific electronic effects, and string effects are essential for the development of efficient electrocatalysts towards electrochemical water splitting application. This comprehensive review serves as a guide for designing and constructing state-of-the-art, high-performance bifunctional electrocatalysts based on TMs, particularly for applications in water splitting. [ABSTRACT FROM AUTHOR]

While direct solar‐driven water splitting has been investigated as an important technology for low‐cost hydrogen production, the systems demonstrated so far either required expensive materials or presented low solar‐to‐hydrogen (STH) conversion efficiencies, both of which increase the levelized cost of hydrogen (LCOH). Here, a low‐cost material system is demonstrated, consisting of perovskite/Si tandem semiconductors and Ni‐based earth‐abundant catalysts for direct solar hydrogen generation. NiMo‐based hydrogen evolution reaction catalyst is reported, which has innovative "flower‐stem" morphology with enhanced reaction sites and presents very low reaction overpotential of 6 mV at 10 mA cm−2. A perovskite solar cell with an unprecedented high open circuit voltage (Voc) of 1.271 V is developed, which is enabled by an optimized perovskite composition and an improved surface passivation. When the NiMo hydrogen evolution catalyst is wire‐connected with an optimally designed NiFe‐based oxygen evolution catalyst and a high‐performance perovskite‐Si tandem cell, the resulting integrated water splitting cell achieves a record 20% STH efficiency. Detailed analysis of the integrated system reveals that STH efficiencies of 25% can be achieved with realistic improvements in the perovskite cell and an LCOH below ≈$3 kg−1 is feasible. [ABSTRACT FROM AUTHOR]

Critical catalysis studies often lack elucidation of the mechanistic role of defect equilibria in solid solubility and charge compensation. This approach is applied to interpret the physicochemical properties and catalytic performance of a free‐standing 2D–3D CeO2−x scaffold, which is comprised of holey 2D nanosheets, and its heterojunctions with MoO3−x and RuO2. The band gap alignment and structural defects are engineered using density functional theory (DFT) simulations and atomic characterization. Further, the heterojunctions are used in hydrogen evolution reaction (HER) and catalytic ozonation applications, and the impacts of the metal oxide heteroatoms are analyzed. A key outcome is that the principal regulator of the ozonation performance is not oxygen vacancies but the concentration of Ce3+ and Ce vacancies. Cation vacancy defects are measured to be as high as 8.1 at% for Ru‐CeO2−x. The homogeneous distribution of chemisorbed, Mo‐oxide, heterojunction nanoparticles on the CeO2−x holey nanosheets facilitates intervalence charge transfer, resulting in the dominant effect and resultant ≈50% decrease in overpotential for HER. The heterojunctions are tested for aqueous‐catalytic ozonation of salicylic acid, revealing excellent catalytic performance from Mo doping despite the adverse impact of Ce vacancies. The present study highlights the use of defect engineering to leverage experimental and DFT results for band alignment. [ABSTRACT FROM AUTHOR]

Photocatalytic hydrogen (H2) production by water splitting provides an alternative to fossil fuels using clean and renewable energy, which gives important requirements about the efficiency of photocatalysts, co-catalysts, and sacrificial agents. To achieve higher H2 production efficiencies from water splitting, the study uses different metals such as yttrium (Y), praseodymium (Pr), magnesium (Mg), Indium (In), calcium (Ca), europium (Eu), and terbium (Tb) doped lanthanum iron oxide (LaFeO3) perovskites. They were synthesized using a co-precipitate method in a citric acid solution, which was loaded with the rhodium chromium oxide (RhCrOx) cocatalysts by an impregnation method along with a detailed investigation of photocatalytic hydrogen evolution performance. Photoluminescence (PL) and UV–Vis diffuse reflectance spectra (DRS) measured the rate of electron–hole recombination for RhCrOx/Pr-LaFeO3 photocatalysts, and X-ray powder diffraction (XRD), scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), and X-ray photoelectron spectra (XPS) analyzed their characteristics. The experimental results obtained show that the samples with 0.5 wt.% RhCrOx loading and 0.1 M Pr-doped LaFeO3 calcined at a temperature of 700 °C (0.1Pr-LaFeO3-700) exhibited the highest photocatalytic H2 evolution rate of 127 µmol h−1 g−1, which is 34% higher photocatalytic H2 evolution performance than undoped LaFeO3 photocatalysts (94.8 μmol h−1 g−1). A measure of 20% of triethanolamine (TEOA) enabled a high hole capture capability and promoted 0.1-Pr-LaFeO3-700 to get the highest H2 evolution rate. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hierarchically structured Fe 2 Ni 3 nanoalloy and N-incorporated flower-like carbon matrix. • Synergism between Fe 2 Ni 3 and NFCM essential to achieve first-rate multifunctional performance. • 1.50 V at 10 mA cm−2 and a maintenance up to 76 h for overall water-splitting. • Power density of ∼ 122 mW cm−2 and robust cycling stability for assembled Zn-air battery. • Active species/sites identified through detailed characterizations/comparison studies. A multifunctional electrocatalyst for water splitting and zinc-air battery involves totally-three reactions, namely, oxygen reduction, oxygen evolution, and hydrogen evolution, and is very demanding and challenging. The current study provided an interesting example to achieve such a goal by establishing hierarchical architecture of Fe 2 Ni 3 nanoalloys/N‑incorporated flower-like carbon matrix (Fe 2 Ni 3 -NFCM). The resulting material is free of noble metals and can simultaneously promote the three reactions with excellent activity and robust durability. Significantly, the outstanding parameters ƞ 10 = 280 mV (oxygen evolution), ƞ 10 = 144 mV (hydrogen evolution), and E 1/2 = 0.84 V vs RHE (oxygen reduction) can be accomplished over Fe 2 Ni 3 -NFCM. Moreover, a voltage as low as 1.50 V (10 mA cm−2) and a 76-h durability for water-splitting has been achieved. The assembled Zn-air battery employing the current material as the electrodes can provide the power density being ∼ 122 mW cm−2 plus robust cyclic durability. The multifunctional performance reaches the top level among the various counterparts, the structure-performance correlation has been elucidated and the active species/sites identified through the advanced characterizations and detailed comparison investigations. [ABSTRACT FROM AUTHOR]