Nickel-iron oxides/hydroxides are among the most active electrocatalysts for the oxygen evolution reaction. In an effort to gain insight into the role of Fe in these catalysts, we have performed operando Mössbauer spectroscopic studies of a 3:1 Ni:Fe layered hydroxide and a hydrous Fe oxide electrocatalyst. The catalysts were prepared by a hydrothermal precipitation method that enabled catalyst growth directly on carbon paper electrodes. Fe(4+) species were detected in the NiFe hydroxide catalyst during steady-state water oxidation, accounting for up to 21% of the total Fe. In contrast, no Fe(4+) was detected in the Fe oxide catalyst. The observed Fe(4+) species are not kinetically competent to serve as the active site in water oxidation; however, their presence has important implications for the role of Fe in NiFe oxide electrocatalysts.

With the intense interest in inorganic cesium lead halide perovskites and their nanostructures for optoelectronic applications, high-quality crystalline nanomaterials with controllable morphologies and growth directions are desirable. Here, we report a vapor-phase epitaxial growth of horizontal single-crystal CsPbX (X = Cl, Br, I) nanowires (NWs) and microwires (MWs) with controlled crystallographic orientations on the (001) plane of phlogopite and muscovite mica. Moreover, single NWs, Y-shaped branches, interconnected NW or MW networks with 6-fold symmetry, and, eventually, highly dense epitaxial network of CsPbBr with nearly continuous coverage were controllably obtained by varying the growth time. Detailed structural study revealed that the CsPbBr wires grow along the [001] directions and have the (100) facets exposed. The incommensurate heteroepitaxial lattice match between the CsPbBr and mica crystal structures and the growth mechanism of these horizontal wires due to asymmetric lattice mismatch were proposed. Furthermore, the photoluminescence waveguiding and good performance from the photodetector device fabricated with these CsPbBr networks demonstrated that these well-connected CsPbBr NWs could serve as straightforward platforms for fundamental studies and optoelectronic applications.

rechargeable metal-air batteries. [1,2] This reaction demands efficient electrocatalysts that can accelerate the reaction rate, lower the overpotential, and remain stable over time. Currently, noble-metal-based compounds such as IrO 2 and RuO 2 provide good OER performance under alkaline conditions, but their large-scale application is restricted by their scarcity and high cost. [3] Accordingly, much research effort has been devoted to the development of high-performance earth-abundant OER electrocatalysts based on transition-metal elements, usually in the form of metal oxides or metal (oxy)hydroxides, that are inexpensive and stable upon prolonged exposure under oxidizing conditions. [4][5][6][7] In addition to the synergistic effects of transition metals and electrical conductivity, the intrinsic activities of these transition metal oxide or (oxy)hydroxide OER catalysts are closely connected to the number of 3d electrons of the metals; the surface transition-metal ions exhibited e g orbitals which could bond with surfaceanion adsorbates and then influence the binding of oxygenic intermediates. [8,9] The binding strength of these intermediates is thought to dictate catalytic activity. [10] Identifying the relationship between OER activity and the catalyst electronic structure can provide a simple rationale for gaining mechanistic insights and finding new design strategies for the earth-abundant OER catalysts.Among various transition metal-based OER catalysts, metal layered double hydroxides (LDHs) and oxyhydroxides have attracted much attention because of their abundance in the earth's crust and their considerable catalytic activity. [5,6,[11][12][13][14][15][16][17][18][19][20][21] NiFe LDH and more generally NiFe (oxy)hydroxides have emerged as the most active OER catalyst compared to other bimetallic earth-abundant LDHs under basic conditions, [6,15,17,22] and several studies have been directed at understanding the role of Fe in increasing the OER intrinsic activity of NiFe-containing (oxy) hydroxide materials. [23] Boettcher and co-workers demonstrated that Fe incorporation into NiOOH lattice enhances the electronic conductivity in the film and Fe exerts a partial-chargetransfer activation effect on Ni centers throughout the catalyst film, but the enhanced catalytic efficiency cannot be completely explained. [17] To better understand the role of Fe, they further studied other incorporated metal cations (Mn, Ti, Ce, Fe, and La) in NiO x H y , finding that only Fe permanently increases the OER The development of efficient and robust earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is an ongoing challenge. Here, a novel and stable trimetallic NiFeCr layered double hydroxide (LDH) electrocatalyst for improving OER kinetics is rationally designed and synthesized. Electrochemical testing of a series of trimetallic NiFeCr LDH materials at similar catalyst loading and electrochemical surface area shows that the molar ratio Ni:Fe:Cr = 6:2:1 exhibits the best intrinsic OER catalytic activity ...

Electrochemical oxidation of biomass-derived platform molecules can enable the production of value-added oxygenated commodity chemicals under mild conditions in a distributed fashion using renewable electricity; however, very few efficient, robust, and inexpensive electrocatalysts are available for such electrochemical oxidation. Here we demonstrate that earth-abundant NiFe layered double hydroxide (LDH) nanosheets grown on carbon fiber paper can efficiently catalyze the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at the anode of an electrochemical cell. A near-quantitative yield of FDCA and 99.4% Faradaic efficiency of HMF conversion under ambient conditions can be achieved in the electrochemical process. HMF has a higher rate of oxidation than water and can act as an alternative anodic reaction for alkaline H 2 evolution in water-splitting cells. As the first report on using bimetallic metal hydroxide/oxide catalysts for electrochemical oxidation of HMF, this work opens up opportunities in electrochemical devices to simultaneously produce building-block chemicals from biomassderived molecules and clean H 2 fuels under ambient conditions with earth-abundant materials.

Finding efficient electrocatalysts for oxygen evolution reaction (OER) that can be effectively integrated with semiconductors is significantly challenging for solar‐driven photo‐electrochemical (PEC) water splitting. Herein, amorphous cobalt–iron hydroxide (CoFeH) nanosheets are synthesized by facile electrodeposition as an efficient catalyst for both electrochemical and PEC water oxidation. As a result of the high electrochemically active surface area and the amorphous nature, the optimized amorphous CoFeH nanosheets exhibit superior OER catalytic activity in alkaline environment with a small overpotential (280 mV) to achieve significant oxygen evolution (j = 10 mA cm−2) and a low Tafel slope (28 mV dec−1). Furthermore, CoFeH nanosheets are simply integrated with BiVO4 semiconductor to construct CoFeH/BiVO4 photoanodes that exhibit a significantly enhanced photocurrent density of 2.48 mA cm−2 (at 1.23 V vs reversible hydrogen electrode (RHE)) and a much lower onset potential of 0.23 V (vs RHE) for PEC‐OER. Careful electrochemical and optical studies reveal that the improved OER kinetics and high‐quality interface at the CoFeH/BiVO4 junction, as well as the excellent optical transparency of CoFeH nanosheets, contribute to the high PEC performance. This study establishes amorphous CoFeH nanosheets as a highly competitive candidate for electrochemical and PEC water oxidation and provides general guidelines for designing efficient PEC systems.