Controllable atoms implantation for inducing high valency nickel towards optimizing electronic structure for enhanced overall water splitting.

Adjusting the electronic structure and intrinsic activity of the active site of the catalyst based on atomic implantation is the crucial to realizing efficient electrochemical water splitting in alkaline media. Thus, we introduce vanadium (V) atoms with abundant vacant d orbitals as dopants into nickel selenides (NiSe), which has abundant variable valence states, and successfully synthesise three-dimensional bi-functional catalysts self-supported on Ni foam (NF). The electron structure characterisation reveals that, compared with the pure NiSe phase, the oxidation states of Ni cations and electron concentration at the Se site in V-NiSe increase due to the V doping. These changes are accompanied by changes in the electronic structure and active sites in V-NiSe. The as-generated V-NiSe nanorods exhibit an optimised electronic structure, high number of active sites and highly rough nanorod array structure with large electrochemically active surface area and in situ growth characteristics of conductive NF. Thus, the as-generated V-NiSe nanorods catalysts exhibit excellent bi-functional catalytic activity, with 50 mA⋅cm-2 at an overpotential of 270.2 and 251.2 mV for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER), respectively, in KOH (1 M). Water electrolysis using V-NiSe as both the anode and cathode requires a cell voltage of 1.76 V to drive 50 mA⋅cm-2, continuously operating for 80 h. This study provides a systematic understanding of the design of transition-metal catalysts using heteroatomic doping to control their electronic structure and catalytic activity.

Interface engineering on super-hydrophilic amorphous/crystalline NiFe-based hydroxide/selenide heterostructure nanoflowers for accelerated industrial overall water splitting at high current density.

Designing heterojunction catalysts with energy effects at the interface, particularly combining the surface structure advantages of super-hydrophilic interfaces with the high activity advantages of bimetal synergistic optimisation, is the key to developing economical and efficient industrial electrocatalytic water-splitting catalysts. In this study, a coupled nanoflower-like NiFe(OH)x/(Ni, Fe)Se heterostructure catalyst supported on Ni foam (NF) (NFSe@NFOH/NF) was designed and successfully prepared using hydrothermal and electrodeposition strategies. Owing to the electron interaction at the heterogeneous amorphous (NFOH)/crystalline (NFSe) interface and the bimetallic synergistic effect of Ni and Fe, the prepared NFSe@NFOH/NF exhibited excellent and stable oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalytic properties, with low overpotentials of 214/276 mV at 100 mA⋅cm-2 and 262/340 mV at 500 mA⋅cm-2. The assembled water electrolyser comprising NFSe@NFOH/NF || NFSe@NFOH/NF needed only small voltages of 1.73 and 1.85 V to yield current densities of 100 and 500 mA⋅cm-2, respectively. This study offers an innovative design idea for the rational adoption of interface engineering and amorphous-crystalline engineering techniques to construct catalysts with excellent catalytic activity and stability for electrocatalytic overall water splitting (EOWS) at a high current density, which further facilitates the advancement of sustainable energy technology in the future.

Construction of micro-nano hierarchical wing-like iron/molybdenum oxide heterojunction with synergistic effect for accelerated overall water splitting.

Designing heterojunction catalysts with high-energy interfacial effects, especially combining the geometrical advantages of hierarchical micro-nano structures with the advantages of bi- or multi-metal syergistically optimised electronic coordination environments, is crucial for achieving efficient and stable water splitting. In this study, a simple one-step hydrothermal method was used to construct a hierarchical wing-like iron/molybdenum oxide heterojunction with a porous structure on nickel foam (FMO/NF). The synergistic effect of Fe, Mo, and the heterostructures can enrich structural defects, overcome the disadvantages of the individual components, and improve material performance by optimising the structural configurations and electronic properties and exploiting the electronic interactions that occur between interfaces composed of different phases. In addition, owing to the high porosity of the hierarchical micro-nano structure and abundant active sites, the wing-like FMO/NF was utilised as an efficient bifunctional catalyst for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), presenting low overpotentials of 278.06 and 263.72 mV, respectively, at a current density of 100 mA·cm-2 in 1 mol/L KOH. Furthermore, assembling FMO/NF as both the anode and cathode (FMO/NF || FMO/NF) required a cell voltage of 1.87 V to drive 100 mA·cm-2 in 1 mol/L KOH, and it proceeded continuously for 110 h with negligible cell voltage decay. This work provides a rational synthetic route for the preparation of innovative double transition metal-based micro-nano hierarchical heterostructured electrocatalysts with a synergistic effect and further advances the development of energy-conversion technology.

Synergistic effect of oxidation etching and phase transformation triggered by controllable ion-bath microenvironments toward constructing ultra-thin porous nanosheets for accelerated industrial water splitting at high current density.

Precisely tailoring the structure of inorganic materials at the micron and nanometer scales, especially in collaboration with component customization to design efficient, stable and low-cost transition-metal-based catalysts for industrial electrocatalytic water splitting (EWS) is a key renewable energy technology, but still facing a daunting challenge. Here, the controllable escape of Ni atom is adopted to disturb the hydrothermal ion-bath environment, thereby resulting in the coexistence of high valence Ni and Fe ions. Combined with a one-step hydrothermal coordination strategy, the timeline-adjusted ion-bath microenvironment can effectively trigger the phase transformation of carbonate hydroxide hydrate nanosheets (NFCH) to nickel ferrite intercalated NFCH ultra-thin porous nanosheets (NF-CH-O). Thanks to the high-energy phase boundary synergistic effect and the rapid mass transfer advantages of ultra-thin porous nanostructures, the as-prepared NF-CH-O nanosheets exhibit remarkable oxygen and hydrogen evolution reaction (OER/HER) catalytic activity and stability, with low overpotentials of 207/191 mV at 50 mA cm-2, respectively, as well as the activity retention for 100 h. The alkaline water electrolyzer set up with NF-CH-O as both anodic and cathodic electrodes only requires a cell potential of 1.688 V to reach 50 mA cm-2 in a continuous operation of 100 h. More impressively, NF-CH-O only requires overpotentials of 266, 292 mV and 1.877 V to drive high current densities up to 500 mA cm-2 for OER, HER and EWS, respectively, and exhibits excellent stability with a reduction in the activity of less than 10% over cycles of more than 65 h. This work highlights the room-temperature controllable ion-bath oxidative etching strategy to design efficient bifunctional catalysts with ultra-thin porous structure and high-current-density activity. Meanwhile, combined with the advantages of direct growth on the substrate for mass production, such meticulous consideration of nanostructured design will be more competitive in the H2-production industry.

Controllable atom implantation for achieving Coulomb-force unbalance toward lattice distortion and vacancy construction for accelerated water splitting.

Engineering lattice strain, especially when it combines with the lattice distortion and vacancy (LDV) induced by locally unbalanced Coulomb forces (LUCFs), can improve the local coordination environment of atoms to achieve synergistically active sites and dynamic regulation of electrocatalysts, which are beneficial to high-performance bifunctional water splitting. Considering that Ni-based selenides possess abundant variable valence states, the Nb/Fe diatomic heterogeneous spin states are purposely introduced to produce LUCFs for improving the electronic coordination environment of the materials. The as-prepared Nb/Fe co-doped Ni-Ses (NbFe-NixSey) electrocatalyst exhibits the prominent oxygen and hydrogen evolution reaction (OER/HER) properties, with low overpotentials of 237 and 226 mV at 50 mA cm-2, respectively. The alkaline water electrolyzer with NbFe-NixSey as both anodic and cathodic electrodes only requires a cell potential of 1.7 V to reach 50 mA cm-2 in a continuous operation of 50 h. This work provides a new insight to regulate the electronic structure of advanced catalyst materials at the atomic level through LUCFs-induced LDV and further push forward the energy conversion technology.