Oxygen-bridged Schottky junction in ZnO-Ni3ZnC0.7 promotes photocatalytic reduction of CO2 to CO: Steering charge flow and modulating electron density of active sites.

Developing carbon dioxide (CO2) photocatalysts from transition metal carbides (TMCs) with abundant active sites, modulable electron cloud density, as well as low cost and high stability is of great significance for artificial photosynthesis. Building an efficient electron transfer channel between the photo-excitation site and the reaction-active site to extract and steer photo-induced electron flow is necessary but challenging for the highly selective conversion of CO2. In this study, we achieved an oxygen-bridged Schottky junction between ZnO and Ni3ZnC0.7 (denoted as Znoxide-O-ZnTMC) through a ligand-vacancy strategy of MOF. The ZnO-Ni3ZnC0.7 heterostructure integrates the photo-exciter (ZnO), high-speed electron transport channel (Znoxide-O-ZnTMC), and reaction-active species (Ni3ZnC0.7), where Znoxide-O-ZnTMC facilitates the transfer of excited electrons in ZnO to Ni3ZnC0.7. The Zn atoms in Ni3ZnC0.7 serve as electron-rich active sites, regulating the CO2 adsorption energy, promoting the transformation of *COOH to CO, and inhibiting H2 production. The ZnO-Ni3ZnC0.7 shows a high CO yield of 2674.80 µmol g-1h-1 with a selectivity of 93.40 % and an apparent quantum yield of 18.30 % (λ = 420 nm) with triethanolamine as a sacrificial agent. The CO production rate remains at 96.40 % after 18 h. Notably, ZnO-Ni3ZnC0.7 exhibits a high CO yield of 873.60 µmol g-1h-1 with a selectivity of 90.20 % in seawater.

Thermal stability of Ni3ZnC0.7: As tunable additive for biomass-derived carbon sheet composites with efficient microwave absorption.

With the rapidly development of radar detection technology and the increasingly complex application environment in military field and electromagnetic pollution surrounded by electron devices, increasingly demand is needed for electromagnetic wave absorbent materials with high absorption efficiency and thermal stability. Herein, a novel Ni3ZnC0.7/Ni loaded puffed-rice derived carbon (RNZC) composites are successfully prepared by vacuum filtration of metal-organic frameworks gel precursor together with layered porous-structure carbon and followed by calcination. The Ni3ZnC0.7 particles uniformly decorate on the surface and pores of puffed-rice derived carbon. The puffed-rice derived carbon@Ni3ZnC0.7/Ni-400 mg (RNZC-4) sample displayed the best electromagnetic wave absorption (EMA) performances among the samples with different Ni3ZnC0.7 loading. The minimum reflection loss (RLmin) of the RNZC-4 composite reaches -39.9 dB at 8.6 GHz, while widest effective absorption bandwidth (EAB) of RNZC-4 for RL < -10 dB can reach 9.9 GHz (8.1-18 GHz, 1.49 mm). High porosity and large specific surface area promote the multiple reflection-absorption effect of the incident electromagnetic waves. The Ni3ZnC0.7 nanoparticles provide a large number of interfaces and dipole factors. Analysis reveals that the RNZC-4 remained general stability under 400 °C with formation of a small amount of NiO and ZnO phases. Surprisingly, at such high temperature, the absorbing properties of the material are improved rather than decreased. Obviously, the material still maintains good electromagnetic wave performance at high temperature, and implies that the absorber shows good performance stability. Therefore, our preparations exhibit potential applications under extreme conditions and a new insight for the design and application of bimetallic carbides.

Synergistic Effects in Ultrafine Molybdenum-Tungsten Bimetallic Carbide Hollow Carbon Architecture Boost Hydrogen Evolution Catalysis and Lithium-Ion Storage.

Constructing hierarchical heterostructures is considered a useful strategy to regulate surface electronic structure and improve the electrochemical kinetics. Herein, the authors develop a hollow architecture composed of MoC1- x and WC1- x carbide nanoparticles and carbon matrix for boosting electrocatalytic hydrogen evolution and lithium ions storage. The hybridization of ultrafine nanoparticles confined in the N-doped carbon nanosheets provides an appropriate hydrogen adsorption free energy and abundant boundary interfaces for lithium intercalation, leading to the synergistically enhanced composite conductivity. As a proof of concept, the as-prepared catalyst exhibits outstanding and durable electrocatalytic performance with a low overpotential of 103 and 163 mV at 10 mA cm-2 , as well as a Tafel slope of 58 and 90 mV dec-1 in alkaline electrolyte and acid electrolyte, respectively. Moreover, evaluated as an anode for a lithium-ion battery, the as-resulted sample delivers a rate capability of 1032.1 mA h g-1 at 0.1 A g-1 . This electrode indicates superior cyclability with a capability of 679.1 mA h g-1 at 5 A g-1 after 4000 cycles. The present work provides a strategy to design effective and stable bimetallic carbide composites as superior electrocatalysts and electrode materials.

Constructing Pure Phase Tungsten-Based Bimetallic Carbide Nanosheet as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N-doped carbon matrix (Co6 W6 C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal-organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen-binding energy. Thus Co6 W6 C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of -10 mA cm-2 . Besides, Co6 W6 C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of -10 mA cm-2 . The water splitting device, by applying Co6 W6 C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm-2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.