Molten Electrolyte-Modulated Electrosynthesis of Multi-Anion Mo-Based Lamellar Nanohybrids Derived from Natural Minerals for Boosting Hydrogen Evolution.

The multi-anion molybdenum-based nanohybrids, N-doped ß-Mo2C/MoP/MoOx (denoted as MoCPO), serving as a highly efficient catalyst for hydrogen evolution reaction (HER), are fabricated via a simple and scalable electrosynthesis in molten NaCl-KCl, which integrates pyrolysis/electroreduction/compounding into a one-pot strategy using polyphosphazenes (PPAs) and earth-abundant molybdenite (mainly MoS2) as precursors. The deliberately selected PPA and molten electrolyte ensure the unique lamellar nanostructures and the blending of multiple anions of C, N, P, and O in the obtained catalyst, specifically, triggering the in situ formation of the structural oxygen vacancies (VO) in MoCPO. The nature of the hybrids can be regulated by adjusting the synthesis condition. The optimized hybrid displays a low overpotential of 99.2 mV at 10 mA cm-2 for HER in 0.5 M H2SO4 and stays active over a broad pH range. The theoretical calculations reveal that VO in the hybrids serves as favorable active sites, thus contributing to the superior HER activity. Moreover, MoCPO is also effective for overall water splitting as a bifunctional catalyst.

Tunable Selectivity and High Efficiency of CO2 Electroreduction via Borate-Enhanced Molten Salt Electrolysis.

Converting CO2 into value-added chemical fuels and functional materials by CO2 reduction reaction (CO2RR) is conducive to achieving a carbon-neutral energy cycle. However, it is still challenging to efficiently navigate CO2RR toward desirable products. Herein, we report a facile strategy to extend product species in borate-containing molten electrolyte at a positively shifted cathodic potential with a high current density (e.g. 100 mA/cm2), which can selectively electro-transform CO2 into desired products (either CO or solid carbon nanofibers, respectively reaching a high selectivity of ∼90%). The borates can act as a controller of electrolyte alkalinity to buffer the concentration of sequentially generated O2- during CO2RR, positively shifting the reduction potential of the captured CO2 and concurrently extending the product species. The sustainable buffering effect is available under CO2 atmosphere. Compared with borate-free electrolyte, the CO2 conversion efficiency is over three times higher, while the electrolysis energy consumption is decreased by over 40%.

Electric Field-Driven Interfacial Alloying for in Situ Fabrication of Nano-Mo2C on Carbon Fabric as Cathode toward Efficient Hydrogen Generation.

A binderless composite cathode for efficient electrocatalytic hydrogen evolution reaction (HER), Mo2C-decorated carbon cloth (denoted as CC/MC), is simply fabricated via a novel and unique strategy which involves a solid-solid phase interfacial electrochemical reaction between carbon fiber and bulk-MoS2 in molten NaCl-KCl (700 °C). MoS2, evenly coated on carbon cloth (CC), is electrochemically reduced in situ and readily reacts with the carbon fibers of CC current collector to form a Mo2C nanoparticle layer. The experiment and calculation results show that the applied electric field results in a declining migration barrier of Mo vacancies in Mo2C lattice, which promotes the diffusion of Mo atoms into carbon across the interfacial Mo2C layer, thereby impelling the combination of Mo with C in depth. The electrochemical tests indicate that the optimized cathode (CC/MC-2) exhibits a small overpotential of 134.4 mV at 10 mA cm-2 and stays stable for HER in acidic media. The catalytic capacity for N2 reduction of CC/MC-2 is analyzed. In addition, a Ni-doped Mo2C-modified carbon fabric electrode with enhanced HER activity (η10 = 96.6 mV) can be prepared through a similar process.