题目：Boosting the bifunctional electrocatalytic performance of nanowire NiCo₂O₄@ultrathin porous carbon via modulating d-band center

作者：Huiqin Yu ^a, Fang Li ^a*, Jing Cao ^a, Shifu Chen ^a, Haili Lin ^a*

单位：^aKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education; College of Chemistry and Materials Science, Huaibei Normal University, Huaibei, Anhui 235000, P. R. China.

摘要：Developing highly active and stable bifunctional electrocatalysts for oxidation of alcohols is critical for energy and chemical conversion. Here a nanowire NiCo₂O₄ on the ultrathin porous carbon (NiCo₂O₄/C) is fabricated and exhibits superior electrocatalytic performance for both hydrogen evolution and benzyl alcohol (BA) oxidation in comparison with pristine NiCo₂O₄ free of carbon. It only needed 1.36 V vs. RHE to afford a current density of 50 mA cm⁻² for BA oxidation. The overpotential for HER (η₁₀) is -93.0 mV vs. RHE. Furthermore, high yield (96.0%) and faradaic efficiency (98.6%) of benzoic acid were achieved in 10 consecutive stability tests. The outstanding electrocatalytic activity can be attributed to the following aspects: 1) the hierarchical architecture exposed more catalytic active sites and enhanced mass transport; 2) the ultrathin porous carbon strengthened the affinity for reaction medium; 3) strong electronic interactions optimized energy band structure. DFT simulations proved that the Gibbs free energy of the rate-determining step was reduced when coupling with ultrathin porous carbon, thus lowering the energy barrier and accelerating the reaction process. Theoretical calculations further reveal that the moderate downshift in E_d energy levels, which balance the adsorption and desorption of the intermediates, is the intrinsic reason for the promoted oxidation activity. This work could provide valuable insights into the design of highly efficient bifunctional electrocatalysts.

影响因子：7.0

分区情况：一区

链接：https://pubs.rsc.org/en/content/articlelanding/2024/qi/d4qi00821a/unauth