Sulfur doping enhanced desorption of intermediates on NiCoP for efficient alkaline hydrogen evolution
Sulfur doping enhanced desorption of intermediates on NiCoP for efficient alkaline hydrogen evolution
复制标题
硫掺杂增强 NiCoP 上中间体的解吸，实现高效碱性析氢
作者：
Yuyang Qi;Long Zhang;Lan Sun;Guanjun Chen;Qiaomei Luo;Hongqiang Xin;Jiahui Peng;Yan Li;Fei Ma
高催化活性、高稳定性、低成本的电催化剂是催化析氢反应的关键。本文在碳纤维纸骨架(S-NiCoP NW/CFP)上制备了硫掺杂镍钴磷纳米线阵列(S-NiCoP NW/CFP)，结果表明，硫掺杂可以很好地改善镍钴磷在碱性溶液中的电催化性能。在1.0M KOH中，S掺杂的NiCoP纳米线在100 mA cm−2时的过电位仅为172 mV(Vs RHE)，在过电位为100 mV时的翻转频率是NiCoP的1.71倍，显示了其优越的本征活性。密度泛函理论计算表明，S掺杂降低了d带中心，从而削弱了NiCoP与中间体之间的相互作用。这导致了优化的氢吸附吉布斯自由能(ΔGH*)和更快的脱附OH*。本研究为设计和优化HER在碱性溶液中的电催化剂提供了一条很有前途的途径。
Electrocatalysts with high catalytic activity, high stability and low cost are critical to the hydrogen evolution reaction (HER). In this paper, sulfur(S)-doped NiCoP nanowire arrays on a carbon fiber paper skeleton (S-NiCoP NW/CFP) are prepared, and it is demonstrated that the electrocatalytic properties of NiCoP in alkaline solution could be well improved by sulfur doping. In 1.0 M KOH, only an overpotential of 172 mV (vs. RHE) at 100 mA cm−2 is required for S doped NiCoP nanowires on CFP, and the turnover frequency (TOF) is 1.71 times that of NiCoP at an overpotential of 100 mV, indicating its superior intrinsic activity. Density functional theory (DFT) calculations show that S doping could lower the center of the d-band, and thus weaken the interaction between NiCoP and the intermediates. This leads to an optimized hydrogen adsorption Gibbs free energy (ΔGH*) and faster desorption of OH*. This study offers a promising way to design and optimize electrocatalysts for the HER in alkaline solution.