Citation:
Yaran Shi, Ying Ma, Liming Li, Anran Zhang, Zhouzhou Wang, Ying Yu. 可放大电沉积的MoNi4合金/非晶NiMoOx电极用于稳定碱性海水析氢[J]. Acta Physico-Chimica Sinica,
;2026, 42(11): 100381.
doi:
10.1016/j.actphy.2026.100381
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在碱性析氢反应(HER)中,Volmer步骤(H2O + e- → H* + OH-)的缓慢动力学以及海水中的腐蚀性氯离子,对高效海水电解构成了双重挑战。本文通过一步电沉积法合成了MoNi4合金/非晶态NiMoOx(MoNi4/NiMoOx)催化剂,在10 mA cm-2下仅需28 mV的过电位,并在碱性天然海水中于500 mA cm-2下稳定运行800 h。该电极可放大至15 cm×15 cm,其切割片(110 cm2)在工业电解槽中于2 A cm-2下稳定工作750 h。X射线光电子能谱(XPS)和X射线吸收精细结构(XAFS)分析表明,MoNi4/NiMoOx通过从MoNi4到NiMoOx的电子转移,生成了富含电子的低价Niδ+(0 < δ < 1)物种。原位拉曼光谱、Bode相分析和局部pH测量证明,MoNi4/NiMoOx中的这种界面电子效应通过促进界面水分解加速了Volmer决速步骤,并维持了热力学上更有利于HER的较低局部pH值。理论计算显示,MoNi4/NiMoOx的d带中心更接近费米能级,提供了更强的H*吸附,近乎热中性的Volmer解离步骤以及固有的Cl-排斥作用,从而实现了在海水中的良好稳定性。该策略为直接海水电解提供了一条简单且可放大的高性能非贵金属催化剂制备途径。
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