文献类型：期刊文献

中文题名：用于海水电解质中高效分解水合肼的镍-钼/钨双金属纳米合金

英文题名：Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency overall hydrazine splitting in seawater electrolytes

作者：王珂宇[1];梁晨[1];易致远[1];徐放[1];王一兴[1];雷林峰[1];庄林洲[1];徐至[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：66

期号：10

起止页码：3846

中文期刊名：Science China Materials

外文期刊名：中国科学（材料科学（英文版）

收录：CSTPCD;;EI(收录号：20233814749271);Scopus;WOS:【SCI-EXPANDED(收录号:WOS:001069440000002)】；CSCD:【CSCD2023_2024】；PubMed;

基金：This work was supported by the National Key R&D Program of China (2021YFB3801301) and the National Natural Science Foundation of China (22075076, 22005098 and 22208092).

语种：中文

中文关键词：bimetallic nanoalloy;synergistic effect;hydrogen evolution;hydrazine splitting

外文关键词：bimetallic nanoalloy; synergistic effect; hydrogen evolution; hydrazine splitting

摘要：利用水合肼氧化反应(HzOR)取代缓慢的析氧反应(OER)是一种可以在海水裂解中长期产生氢气并抑制不利的析氯反应(ClER)的方法.然而,很少有催化剂能够满足在双电极系统中同时呈现出优异的析氢反应(HER)和HzOR以达到较低的电池电压的要求.在此,我们报道了双金属Ni_(4)Mo/Ni_(4)W纳米合金作为双功能催化剂,该催化剂对HER(-7 mV,10 mA cm^(-2))和HzOR(-16 mV,10 mA cm^(-2))具有显著的催化活性.在1.0 mol L^(-1)KOH/2.0 molL^(-1)NaCl/0.1 mol L^(-1)N_(2)H_(4)电解液中,双电极系统需要34,295和548 mV的低电池电压就能达到10,100和200mAcm^(-2).密度泛函理论计算表明,Ni-Mo/W耦合不仅可以降低水解离的自由能和氢的吸附/脱附,而且可以优化吸附水合肼中间体的脱氢动力学.
Replacing sluggish oxygen evolution reaction(OER)by hydrazine oxidation reaction(HzOR)is a promising way to produce hydrogen and suppress unfavorable chlorine evolution reaction(ClER)in long-term seawater splitting.However,few catalysts can meet the demand to process outstanding hydrogen evolution reaction(HER)and HzOR simultaneously to achieve relatively low cell voltage in a twoelectrode system.Herein,we report bimetallic Ni_(4)Mo/Ni_(4)W nanoalloys as bifunctional catalysts with remarkable catalytic activity towards both HER(-7 mV at 10 mA cm^(-2))and HzOR(-16 mV at 10 mA cm^(-2)).Surprisingly,low cell voltages of 34,295 and 548 mV are required to achieve 10,100 and 200 mA cm^(-2) in a two-electrode system with ideal stability in 1.0 mol L^(-1) KOH/2.0 mol L^(-1) NaCl/0.1 mol L^(-1) N_(2)H_(4) electrolyte.Density functional theory calculations disclose that the Ni-Mo/W coupling can not only reduce the free energy of water dissociation as well as hydrogen adsorption/desorption,but also optimize the dehydrogenation kinetics of adsorbed intermediates.