摘要
Single-atom catalysts(SACs)have attracted increasing concerns in electrocatalysis because of their maximal metal atom utilization,distinctive electronic properties,and catalytic performance.However,the isolated single sites are disadvantageous for reactions that require simultaneously activating different reactants/intermediates.Fully exposed metal cluster catalyst(FECC),inheriting the merits of SACs and metallic nanoparticles,can synergistically adsorb and activate reactants/intermediates on their multi-atomic sites,demonstrating great promise in electrocatalytic reactions.Here a facile method to regulate the atomic dispersion of Ni species from cluster to single-atom scale for efficient CO_(2) reduction was developed.The obtained Ni FECC exhibits high Faradaic efficiency of CO up to 99%,high CO partial current density of 347.2 mA cm^(−2),and robust durability under 20 h electrolysis.Theoretical calculations illuminate that the ensemble of multiple Ni atoms regulated by sulfur atoms accelerates the reaction kinetics and thus improves CO production.
单原子催化剂(SAC)因其最大化的金属原子利用率、独特的电子结构和优异的催化性能在电催化领域引起越来越多的关注.然而,对于需要同时活化不同反应物/中间体的反应来说,孤立的位点是不利的.完全暴露的金属簇催化剂(FECC),继承了SACs和金属纳米颗粒的优点,可以在其多原子位点上协同吸附和活化反应物/中间物,在电催化反应中显示了巨大的前景.文本开发了一种简便的方法从团簇到单原子尺度来调节Ni物种的原子分散度,以实现高效的二氧化碳还原.所制备的Ni FECC在CO合成中表现出了高达99%的法拉第效率,347.2 mA cm^(-2)的高CO分电流密度,以及在20 h电解下的优异稳定性.理论计算表明,多原子中心的构建和硫原子掺杂共同加速了反应动力学,从而提高了电化学CO_(2)还原合成CO的活性与选择性.
作者
Qi Hao
Qi Tang
Hai-Xia Zhong
Jia-Zhi Wang
Dong-Xue Liu
Xin-Bo Zhang
郝琦;汤淇;钟海霞;王家志;刘冬雪;张新波(State Key Laboratory of Rare Earth Resource Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;Key Laboratory of Automobile Materials(Jilin University),Ministry of Education,School of Materials Science and Engineering,Jilin University,Changchun 130022,China;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China;Center for Advancing Electronics Dresden(CFAED)and Faculty of Chemistry and Food Chemistry,Technische Universität Dresden,Dresden 01062,Germany)
基金
funding from the Alexander von Humboldt Foundation(Germany)
supported by the National Key R&D Program of China(2020YFB1505603)
the National Natural Science Foundation of China(51925102)
Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3)
Youth Innovation Promotion Association CAS(E1202002)。
