Zhang Yue, Fang Lei, Cao Zexing
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen 360015 China
RSC Adv. 2020 Nov 26;10(70):43075-43084. doi: 10.1039/d0ra08857a. eCollection 2020 Nov 23.
CO electroreduction reaction (COER) by single metal sites embedded in N-doped graphene (M@N-Gr, M = Cu and Fe) and carbon nanotubes (M@N-CNT, M = Cu and Fe) has been explored by extensive first-principles calculations in combination with the computational hydrogen electrode model. Both atomically dispersed Cu and Fe nanostructures, as the single atom catalysts (SACs), have higher selectivity towards COER, compared to hydrogen evolution reduction (HER), and they can catalyze COER to CO, HCOOH, and CHOH. In comparison with Cu@N-Gr, the limiting potentials for generating CO, HCOOH, and CHOH are reduced obviously on the high-curvature Cu@N-CNT. However, the curvature effect is less notable for the single-Fe-atom catalysts. Such discrepancies can be attributed to the d-band center changes of the single Cu and Fe sites and their different dependences on the curvature of carbon-based support materials.
通过结合计算氢电极模型的广泛第一性原理计算，研究了嵌入氮掺杂石墨烯（M@N-Gr，M = Cu和Fe）和碳纳米管（M@N-CNT，M = Cu和Fe）中的单金属位点的CO电还原反应（COER）。与析氢还原反应（HER）相比，作为单原子催化剂（SAC）的原子分散的Cu和Fe纳米结构对COER具有更高的选择性，并且它们可以将COER催化为CO、HCOOH和CHOH。与Cu@N-Gr相比，在高曲率的Cu@N-CNT上生成CO、HCOOH和CHOH的极限电位明显降低。然而，对于单Fe原子催化剂，曲率效应不太明显。这种差异可归因于单个Cu和Fe位点的d带中心变化以及它们对碳基载体材料曲率的不同依赖性。
