Ku Ruiqi, Yu Guangtao, Gao Jing, Huang Xuri, Chen Wei
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China and College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China.
Phys Chem Chem Phys. 2020 Feb 14;22(6):3254-3263. doi: 10.1039/c9cp06057j. Epub 2020 Jan 29.
On the basis of density functional theory (DFT) calculations, we have systematically investigated the structures and hydrogen evolution reaction (HER) catalytic activities for a series of new composite systems TM@GDY (TM = Sc, Ti, Mn, Fe, Co, Ni and Cu), which are constructed by embedding tetrahedral 3d transition metal TM clusters in the in-plane cavity of two-dimensional (2D) π-conjugated graphdiyne (GDY). Our computed results reveal that compared with the constituent subunits, namely the sole TM cluster and GDY, all these composite TM@GDY nanostructures can uniformly exhibit considerably high HER catalytic activity over a wide range of hydrogen coverage, and especially the Fe@GDY and Co@GDY systems can possess higher HER activity, in view of their higher number of active sites. The high HER catalytic activity for TM@GDY can be mainly due to the occurrence of obvious electron transfer from TM cluster to GDY, significantly activating the correlative C and TM atoms. Moreover, all these composite TM@GDY systems can also exhibit high structural stability and good conductivity. Therefore, all of them can be considered as a new kind of promising HER catalyst, and this study can provide new strategies for designing low-cost and high-performance 2D carbon-based electrocatalysts.
基于密度泛函理论（DFT）计算，我们系统地研究了一系列新型复合体系TM@GDY（TM = Sc、Ti、Mn、Fe、Co、Ni和Cu）的结构和析氢反应（HER）催化活性，这些复合体系是通过将四面体3d过渡金属TM簇嵌入二维（2D）π共轭石墨炔（GDY）的面内空腔构建而成的。我们的计算结果表明，与组成亚单元，即单独的TM簇和GDY相比，所有这些复合TM@GDY纳米结构在较宽的氢覆盖范围内都能均匀地表现出相当高的HER催化活性，特别是Fe@GDY和Co@GDY体系，鉴于它们有更多的活性位点，能够具有更高的HER活性。TM@GDY具有高HER催化活性的主要原因可能是从TM簇到GDY发生了明显的电子转移，显著激活了相关的C和TM原子。此外，所有这些复合TM@GDY体系还能表现出高结构稳定性和良好的导电性。因此，它们都可被视为一种新型的有前景的HER催化剂，本研究可为设计低成本、高性能的二维碳基电催化剂提供新策略。
