Su Jingnan, Yu Linke, Han Bing, Li Fengyu, Chen Zhongfang, Zeng Xiao Cheng
School of Physical Science and Technology, Inner Mongolia University, Hohhot 010021, China.
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518000, China.
J Phys Chem Lett. 2024 Aug 22;15(33):8600-8607. doi: 10.1021/acs.jpclett.4c01858. Epub 2024 Aug 15.
The highly active and selective electrochemical CO reduction reaction (CORR) can be exploited to produce valuable chemicals and fuels and is also crucial for achieving clean energy goals and environmental remediation. Decorated single-atom catalysts (D-SACs), which feature synergistic interactions between the active metal site (M) and an axially decorated ligand, have been extensively explored for the CORR. Very recently, novel double-atom catalysts (DACs) featuring inverse sandwich structures were theoretically proposed and identified as promising CORR electrocatalysts. However, the experimental synthesis of DACs remains a challenge. To facilitate the fabrication and to realize the potential of these novel DACs, we designed a D-SAC system, denoted as M@gra+Cu. This system features a graphene layer with a vacancy-anchored SAC, all stacked on a Cu(111) surface, thereby embodying a Cu slab-supported inverse sandwich M-graphene-Cu structure. Using density functional theory calculations, we evaluated the stability, selectivity, and activity of 27 M@gra+Cu systems (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, or Au) and showed five M@gra+Cu (M = Co, Ni, Cu, Rh, or Pd) systems exhibit optimal characteristics for the CORR and can potentially outperform their SAC and DAC counterparts. This study offers a new strategy for developing highly efficient CORR D-SACs with an inverse sandwich structural moiety.
高活性和选择性的电化学一氧化碳还原反应（CORR）可用于生产有价值的化学品和燃料，对于实现清洁能源目标和环境修复也至关重要。具有活性金属位点（M）与轴向修饰配体之间协同相互作用的修饰单原子催化剂（D-SAC）已被广泛用于CORR研究。最近，理论上提出了具有反三明治结构的新型双原子催化剂（DAC），并被确定为有前景的CORR电催化剂。然而，DAC的实验合成仍然是一个挑战。为了便于制备并实现这些新型DAC的潜力，我们设计了一种D-SAC体系，记为M@gra+Cu。该体系的特点是具有一个空位锚定SAC的石墨烯层，全部堆叠在Cu(111)表面上，从而体现出一种Cu板支撑的反三明治M-石墨烯-Cu结构。利用密度泛函理论计算，我们评估了27种M@gra+Cu体系（M = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt或Au）的稳定性、选择性和活性，结果表明五种M@gra+Cu（M = Co、Ni、Cu、Rh或Pd）体系对CORR表现出最佳特性，并且可能优于它们的SAC和DAC同类物。本研究为开发具有反三明治结构部分的高效CORR D-SAC提供了一种新策略。
