Selective CO2-to-HCOOH Electroreduction on Graphdiyne-Supported Bimetallic Single-Cluster Catalysts

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-06-26 DOI:10.1021/acscatal.4c00858

Bin Chen, Ya-Fei Jiang, Hai Xiao* and Jun Li*,

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引用次数: 0

Abstract

The oxophilic elements may stabilize the O-intermediate in electrochemical CO₂ reduction reaction (eCO₂RR), yet their applications for formic acid (HCOOH) production may be limited by the Sabatier principle. Here we explore the bimetallic M₁Ti₃ (M = Ni, Pd, Pt, Cu, Ag, Au) single-cluster catalysts (SCCs) anchored on graphdiyne (GDY) for eCO₂RR to produce HCOOH. First-principles calculations show that the M₁Ti₃/GDY SCCs prefer to activate and hydrogenate CO₂ to the *OCHO intermediate (*denotes the active site of the catalyst) due to the oxophilic Ti sites, while the M₁ site plays a key role in suppressing the adsorption of *H and tuning the adsorption of *OCHO and *HCOOH for the HCOOH production, which is attributed to the modulation of Ti–O bonding strength by the M₁ atom. We predict that the Au₁Ti₃/GDY SCC is an efficient electrocatalyst for the selective eCO₂RR to produce HCOOH. The directions for further improvements for the selective eCO₂RR to produce HCOOH are discussed.

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在石墨炔支撑的双金属单簇催化剂上实现 CO2 到 HCOOH 的选择性电还原

亲氧化元素可以稳定电化学二氧化碳还原反应（eCO2RR）中的中间产物 O，但它们在甲酸（HCOOH）生产中的应用可能会受到萨巴蒂尔原理的限制。在此，我们探索了锚定在石墨二乙烯（GDY）上的双金属 M1Ti3（M = Ni、Pd、Pt、Cu、Ag、Au）单簇催化剂（SCCs），用于 eCO2RR 生产 HCOOH。第一性原理计算表明，M1Ti3/GDY SCC 由于具有亲氧化 Ti 位点，因此更倾向于活化和氢化 CO2，使其成为 *OCHO 中间体（*表示催化剂的活性位点），而 M1 位点则在抑制 *H 的吸附以及调整 *OCHO 和 *HCOOH 的吸附以产生 HCOOH 方面起着关键作用，这归因于 M1 原子对 Ti-O 键强度的调节。我们预测 Au1Ti3/GDY SCC 是选择性 eCO2RR 生成 HCOOH 的高效电催化剂。我们还讨论了进一步改进选择性 eCO2RR 以产生 HCOOH 的方向。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.