基于密度泛函理论的Pd掺杂Cu(111)表面CO<sub>2</sub>加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理

张依燃; 张海涛; 马宏方; 钱炜鑫; 应卫勇

doi:10.12434/j.issn.2097-2547.20260059

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基于密度泛函理论的Pd掺杂Cu(111)表面CO₂加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理

更新时间：2026-06-05

- 基于密度泛函理论的Pd掺杂Cu(111)表面CO₂加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理
- DFT study on CO₂ hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways
- 低碳化学与化工 2026: 1-11.
- 作者机构：
  
  1.华东理工大学化工学院大型工业反应器工程教育部工程研究中心，上海 200237
  2.华东理工大学煤液化气化及高效低碳利用全国重点实验室，上海 200237
- 作者简介：
  
  张依燃（2000—），硕士研究生，研究方向为低碳化工，E-mail：y82230100@mail.ecust.edu.cn。
  钱炜鑫（1983—），博士，副教授，研究方向为低碳化工，E-mail：wxqian@ecust.edu.cn。
- 基金信息：
  
  国家自然科学基金(22178113);中央高校基本科研业务费专项资金(JKA01231712;JKCA1241202)
- DOI：10.12434/j.issn.2097-2547.20260059
  中图分类号：
- 收稿：2026-02-03，
  
  修回：2026-03-18，
  
  网络首发：2026-06-03，
- 稿件说明：
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张依燃,张海涛,马宏方等.基于密度泛函理论的Pd掺杂Cu(111)表面CO₂加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理[J].低碳化学与化工,

ZHANG Yiran,ZHANG Haitao,MA Hongfang,et al.DFT study on CO₂ hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways[J].Low-Carbon Chemistry and Chemical Engineering,
张依燃,张海涛,马宏方等.基于密度泛函理论的Pd掺杂Cu(111)表面CO₂加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260059.

ZHANG Yiran,ZHANG Haitao,MA Hongfang,et al.DFT study on CO₂ hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260059.

摘要

绿氢驱动的CO

加氢制甲醇技术是构建可持续碳循环体系的关键环节，然而其大规模应用仍受到催化剂催化活性不足和微观反应机理认识不清的限制。针对传统Cu基催化剂催化活性较低

的挑战，通过Pd掺杂构建Pd-Cu双金属催化剂可显著提升催化性能，但其微观调控机制尚不明确。采用密度泛函理论（DFT）分析了CuPd(111)表面甲酸盐（HCOO*）与逆水煤气变换（RWGS）加氢路径的竞争机理。动力学分析结果表明，RWGS加氢路径为最佳反应路径，其限速步（生成

trans

-COOH*）能垒为1.34 eV，显著低于HCOO*路径的限速步（CO

活化生成HCOO*）能垒（1.52 eV）。与Cu(111)表面相比， Pd掺杂使催化剂中形成了高催化活性的Cu-Pd协同位点，该位点可通过电子效应稳定RWGS加氢路径限速步的过渡态，使该步能垒由1.97 eV降至1.34 eV，并将

cis

-COOH*解离为CO*的能垒由0.68 eV降至0.24 eV。相比之下，HCOO*路径中不仅限速步能垒高达1.52 eV，其生成H

COO*的竞争分支更因H*迁移距离过长（3.98 Å，1 Å = 0.1 nm）及表面畸变，导致能垒升高至2.57 eV而被完全阻断。该研究可为CO

加氢制甲醇的催化剂设计及反应工艺优化提供借鉴。

Abstract

Green hydrogen-driven CO

hydrogenation to methanol represents a pivotal component in establishing a sustainable carbon cycle. However

its large-scale implementation remains constrained by insufficient catalytic activity and a lack of fundamental understanding regarding microscopic reaction mechanisms. To address the limited activity of traditional Cu-based catalysts

the incorporation of Pd to form Pd-Cu bimetallic catalysts has demonstrated significant performance enhancements

yet the underlying regulatory mechanisms remain elusive. Density functional theory (DFT) was employed to investigate the competitive mechanisms between the formate (HCOO*) and reverse water-gas shift (RWGS) hydrogenation pathways on the CuPd(111) surface. Kinetic analysis reveals that the RWGS pathway is the energetically preferred route. The rate-determining step (the formation of

trans

-COOH*) for the pathway exhibits an energy barrier of 1.34 eV

which is markedly lower than the energy barrier (1.52 eV) of the rate-determining step (activation of CO

to HCOO*) of the HCOO* pathway. Compared to the pristine Cu(111) surface

Pd doping facilitates the formation of highly active Cu-Pd synergistic sites. These sites stabilize the transition state of the RWGS rate-determining step via electronic effects

reducing the activation barrier from 1.97 eV to 1.34 eV

while simultaneously lowering the barrier for

cis

-COOH* dissociation into CO* from 0.68 eV to 0.24 eV. Conversely

the HCOO* pathway is hindered not only by its high rate-determining step barrier but also by the complete blockage of the H

COO* formation branch

and the latter’s barrier escalates to 2.57 eV due to excessive H* migration distances (3.98 Å

1 Å = 0.1 nm) and significant surface distortion. The research can provide reference for the rational design of catalysts and the optimization of reaction processes of CO

hydrogenation to methanol.

关键词

Keywords

references

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DFT study on CO2 hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways

DOI：10.12434/j.issn.2097-2547.20260059

摘要

Abstract

关键词

Keywords

references

基于密度泛函理论的Pd掺杂Cu(111)表面CO₂加氢制甲醇：甲酸盐与逆水煤气变换加氢路径竞争机理

DFT study on CO₂ hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways