DFT study on CO<sub>2</sub> hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways

ZHANG Yiran; ZHANG Haitao; MA Hongfang; QIAN Weixin; YING Weiyong

doi:10.12434/j.issn.2097-2547.20260059

您当前的位置：

首页 >

文章列表页 >

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

更新时间：2026-06-05

- DFT study on CO₂ hydrogenation to methanol on Pd-doped Cu(111) surface: Competitive mechanism between formate and RWGS hydrogenation pathways
- Pages: 1-11(2026)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20260059
  CLC：
- Received：03 February 2026，
  
  Revised：2026-03-18，
  
  Online First：03 June 2026，
- 稿件说明：
移动端阅览
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

WANG W H , HIMEDA Y , MUCKERMAN J T , et al . CO 2 hydrogenation to formate and methanol as an alternative to photo-and electrochemical CO 2 reduction [J ] . Chemical Reviews , 2015 , 115 ( 23 ): 12936 - 12973 .

KATTEL S , RAMÍREZ P J , CHEN J G , et al . Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts [J ] . Science , 2017 , 355 ( 6331 ): 1296 - 1299 .

POROSOFF M D , CHEN J G . Trends in the catalytic reduction of CO 2 by hydrogen over supported monometallic and bimetallic catalysts [J ] . Journal of Catalysis , 2013 , 301 : 30 - 37 .

ZHOU H , CHEN Z X , LÓPEZ A V , et al . Engineering the Cu/Mo 2 CT x (MXene) interface to drive CO 2 hydrogenation to methanol [J ] . Nature Catalysis , 2021 , 4 ( 10 ): 860 - 871 .

KONDRATENKO E V , MUL G , BALTRUSAITIS J , et al . Status and perspectives of CO 2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes [J ] . Energy environmental science , 2013 , 6 ( 11 ): 3112 - 3135 .

YANG Y , WHITE M G , LIU P . Theoretical study of methanol synthesis from CO 2 hydrogenation on metal-doped Cu(111) surfaces [J ] . The Journal of Physical Chemistry C , 2012 , 116 ( 1 ): 248 - 256 .

YANG Y , MIMS C A , MEI D H , et al . Mechanistic studies of methanol synthesis over Cu from CO/CO 2 /H 2 /H 2 O mixtures: The source of C in methanol and the role of water [J ] . Journal of Catalysis , 2013 , 298 : 10 - 17 .

LI Y W , CHAN S H , SUN Q . Heterogeneous catalytic conversion of CO 2 : A comprehensive theoretical review [J ] . Nanoscale , 2015 , 7 ( 19 ): 8663 - 8683 .

NAKATSUJI H , HU Z M . Mechanism of methanol synthesis on Cu(100) and Zn/Cu(100) surfaces: Comparative dipped adcluster model study [J ] . International Journal of Quantum Chemistry , 2000 , 77 ( 1 ): 341 - 349 .

NEETU K , ALI H M , MANISH A , et al . Role of reduced CeO 2 (110) surface for CO 2 reduction to CO and methanol [J ] . The Journal of Physical Chemistry C , 2016 , 120 ( 30 ): 16626 - 16635 .

CUI Z L , MENG S Y , YI Y H , et al . Plasma-catalytic methanol synthesis from CO 2 hydrogenation over a supported Cu cluster catalyst: insights into the reaction mechanism [J ] . ACS Catalysis , 2022 , 12 ( 2 ): 1326 - 1337 .

JIANG X , KOIZUMI N , GUO X , et al . Bimetallic Pd-Cu catalysts for selective CO 2 hydrogenation to methanol [J ] . Applied Catalysis B: Environmental , 2015 , 170 : 173 - 185 .

BLAYLOCK D W , ZHU Y A , GREEN W H . Computational investigation of the thermochemistry and kinetics of steam methane reforming over a multi-faceted nickel catalyst [J ] . Topics in Catalysis , 2011 , 54 ( 13 ): 828 .

NIU J , WANG Y , QI Y , et al . New mechanism insights into methane steam reforming on Pt/Ni from DFT and experimental kinetic study [J ] . Fuel , 2020 , 266 : 117143 .

LIU L , FAN F , JIANG Z , et al . Mechanistic study of Pd-Cu bimetallic catalysts for methanol synthesis from CO 2 hydrogenation [J ] . The Journal of Physical Chemistry C , 2017 , 121 ( 47 ): 26287 - 26299 .

PERDEW J P , BURKE K , ERNZERHOF M . Generalized gradient approximation made simple [J ] . Physical Review Letters , 1996 , 77 ( 18 ): 3865 .

PERDEW J P , WANG Y . Accurate and simple analytic representation of the electron-gas correlation energy [J ] . Physical Review B , 1992 , 45 ( 23 ): 13244 .

BERGNER A , DOLG M , KÜCHLE W , et al . Ab initio energy-adjusted pseudopotentials for elements of groups 13-17 [J ] . Molecular Physics , 1993 , 80 ( 6 ): 1431 - 1441 .

MONKHORST H J , PACK J D . Special points for brillouin-zone integrations [J ] . Physical Review B , 1976 , 13 ( 12 ): 5188 .

OU Z L , RAN J Y , NIU J T , et al . A density functional theory study of CO 2 hydrogenation to methanol over Pd/TiO 2 catalyst: The role of interfacial site [J ] . International Journal of Hydrogen Energy , 2020 , 45 ( 11 ): 6328 - 6340 .

张东健 , 查雅君 , 刘冰 , 等 . Pd 2 /CeO 2 上O V 和H 2 O对催化CO 2 加氢反应影响的理论计算研究 [J ] . 低碳化学与化工 , 2025 , 50 ( 5 ): 11 - 7 .

ZHANG D J , ZHA Y J , LIU B , et al . Theoretical calculation study on effects of O V and H 2 O on CO 2 hydrogenation over Pd 2 /CeO 2 [J ] . Low-Carbon Chemistry Chemical Engineering , 2025 , 50 ( 5 ): 11 - 17 .

QIU M , TAO H , LI Y , et al . Insight into the mechanism of CO 2 and CO methanation over Cu(100) and Co-modified Cu(100) surfaces: A DFT study [J ] . Applied Surface Science , 2019 , 495 : 143457 .

GOKHALE A A , DUMESIC J A , MAVRIKAKIS M . On the mechanism of low-temperature water gas shift reaction on copper [J ] . Journal of the American Chemical Society , 2008 , 130 ( 4 ): 1402 - 1414 .

NIE X , JIANG X , WANG H , et al . Mechanistic understanding of alloy effect and water promotion for Pd-Cu bimetallic catalysts in CO 2 hydrogenation to methanol [J ] . ACS Catalysis , 2018 , 8 ( 6 ): 4873 - 4892 .

ZHANG R , LIU H , WANG B , et al . Insights into the preference of CO 2 formation from HCOOH decomposition on Pd surface: A theoretical study [J ] . The Journal of Physical Chemistry C , 2012 , 116 ( 42 ): 22266 - 22280 .

YANG Y , EVANS J , RODRIGUEZ J A , et al . Fundamental studies of methanol synthesis from CO 2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO (0001 [combining macron ] ) [J ] . Physical Chemistry Chemical Physics , 2010 , 12 : 9909 - 9917 .

WANG G R , ZHANG R G , WANG B J . Insight into the preference mechanism for CC chain formation of C 2 oxygenates and the effect of promoters in syngas conversion over Cu-based catalysts [J ] . Applied Catalysis A: General , 2013 , 466 : 77 - 89 .

GU X K , LI W X . First-principles study on the origin of the different selectivities for methanol steam reforming on Cu(111) and Pd(111) [J ] . The Journal of Physical Chemistry C , 2010 , 114 ( 49 ): 21539 - 21547 .

JIANG Z , GUO S , FANG T . Theoretical investigation on the dehydrogenation mechanism of CH 3 OH on Cu(100) surface [J ] . Journal of Alloys Compounds , 2017 , 698 : 617 - 625 .

ZUO Z J , WANG L , HAN P D , et al . Insights into the reaction mechanisms of methanol decomposition, methanol oxidation and steam reforming of methanol on Cu(111): A density functional theory study [J ] . International Journal of Hydrogen Energy , 2014 , 39 ( 4 ): 1664 - 1679 .

YE J , LIU C J , MEI D , et al . Methanol synthesis from CO 2 hydrogenation over a Pd 4 /In 2 O 3 model catalyst: A combined DFT and kinetic study [J ] . Journal of Catalysis , 2014 , 317 : 44 - 53 .

NIE X , LUO W , JANIK M J , et al . Reaction mechanisms of CO 2 electrochemical reduction on Cu(111) determined with density functional theory [J ] . Journal of Catalysis , 2014 , 312 : 108 - 122 .

LIU L , FAN F , BAI M , et al . Mechanistic study of methanol synthesis from CO 2 hydrogenation on Rh-doped Cu(111) surfaces [J ] . Molecular Catalysis , 2019 , 466 : 26 - 36 .

ZHAO Y F , YANG Y , MIMS C , et al . Insight into methanol synthesis from CO 2 hydrogenation on Cu (111): Complex reaction network and the effects of H 2 O [J ] . Journal of catalysis , 2011 , 281 ( 2 ): 199 - 211 .

LIANG H , ZHANG B , GAO P , et al . Strong Co—O—Si bonded ultra-stable single-atom Co/SBA-15 catalyst for selective hydrogenation of CO 2 to CO [J ] . Chem Catalysis , 2022 , 2 ( 3 ): 610 - 621 .

刘婷婷 , 白慧 , 白冰 , 等 . 阶梯Cu(221)面催化还原CO制甲醇反应机理及其电子效应的理论研究 [J ] . 低碳化学与化工 , 2025 , 50 ( 4 ): 29 - 37+54 .

LIU T T , BAI H , BAI B , et al . Theoretical study on reaction mechanisms and electron effects of CO catalytic reduction to methanol on stepped Cu(221) surface [J ] . Low-Carbon Chemistry Chemical Engineering , 2025 , 50 ( 4 ): 29 - 37+54 .

SHENG Y , POLYNSKI M V , ESWARAN M K , et al . A review of mechanistic insights into CO 2 reduction to higher alcohols for rational catalyst design [J ] . Applied Catalysis B: Environmental , 2024 , 343 : 123550 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO3 oxygen carrier based on DFT

Study on electrospinning Pd-doping TiO2-ZrO2 nanofiber membranes and their catalytic performances in infrared combustion of liquefied petroleum gas

Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO2 hydrogenation to light olefins on Fe(111) surface

Mechanisms of direct synthesis of ethanol from syngas catalyzed by heterojunction CoCu(100)/(111) surface based on density functional theory

Influence of Cu valence states on dehydrogenation of 1,4-butanediol to γ-butyrolactone based on density functional theory calculation

Related Author

ZHOU Haozhe

LIANG Zhiyong

FANG Junfei

ZHAO Qiying

LU Jianwei

JIANG Qunhui

MA Haile

TIAN Jiarong

Related Institution

Shaanxi Key Laboratory of Industrial Automation, Shaanxi University of Technology

School of Mechanical Engineering, Shaanxi University of Technology

Zhenjiang Meibo Infrared Technology Co., Ltd.

School of Materials Science and Engineering, Jiangsu University

School of Food and Biological Engineering, Jiangsu University

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：459257 Visits Today：673

⁰

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

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