基于密度泛函理论的异质结CoCu(100)/(111)表面催化合成气直接制乙醇机理研究

杜鹏龙; 孟园园; 王俊文; 丁传敏; 王莲; 李刚森; 段东红

doi:10.12434/j.issn.2097-2547.20250074

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基于密度泛函理论的异质结CoCu(100)/(111)表面催化合成气直接制乙醇机理研究

C1化学与催化转化 | 更新时间：2025-12-25

- 基于密度泛函理论的异质结CoCu(100)/(111)表面催化合成气直接制乙醇机理研究
- Mechanisms of direct synthesis of ethanol from syngas catalyzed by heterojunction CoCu(100)/(111) surface based on density functional theory
- 低碳化学与化工 2025, 50(12): 21-29.
- 作者机构：
  
  1.太原理工大学化学与化工学院，山西太原 030024
  2.山西省超级计算中心，山西吕梁 033015
- 作者简介：
  
  杜鹏龙（1998—），硕士研究生，研究方向为C1化学与化工，E-mail：dpl1824363332@163.com。
  孟园园（1989—），博士，讲师，研究方向为C1化学与化工，E-mail：mengyuanyuan@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(21978189;22308244);山西自然科学基金面上项目(202203021221091)
- DOI：10.12434/j.issn.2097-2547.20250074
  中图分类号： TE6;O643.3
- 收稿：2025-02-27，
  
  修回：2025-03-27，
  
  纸质出版：2025-12-25
- 稿件说明：
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杜鹏龙,孟园园,王俊文等.基于密度泛函理论的异质结CoCu(100)/(111)表面催化合成气直接制乙醇机理研究[J].低碳化学与化工,2025,50(12):21-29.

DU Penglong,MENG Yuanyuan,WANG Junwen,et al.Mechanisms of direct synthesis of ethanol from syngas catalyzed by heterojunction CoCu(100)/(111) surface based on density functional theory[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):21-29.
杜鹏龙,孟园园,王俊文等.基于密度泛函理论的异质结CoCu(100)/(111)表面催化合成气直接制乙醇机理研究[J].低碳化学与化工,2025,50(12):21-29. DOI： 10.12434/j.issn.2097-2547.20250074.

DU Penglong,MENG Yuanyuan,WANG Junwen,et al.Mechanisms of direct synthesis of ethanol from syngas catalyzed by heterojunction CoCu(100)/(111) surface based on density functional theory[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):21-29. DOI： 10.12434/j.issn.2097-2547.20250074.

摘要

合成气直接制乙醇作为一种新兴的新能源技术，目前仍面临催化剂催化效率低、产物选择性低等问题。这些问题主要源于C—O键断裂和C—C键形成的能垒较高以及反应难以调控。因此，通过密度泛函理论（DFT），系统研究了在CoCu(100)、CoCu(111)和异质结CoCu(100)/(111)表面上合成气直接制乙醇的反应机理，重点探讨了异质结CoCu(100)/(111)表面对CO活化、C—O键断裂及C—C键形成的影响。结果表明，CO在Co位点加氢生成CHO，进一步解离加氢生成中间体CH

，CO再插入中间体CH

生成中间体CH

CO，最终通过连续加氢转化为乙醇。与CoCu(100)和CoCu(111)表面相比，异质结CoCu(100)/(111)表面因具有良好的局部电子结构，在促进CO活化、C—O键断裂和C—C键形成中展现出优势。本结果可为设计和优化高效Cu基催化剂提供重要的理论依据，为合成气制乙醇技术的工业化应用提供借鉴。

Abstract

As an emerging new energy technology

the direct synthesis of ethanol from syngas still faces problems such as low catalytic efficiency of catalysts and product selectivities. These problems are mainly due to the high energy barriers of C—O bond breakage and C—C bond formation

as well as the difficulty of controlling reaction. So

the reaction mechanisms of direct synthesis of ethanol from syngas on CoCu(100)

CoCu(111) and heterojunction CoCu(100)/(111) surfaces were systematically studied by density functional theory (DFT)

and the effects of heterojunction CoCu(100)/(111) on CO activation

C—O bond breakage and C—C bond formation were emphatically discussed. The results show that CO is hydrogenated at the Co site to generate CHO

further dissociated and hydrogenated to generate intermediate CH

and CO is then inserted into intermediate CH

to generate intermediate CH

and finally converted to ethanol by continuous hydrogenation. Compared with CoCu(100) and CoCu(111) surfaces

heterojunction CoCu(100)/(111) surface has advantages in promoting CO activation

C—O bond breakage and C—C bond formation due to its good local electronic structure. The results can provide an important theoretical basis for the design and optim

ization of high-efficiency Cu-based catalysts

and provide reference for the industrial application of synthesis of ethanol from syngas.

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references

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