Zn、Zr电子间相互作用对ZnZr催化剂CO<sub>2</sub>加氢制甲醇性能的影响

周宇; 毛晓瑛; 张博雅; 张亚平

doi:10.12434/j.issn.2097-2547.20240365

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Zn、Zr电子间相互作用对ZnZr催化剂CO₂加氢制甲醇性能的影响

甲醇合成与催化转化 | 更新时间：2025-05-29

- Zn、Zr电子间相互作用对ZnZr催化剂CO₂加氢制甲醇性能的影响
- Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO₂ hydrogenation to methanol
- 低碳化学与化工 2025, 50(5): 120-131.
- 作者机构：
  
  东南大学能源与环境学院能源热转换及其过程测控教育部重点实验室，江苏南京 210096
- 作者简介：
  
  周宇（1997—），博士研究生，研究方向为CO2资源化利用技术，E-mail：zy15856926003@163.com。
  张亚平（1979—），博士，教授，研究方向为大气污染物控制及利用，E-mail：amflora@seu.edu.cn。
- 基金信息：
  
  江苏省重点研发计划(BE2022602-3)
- DOI：10.12434/j.issn.2097-2547.20240365
  中图分类号： TQ426.82
- 收稿日期：2024-09-02，
  
  修回日期：2024-09-20，
  
  纸质出版日期：2025-05-25
- 稿件说明：
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周宇,毛晓瑛,张博雅等.Zn、Zr电子间相互作用对ZnZr催化剂CO₂加氢制甲醇性能的影响[J].低碳化学与化工,2025,50(05):120-131.

ZHOU Yu,MAO Xiaoying,ZHANG Boya,et al.Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO₂ hydrogenation to methanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):120-131.
周宇,毛晓瑛,张博雅等.Zn、Zr电子间相互作用对ZnZr催化剂CO₂加氢制甲醇性能的影响[J].低碳化学与化工,2025,50(05):120-131. DOI： 10.12434/j.issn.2097-2547.20240365.

ZHOU Yu,MAO Xiaoying,ZHANG Boya,et al.Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO₂ hydrogenation to methanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):120-131. DOI： 10.12434/j.issn.2097-2547.20240365.

摘要

将CO

进行化学转化利用有助于CO

减排，从而减缓温室效应，且CO

加氢制甲醇可在一定程度上弥补未来能源缺口。目前，开发高性能的催化剂成为CO

加氢制甲醇技术发展的关键。以ZnZr催化剂为研究对象，采用浸渍法合成了不同

(Zn)/

(Zr)的

Zn-ZrO

和不同

(Zr)/

(Zn)的

Zr-ZnO催化剂，并采用XRD、N

吸/脱附、XPS、H

-TPR和in situ DRIFTS等手段对催化剂进行了表征。结果表明，在

Zn-ZrO

催化剂中，0.50 Zn-ZrO

（

(Zn)/

(Zr) = 0.50）的甲醇时空产率最高，在320 ℃、5 MPa下达141 mg/(g·h)。在相同测试条件下，在

Zr-ZnO催化剂中，0.20 Zr-ZnO（

(Zr)/

(Zn) = 0.20）的甲醇时空产率最高（165 mg/(g·h) ）。

Zn-ZrO

催化剂中，Zn与Zr之间存在电子相互作用，导致富电子Zn位点和缺电子Zr位点形成，更多的电子从Zr转移到Zn，有利于提高甲醇选择性和时空产率。

Zr-ZnO催化剂中，表面吸附氧成为影响CO

转化率的关键因素。此外，HCOO*中间物种扮演着关键角色，在

Zn-ZrO

和

Zr-ZnO催化剂催化下的CO

加氢制甲醇中，HCOO*物种越多，越有利于甲醇合成。

Abstract

chemical conversion is beneficial for CO

ission reduction to reduce the greenhouse effect

and CO

hydrogenation to methanol can make up for the future energy gap to a certain extent. At present

the development of high-performance catalysts has become a key target for the development of CO

hydrogenation to methanol technology.

Zn-ZrO

with different

(Zn)/

(Zr) and

Zr-ZnO with different

(Zr)/

(Zn) catalysts were synthesized by impregnation method

using ZnZr catalyst as the research object

and the catalysts were characterized by XRD

adsorption/desorption

XPS

-TPR

insitu DRIFTS and so on. The results show that 0.50 Zn-ZrO

catalyst (

(Zn)/

(Zr) = 0.50) among

Zn-ZrO

catalysts

has the highest methanol space time yield with 141 mg/(g·h) at 320 ℃ and 5 MPa. 0.20 Zr-ZnO (

(Zr)/

(Zn) = 0.20) among

Zr-ZnO catalysts has highest methanol space time yield with 165 mg/(g·h) under the same test conditions. In

Zn-ZrO

catalysts

there are electron interactions between Zn and Zr

resulting in the formation of electron-rich Zn sites and electron-deficient Zr sites

and more electrons are transferred from Zr to Zn

which is beneficial for improving methanol selectivity and space time yield. In

Zr-ZnO catalysts

surface adsorbed oxygen becomes a key factor affecting CO

conversion rate. In addition

the HCOO* intermediate species play a key role. It is confirmed that in the CO

hydrogenation to methanol catalyzed by

Zn-ZrO

and

Zr-ZnO catalysts

the more HCOO* species there are

the more favorable it is for methanol synthesis.

关键词

Keywords

references

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Zn、Zr电子间相互作用对ZnZr催化剂CO2加氢制甲醇性能的影响

Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO2 hydrogenation to methanol

DOI：10.12434/j.issn.2097-2547.20240365

摘要

Abstract

关键词

Keywords

references

Zn、Zr电子间相互作用对ZnZr催化剂CO₂加氢制甲醇性能的影响

Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO₂ hydrogenation to methanol