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Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO2 hydrogenation to methanol
- Low-Carbon Chemistry and Chemical Engineering Vol. 50, Issue 5, Pages: 120-131(2025)
- 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：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240365
CLC： TQ426.82Received：02 September 2024，
Revised：20 September 2024，
Published：25 May 2025
- 稿件说明：
移动端阅览
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
2
进行化学转化利用有助于CO
2
减排，从而减缓温室效应，且CO
2
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
2
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
n
(Zn)/
n
(Zr)的
x
Zn-ZrO
2
和不同
n
(Zr)/
n
(Zn)的
y
Zr-ZnO催化剂，并采用XRD、N
2
吸/脱附、XPS、H
2
-TPR和in situ DRIFTS等手段对催化剂进行了表征。结果表明，在
x
Zn-ZrO
2
催化剂中，0.50 Zn-ZrO
2
（
n
(Zn)/
n
(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
y
Zr-ZnO催化剂中，0.20 Zr-ZnO（
n
(Zr)/
n
(Zn) = 0.20）的甲醇时空产率最高（165 mg/(g·h) ）。
x
Zn-ZrO
2
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。
y
Zr-ZnO催化剂中，表面吸附氧成为影响CO
2
转化率的关键因素。此外，HCOO*中间物种扮演着关键角色，在
x
Zn-ZrO
2
和
y
Zr-ZnO催化剂催化下的CO
2
加氢制甲醇中，HCOO*物种越多，越有利于甲醇合成。
Abstract
CO
2
chemical conversion is beneficial for CO
2
em
ission reduction to reduce the greenhouse effect
and CO
2
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
2
hydrogenation to methanol technology.
x
Zn-ZrO
2
with different
n
(Zn)/
n
(Zr) and
y
Zr-ZnO with different
n
(Zr)/
n
(Zn) catalysts were synthesized by impregnation method
using ZnZr catalyst as the research object
and the catalysts were characterized by XRD
N
2
adsorption/desorption
XPS
H
2
-TPR
insitu DRIFTS and so on. The results show that 0.50 Zn-ZrO
2
catalyst (
n
(Zn)/
n
(Zr) = 0.50) among
x
Zn-ZrO
2
catalysts
has the highest methanol space time yield with 141 mg/(g·h) at 320 ℃ and 5 MPa. 0.20 Zr-ZnO (
n
(Zr)/
n
(Zn) = 0.20) among
y
Zr-ZnO catalysts has highest methanol space time yield with 165 mg/(g·h) under the same test conditions. In
x
Zn-ZrO
2
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
y
Zr-ZnO catalysts
surface adsorbed oxygen becomes a key factor affecting CO
2
conversion rate. In addition
the HCOO* intermediate species play a key role. It is confirmed that in the CO
2
hydrogenation to methanol catalyzed by
x
Zn-ZrO
2
and
y
Zr-ZnO catalysts
the more HCOO* species there are
the more favorable it is for methanol synthesis.
关键词
Keywords
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