形貌调控TiO<sub>2</sub>负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响

张雨; 张旭妍; 邵旭浩; 艾培培; 黄伟

doi:10.12434/j.issn.2097-2547.20250174

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形貌调控TiO₂负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响

低碳分子转化合成 | 更新时间：2026-04-23

- 形貌调控TiO₂负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响
- Effects of morphology modulation on TiO₂-supported Cu catalysts for selective hydrogenation of dimethyl oxalate to methyl glycolate
- 低碳化学与化工 2026, 51(4): 59-69.
- 作者机构：
  
  太原理工大学化学与化工学院省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
- 作者简介：
  
  张雨（2000—），硕士研究生，研究方向为碳一化学与多相催化，E-mail：zhangyu0739@link.tyut.edu.cn。
  艾培培（1986—），博士，副教授，研究方向为碳一化学与多相催化，E-mail：aipeipei@tyut.edu.cn；
  黄伟（1962—），博士，教授，研究方向为碳一化学，E-mail：huangwei@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(22008166);山西省基础研究项目(202403021211029;201901D211047)
- DOI：10.12434/j.issn.2097-2547.20250174
  中图分类号： TQ426;TQ530.2
- 收稿：2025-04-10，
  
  修回：2025-05-12，
  
  纸质出版：2026-04-25
- 稿件说明：
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张雨,张旭妍,邵旭浩等.形貌调控TiO₂负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响[J].低碳化学与化工,2026,51(4):59-69.

ZHANG Yu,ZHANG Xuyan,SHAO Xuhao,et al.Effects of morphology modulation on TiO₂-supported Cu catalysts for selective hydrogenation of dimethyl oxalate to methyl glycolate[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(4):59-69.
张雨,张旭妍,邵旭浩等.形貌调控TiO₂负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响[J].低碳化学与化工,2026,51(4):59-69. DOI： 10.12434/j.issn.2097-2547.20250174.

ZHANG Yu,ZHANG Xuyan,SHAO Xuhao,et al.Effects of morphology modulation on TiO₂-supported Cu catalysts for selective hydrogenation of dimethyl oxalate to methyl glycolate[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(4):59-69. DOI： 10.12434/j.issn.2097-2547.20250174.

摘要

乙醇酸甲酯（MG）作为重要的化工中间体，在医药及精细化学品等领域应用广泛。以合成气为原料，经草酸二甲酯（DMO）加氢制备MG的路线，契合绿色发展理念，具有较高的发展潜力。Cu基催化剂在DMO加氢反应中表现出良好的催化性能，但容易导致深度加氢。为实现DMO高效转化与MG定向合成的协同优化，首先制备了具有不同形貌的TiO

作为载体，然后采用超声浸渍法制备了一系列Cu基催化剂（Cu/TO-N

）。通过SEM、N

物理吸/脱附和XRD等对所得载体、催化剂进行了表征，并研究了Cu/TO-N

在DMO加氢制MG反应中的催化性能。结果表明，具有纳米片结构的载体（TO-NF）的缺陷程度最高、酸性位点最少，有利于Cu物种均匀分散并抑制副反应。Cu/TO-NF的Cu

物种占比（

(Cu

+ Cu

)）最高（74.80%），其Cu物种尺寸为5.45 nm，且Cu物种与TO-NF之间存在电子相互作用。在温度为230 ℃、压力为2.5 MPa、质量空速为0.7 h

-1

和

(DMO) = 30的反应条件下，Cu/TO-NF的DMO转化率、MG选择性和MG产率分别可达到87.73%、82.38%和72.27%。在该反应条件下连续反应550 h，Cu/TO-NF的催化性能可基本保持稳定。

Abstract

As a crucial chemical intermediate

methyl glycolate (MG) has extensive applications in fields such as pharmaceuticals and fine chemicals. The route for preparing MG through the hydrogenation of dimethyl oxalate (DMO) using syngas as the raw material has green development concept and boasts high growth potential. Cu-based catalysts exhibit good catalytic performance in DMO hydrogenation reaction but tend to induce deep hydrogenation. To achieve the synergistic optimization of efficient DMO conversion and selective MG synthesis

TiO

with different morphologies were prepared as the supports firstly

and then a series of Cu-based catalysts (Cu/TO-N

) were fabricated via the ultrasonic impregnation method. The obtained supports and catalysts were characterized by SEM

physical adsorption/desorption

XRD and so on

and the catalytic performances of Cu/TO-N

in DMO hydrogenation to MG were investigated. The results demonstrate that support with nanosheet structure (TO-NF) possesses the highest defect degree and the fewest acidic sites

which are conducive to the uniform dispersion of Cu species and the inhibition of side reactions. The Cu/TO-NF catalyst has the highest proportion (

(Cu

+ Cu

)) of Cu⁰ species at 74.80%

with Cu

particle size of 5.45 nm

and there exists an electronic interaction between the Cu species and TO-NF. Under the reaction conditions of temperature of 230 ℃

pressure of 2.5 MPa

weight hourly space velocity of 0.7 h

-1

and

(DMO) of 30

the DMO conversion rate

MG selectivity and MG yield of Cu/TO-NF can reach 87.73%

82.38% and 72.27%

respectively. Moreover

the catalytic performance of

Cu/TO-NF can remain basically stable after 550 h continuous reaction under the aforementioned conditions.

关键词

Keywords

references

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Effects of morphology modulation on TiO2-supported Cu catalysts for selective hydrogenation of dimethyl oxalate to methyl glycolate

DOI：10.12434/j.issn.2097-2547.20250174

摘要

Abstract

关键词

Keywords

references

形貌调控TiO₂负载Cu催化剂对草酸二甲酯选择性加氢制乙醇酸甲酯的影响

Effects of morphology modulation on TiO₂-supported Cu catalysts for selective hydrogenation of dimethyl oxalate to methyl glycolate