Ti<sub>3</sub>C<sub>2</sub> MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能

石晓丹; 赵江涛; 张雨; 艾培培; 黄伟

doi:10.12434/j.issn.2097-2547.20240193

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Ti₃C₂ MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能

低碳分子转化合成 | 更新时间：2025-03-27

- Ti₃C₂ MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能
- Catalytic performance of Cu-based catalyst supported on Ti₃C₂ MXene for hydrogenation of dimethyl oxalate to methyl glycolate
- 低碳化学与化工 2025, 50(3): 47-57.
- 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：
  
  石晓丹（1998—），硕士研究生，研究方向为碳一化学与多相催化，E-mail：shixiaodan170902@163.com。
  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：
  
  国家自然科学基金青年科学基金(22008166);山西省自然科学研究面上项目(202403021211029);山西省面上青年基金(201901D211047);山西省高等学校科技创新项目(2019L0185)
- DOI：10.12434/j.issn.2097-2547.20240193
  中图分类号： TQ530.2
- 收稿日期：2024-04-30，
  
  修回日期：2024-05-28，
  
  纸质出版日期：2025-03-25
- 稿件说明：
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石晓丹,赵江涛,张雨等.Ti₃C₂ MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能[J].低碳化学与化工,2025,50(03):47-57.

Xiaodan SHI,ZHAO Jiangtao,ZHANG Yu,et al.Catalytic performance of Cu-based catalyst supported on Ti₃C₂ MXene for hydrogenation of dimethyl oxalate to methyl glycolate[J].Low-carbon Chemistry and Chemical Engineering,2025,50(03):47-57.
石晓丹,赵江涛,张雨等.Ti₃C₂ MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能[J].低碳化学与化工,2025,50(03):47-57. DOI： 10.12434/j.issn.2097-2547.20240193.

Xiaodan SHI,ZHAO Jiangtao,ZHANG Yu,et al.Catalytic performance of Cu-based catalyst supported on Ti₃C₂ MXene for hydrogenation of dimethyl oxalate to methyl glycolate[J].Low-carbon Chemistry and Chemical Engineering,2025,50(03):47-57. DOI： 10.12434/j.issn.2097-2547.20240193.

摘要

乙醇酸甲酯（MG）作为生产可降解塑料聚乙醇酸的关键原料，具有广阔的市场空间和较高的经济价值。草酸二甲酯（DMO）加氢制MG是实现煤炭和天然气资源转化与增值利用的途径之一。但MG是DMO不饱和加氢的产物，现有催化剂难以实现其高效制备。Cu基催化剂虽在DMO加氢反应中应用广泛，但其更倾向于催化DMO深度加氢。选用二维层状Ti

MXene为载体，对其进行碱处理制备了alk-Ti

MXene，进而通过超声浸渍法制备了alk-Ti

MXene负载Cu基催化剂。结果表明，碱处理不仅可以增大载体的层间距（由1.02 nm增大至1.25 nm左右）和比表面积（由3.61 m

/g增大至7.10 m

/g以上），同时也能增加载体表面—OH数量，进而调控载体表面—OH和Cu物种之间的相互作用，最终影响Cu物种的粒径以及价态组成。NaOH处理后的Na-Ti

MXene载体负载Cu催化剂（Cu/Na-Ti

MXene）表现出良好的催化性能和稳定性，其MG收率高达60.63%（反应26 h），且230 h内未出现失活现象。相对适宜的Cu粒径（43.4 n

m）、较高的

(Cu

+ Cu

)（71.17%）以及Cu物种与载体表面—OH间的强相互作用，使Cu/Na-Ti

MXene具有良好的催化性能和稳定性。

Abstract

Methyl glycolate (MG)

as a key raw material for the production of degradable plastic polyethylene glycol acid

has broad market space and high economic value. Hydrogenation of dimethyl oxalate (DMO) to MG is one of the ways to realize the conversion and value-added utilization of coal and natural gas resources. However

MG is the product of unsaturated hydrogenation of DMO

and the existing catalysts are difficult to achieve its efficient preparation. Although Cu-based catalysts are widely used in DMO hydrogenation

they are more inclined to catalyze deep hydrogenation of DMO. Alk-Ti

MXene supports were prepared through alkali treatment using two-dimensional layered Ti

MXene as the support

and alk-Ti

MXene supported Cu-based catalyst was prepared by ultrasonic impregnation method. The results show that the alkali treatment can not only increase the interlayer spacing (from 1.02 nm to about 1.25 nm) and surface area of the supports (from 3.61 m

/g to more than 7.10 m

/g)

but also increase the number of —OH on the support surface

thereby regulating the interaction between —OH on the support surface and Cu species

ultimately affecting the particle size and valence state composition of Cu species. It is worth mentioning that the Cu/Na-Ti

MXene catalyst supported on Na-Ti

MXene after NaOH treatment shows good catalytic performance and stability. The MG yield is up to 60.63% (reaction time of 26 h) and no deactivation occurs within 230 h. The relatively suitable Cu particle size (43.4 nm)

high

(Cu

+ Cu

) (71.17%) and the strong interaction between

Cu species and the surface —OH on the support together endow the Cu/Na-Ti

MXene catalyst with good catalytic performance and stability.

关键词

Keywords

references

WENG Y J , ZOU M , LIU X Y , et al . Conversion of glucose to methyl glycolate in subcritical methanol [J ] . Chemical Communications , 2023 , 59 ( 29 ): 4340 - 4343 .

AI P P , ZHANG L , NIU J C , et al . Boron-doped lamellar porous carbon supported copper catalyst for dimethyl oxalate hydrogenation [J ] . Chinese Journal of Chemical Engineering , 2023 , 55 ( 3 ): 222 - 229 .

YAO J , CAO F H , HAN Y , et al . C1 Chemistry: The stories of research and applications from toyama [J ] . Resources Chemicals and Materials , 2024 , 3 ( 1 ): 62 - 92 .

YAN W Q , ZHANG J B , XIAO L , et al . Toward rational catalyst design for partial hydrogenation of dimethyl oxalate to methyl glycolate: A descriptor-based microkinetic analysis [J ] . Catalysis Science & Technology , 2019 , 9 ( 20 ): 5763 - 5773 .

WANG X , QIN S Q , ZHANG H Q , et al . Effect of Ce addition to Ag/ZrO 2 catalyst on the hydrogenation of DMO to MG [J ] . ChemistrySelect , 2023 , 8 ( 11 ): e202300192 .

YAN W Q , ZHOU R J , JING L J , et al . Computer-aided bimetallic catalyst screening for ester selective hydrogenation [J ] . Catalysis Science & Technology , 2022 , 12 ( 9 ): 2761 - 2765 .

ZHENG X L , LIN H Q , ZHENG J W , et al . Lanthanum oxide-modified Cu/SiO 2 as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol [J ] . ACS Catalysis , 2013 , 3 ( 12 ): 2738 - 2749 .

ZHENG J W , ZHOU J F , LIN H Q , et al . CO-mediated deactivation mechanism of SiO 2 -supported copper catalysts during dimethyl oxalate hydrogenation to ethylene glycol [J ] . The Journal of Physical Chemistry C , 2015 , 119 ( 24 ): 13758 - 13766 .

张大洲 , 卢文新 , 商宽祥 , 等 . 草酸二甲酯加氢制乙醇酸甲酯反应网络分析及其多相加氢催化剂研究进展 [J ] . 化工进展 , 2023 , 42 ( 1 ): 204 - 214 .

ZHANG D Z , LU W X , SHANG K X , et al . Reaction network analysis of dimethyl oxalate hydrogenation to methyl glycolate and recent progress in the heterogeneous catalysts [J ] . Chemical Industry and Engineering Progress , 2023 , 42 ( 1 ): 204 - 214 .

LU X D , WANG G F , YANG Y , et al . A boron-doped carbon aerogel-supported Cu catalyst for the selective hydrogenation of dimethyl oxalate [J ] . New Journal of Chemistry , 2020 , 44 ( 8 ): 3232 - 3240 .

CHEN C C , LIN L , YE R P , et al . Construction of Cu-Ce composite oxides by simultaneous ammonia evaporation method to enhance catalytic performance of Ce-Cu/SiO 2 catalysts for dimethyl oxalate hydrogenation [J ] . Fuel , 2021 , 290 : 120083 .

HUANG H J , WANG B , WANG Y , et al . Partial hydrogenation of dimethyl oxalate on Cu/SiO 2 catalyst modified by sodium silicate [J ] . Catalysis Today , 2020 , 358 : 68 - 73 .

WEN C , CUI Y Y , DAI W L , et al . Solvent feedstock effect: The insights into the deactivation mechanism of Cu/SiO 2 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Chemical Communications , 2013 , 49 ( 45 ): 5195 - 5197 .

CUI Y Y , WANG B , Wen C , et al . Investigation of activated-carbon-supported copper catalysts with unique catalytic performance in the hydrogenation of dimethyl oxalate to methyl glycolate [J ] . ChemCatChem , 2016 , 8 ( 3 ): 527 - 531 .

ABBAS M , CHEN Z , CHEN J G . Shape- and size-controlled synthesis of Cu nanoparticles wrapped on rGO nanosheet catalyst and their outstanding stability and catalytic performance in the hydrogenation reaction of dimethyl oxalate [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 39 ): 19133 - 19142 .

CHEN Y F , HAN L P , ZHU J , et al . High-performance Ag-CuO x nanocomposite catalyst galvanically deposited onto a Ni-foam for gas-phase dimethyl oxalate hydrogenation to methyl glycolate [J ] . Catalysis Communications , 2017 , 96 : 58 - 62 .

DING J , LIU H M , FAN H Y , et al . Effective “exfoliation” of Cu/ZrO 2 by varying Cu content as high performance catalysts for dimethyl oxalate hydrogenation to ethylene glycol [J ] . Catalysis Communications , 2019 , 121 : 62 - 67 .

张庆萧 , 付雪力 , 赖慧荣 , 等 . Rh/Ti 3 C 2 T x MXene催化剂用于氨硼烷催化产氢 [J ] . 上海师范大学学报（自然科学版） , 2021 , 50 ( 5 ): 546 - 552 .

ZHANG Q X , FU X L , LAI H R , et al . Rh/Ti 3 C 2 T x MXene catalyst: Its synthesis and application in the decomposition of ammonia borane to hydrogen [J ] . Journal of Shanghai Normal University (Natural Sciences) , 2021 , 50 ( 5 ): 546 - 552 .

LU X , HUANG H W , ZHANG X Y , et al . Novel light-driven and electro-driven polyethylene glycol/two-dimensional MXene form-stable phase change material with enhanced thermal conductivity and electrical conductivity for thermal energy storage [J ] . Composites Part B: Engineering , 2019 , 177 : 107372 .

QIN Y , LI L H , LI M H , et al . Flexible MXene/copper/cellulose nanofiber heat spreader films with enhanced thermal conductivity [J ] . Nanotechnology Reviews , 2022 , 11 ( 1 ): 1583 - 1591 .

YEN Z H , SALIM T , BOOTHROYD C , et al . MXene nanosheets functionalized with Cu atoms for urea adsorption in aqueous media [J ] . ACS Applied Nano Materials , 2023 , 6 ( 18 ): 16486 - 16496 .

PENG C , WEI P , CHEN X , et al . A hydrothermal etching route to synthesis of 2D MXene (Ti 3 C 2 , Nb 2 C): Enhanced exfoliation and improved adsorption performance [J ] . Ceramics International , 2018 , 44 ( 15 ): 18886 - 18893 .

RONCHI R M , MARCHIORI C F N , ARAUJO C M , et al . Thermoplastic polyurethane-Ti 3 C 2 (T x ) MXene nanocomposite: The influence of functional groups upon the matrix-reinforcement interaction [J ] . Applied Surface Science , 2020 , 528 : 146526 .

李能 , 史祖皓 , 陈星竹 , 等 . 插层限域工程制备MXene及其复合材料的研究进展 [J ] . 武汉工程大学学报 , 2019 , 41 ( 1 ): 46 - 54 .

LI N , SHI Z H , CHEN X Z , et al . Advance progress in synthesis of MXene and MXene-based composites by intercalation confinement engineering [J ] . Journal of Wuhan Institute of Technology , 2019 , 41 ( 1 ): 46 - 54 .

冯万林 . Ti 3 C 2 MXene的合成及其吸波性能的研究 [D ] . 绵阳 : 中国工程物理研究院 , 2019 .

FENG W L . Study on synthesis and microwave absorption properties of Ti 3 C 2 MXene [D ] . Mianyang : China Academy of Engineering Physics , 2019 .

魏文慧 . MXene (Ti 3 C 2 T x )基复合材料的制备及其电容脱盐性能和超级电容特性研究 [D ] . 银川 : 宁夏大学 , 2021 .

WEI W H . Preparation of MXene (Ti 3 C 2 T x )-based composites for capacitive deionization and supercapacitor [D ] . Yinchuan : Ningxia University , 2021 .

LI L , ZHANG N , ZHANG M Y , et al . Ag-nanoparticle-decorated 2D titanium carbide (MXene) with superior electrochemical performance for supercapacitors [J ] . ACS Sustainable Chemistry & Engineering , 2018 , 6 ( 6 ): 7442 - 7450 .

FAN G Y , LI X J , XU C L , et al . Palladium supported on titanium carbide: A highly efficient, durable, and recyclable bifunctional catalyst for the transformation of 4-chlorophenol and 4-nitrophenol [J ] . Nanomaterials , 2018 , 8 ( 3 ): 141 .

YING Y L , LIU Y , WANG X Y , et al . Two-dimensional titanium carbide for efficiently reductive removal of highly toxic chromium(VI) from water [J ] . ACS Applied Materials & Interfaces , 2015 , 7 ( 3 ): 1795 - 1803 .

ZOU G D , ZHANG Z W , GUO J X , et al . Synthesis of MXene/Ag composites for extraordinary long cycle lifetime lithium storage at high rates [J ] . ACS Applied Materials & Interfaces , 2016 , 8 ( 34 ): 22280 - 22286 .

邹国栋 . 新型MAX/MXene基复合电极材料的构筑及电化学性能研究 [D ] . 秦皇岛 : 燕山大学 , 2019 .

ZOU G D . Architecture and electrochemical properties of novel MAX/MXene-based composite electrode materials [D ] . Qinhuangdao : Yanshan University , 2019 .

张庆萧 . 二维MXenes绿色催化材料的合成与设计研究 [D ] . 上海 : 上海师范大学 , 2022 .

ZHANG Q X . Research on synthesis and design of two-dimensional MXenes green catalytic materials [D ] . Shanghai : Shanghai Normal University , 2022 .

LOW J X , ZHANG L Y , TONG T , et al . TiO 2 /MXene Ti 3 C 2 composite with excellent photocatalytic CO 2 reduction activity [J ] . Journal of Catalysis , 2018 , 361 : 255 - 266 .

PENG C , YANG X F , LI Y H , et al . Hybrids of two-dimensional Ti 3 C 2 and TiO 2 Exposing {001} facets toward enhanced photocatalytic activity [J ] . ACS Applied Materials & Interfaces , 2016 , 8 ( 9 ): 6051 - 6060 .

ZU D Y , SONG H R , LI C P , et al . Understanding the self-catalyzed decomplexation mechanism of Cu-EDTA in Ti 3 C 2 T x MXene/peroxymonosulfate process [J ] . Applied Catalysis B: Environmental , 2022 , 306 : 121131 .

李肖瑶 . Ru/Ti 3 C 2 催化剂的制备及其光催化、光热催化性能研究 [D ] . 广州 : 华南理工大学 , 2019 .

LI X Y . Synthesis of Ru/Ti 3 C 2 for photocatalysis and photothermal catalysis [D ] . Guangzhou : South China University of Technology , 2019 .

JIANG K , ZHAO H B , CHEN Y , et al . Tuning interfaces between Cu and oxide via atomic layer deposition method for CO 2 hydrogenation to methanol [J ] . Catalysis Science & Technology , 2024 , 14 ( 2 ): 261 - 266 .

ZHAO H B , YU R F , MA S C , et al . The role of Cu 1 —O 3 species in single-atom Cu/ZrO 2 catalyst for CO 2 hydrogenation [J ] . Nature Catalysis , 2022 , 5 : 818 - 831 .

YIN A Y , GUO X Y , FAN K N , et al . Influence of copper precursors on the structure evolution and catalytic performance of Cu/HMS catalysts in the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Applied Catalysis A: General , 2010 , 377 ( 1/2 ): 128 - 133 .

LIU Y J , DENG X , HAN P D , et al . Higher alcohols synthesis from syngas over P-promoted non-noble metal Cu-based catalyst [J ] . Fuel , 2017 , 208 : 423 - 429 .

SAN X G , ZHANG Y , SHEN W J , et al . New synthesis method of ethanol from dimethyl ether with a synergic effect between the zeolite catalyst and metallic catalyst [J ] . Energy & Fuels , 2009 , 23 ( 5 ): 2843 - 2844 .

WANG Y , YANG W L , YAO D W , et al . Effect of surface hydroxyl group of ultra-small silica on the chemical states of copper catalyst for dimethyl oxalate hydrogenation [J ] . Catalysis Today , 2020 , 350 : 127 - 135 .

SHI X P , YU H B , GAO S , et al . Synergistic effect of nitrogen-doped carbon-nanotube-supported Cu-Fe catalyst for the synthesis of higher alcohols from syngas [J ] . Fuel , 2017 , 210 : 241 - 248 .

俞金山 , 冯翀 , 刘甜甜 , 等 . 可抑制1,2-丁二醇生成的高性能草酸二甲酯加氢B-Cu/MS催化剂的研究 [J ] . 天然气化工—C1化学与化工 , 2021 , 46 ( 4 ): 33 - 40 .

YU J S , FENG C , LIU T T , et al . Study on high performance B-Cu/MS catalyst for suppressing by-product 1,2-butanediol in hydrogenation of dimethyl oxalate [J ] . Natural Gas Chemical Industry , 2021 , 46 ( 4 ): 33 - 40 .

SUN J , YU J F , MA Q X , et al . Freezing copper as a noble metal-like catalyst for preliminary hydrogenation [J ] . Science Advances , 2018 , 4 ( 12 ): eaau3275 .

AN J W , WANG X H , ZHAO J X , et al . Density-functional theory study on hydrogenation of dimethyl oxalate to methyl glycolate over copper catalyst: Effect of copper valence state [J ] . Molecular Catalysis , 2020 , 110667 .

FANG Y , WANG F , CHEN Y , et al . Realizing methanol synthesis from CO and water via the synergistic effect of Cu 0 /Cu + over Cu/ZrO 2 catalyst [J ] . Journal of Energy Chemistry , 2024 , 93 : 126 - 134 .

YE R P , LIN L , WANG L C , et al . Perspectives on the active sites and catalyst design for the hydrogenation of dimethyl oxalate [J ] . ACS Catalysis , 2020 , 10 ( 8 ): 4465 - 4490 .

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DOI：10.12434/j.issn.2097-2547.20240193

摘要

Abstract

关键词

Keywords

references

Ti₃C₂ MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能

Catalytic performance of Cu-based catalyst supported on Ti₃C₂ MXene for hydrogenation of dimethyl oxalate to methyl glycolate