Pd-CuxO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol

doi:10.1016/j.cjche.2025.05.018

中国化学工程学报 ›› 2025, Vol. 86 ›› Issue (10): 104-113.DOI: 10.1016/j.cjche.2025.05.018

• Special Issue on Celebrating the 100th Anniversary of the School of Chemical Engineering and Technology of Tianjin University • 上一篇下一篇

Pd-Cu_xO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol

Jian Zhang^1,2, Jieqiong Zhao¹, Caifeng Qi¹, Zhe An^1,2, Yanru Zhu^1,2, Xin Shu¹, Hongyan Song¹, Jing He^1,2

1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
2. Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou 324000, China

收稿日期:2025-03-30 修回日期:2025-05-07 接受日期:2025-05-08 出版日期:2025-10-28 发布日期:2025-06-19
通讯作者: Jing He,E-mail:hejing@mail.buct.edu.cn
基金资助:
Financial support from the National Natural Science Foundation of China (22138001 and 22288102) is gratefully acknowledged.

Pd-Cu_xO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol

Jian Zhang^1,2, Jieqiong Zhao¹, Caifeng Qi¹, Zhe An^1,2, Yanru Zhu^1,2, Xin Shu¹, Hongyan Song¹, Jing He^1,2

1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
2. Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou 324000, China

Received:2025-03-30 Revised:2025-05-07 Accepted:2025-05-08 Online:2025-10-28 Published:2025-06-19
Contact: Jing He,E-mail:hejing@mail.buct.edu.cn
Supported by:
Financial support from the National Natural Science Foundation of China (22138001 and 22288102) is gratefully acknowledged.

摘要/Abstract

摘要： Oxidative carbonylation of ethanol to diethyl carbonate (DEC), an essential electrolyte for lithium-ion battery, has attracted broad interest from both academia and industry in recent years. But high selective formation of DEC is a great challenge due to the difficulty in efficient activation of CO at the same time as the site-specific activation of O—H bond in ethanol. Herein, we propose a Pd-Cu_xO synergetic catalysis toward oxidative carbonylation of ethanol, where the synergy between Pd and Cu_xO promotes CO activation and carbonylation, thus increasing the selectivity to the site-specific activation of O—H bond in ethanol. A nitrogen-doped carbon nanotubes supported Pd-Cu_xO (Pd-Cu_xO/NCNTs) has been designed via galvanic displacement of Pd on Cu_xO to form the strong interactions between Pd and Cu_xO, affording a selectivity of 94.7% to DEC and a space-time yield (STY) of up to 5966 mg·g^-1·h^-1, which is an order of magnitude higher than that reported in the literatures. This work offers novel insights for the design of highly efficient catalysts and advances the industrial development for the oxidative carbonylation of ethanol.

关键词: Pd-Cu_xO synergetic catalysis, Ethanol conversion, Oxidative carbonylation, Activation of O—H bond, Diethyl carbonate

Abstract: Oxidative carbonylation of ethanol to diethyl carbonate (DEC), an essential electrolyte for lithium-ion battery, has attracted broad interest from both academia and industry in recent years. But high selective formation of DEC is a great challenge due to the difficulty in efficient activation of CO at the same time as the site-specific activation of O—H bond in ethanol. Herein, we propose a Pd-Cu_xO synergetic catalysis toward oxidative carbonylation of ethanol, where the synergy between Pd and Cu_xO promotes CO activation and carbonylation, thus increasing the selectivity to the site-specific activation of O—H bond in ethanol. A nitrogen-doped carbon nanotubes supported Pd-Cu_xO (Pd-Cu_xO/NCNTs) has been designed via galvanic displacement of Pd on Cu_xO to form the strong interactions between Pd and Cu_xO, affording a selectivity of 94.7% to DEC and a space-time yield (STY) of up to 5966 mg·g^-1·h^-1, which is an order of magnitude higher than that reported in the literatures. This work offers novel insights for the design of highly efficient catalysts and advances the industrial development for the oxidative carbonylation of ethanol.

Key words: Pd-Cu_xO synergetic catalysis, Ethanol conversion, Oxidative carbonylation, Activation of O—H bond, Diethyl carbonate

Jian Zhang, Jieqiong Zhao, Caifeng Qi, Zhe An, Yanru Zhu, Xin Shu, Hongyan Song, Jing He. Pd-Cu_xO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol[J]. 中国化学工程学报, 2025, 86(10): 104-113.

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Pd-Cu_xO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol

Pd-Cu_xO synergetic catalysis towards high-efficient oxidative carbonylation of ethanol

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