晶界工程诱导二氧化铈电子重分布催化二氧化碳制碳酸二甲酯

doi:10.1016/S1872-2067(25)64871-6

催化学报 ›› 2026, Vol. 80: 316-329.DOI: 10.1016/S1872-2067(25)64871-6

晶界工程诱导二氧化铈电子重分布催化二氧化碳制碳酸二甲酯

侯国强, 许狄(), 范海峰, 李洋洋, 黄思懿, 定明月()

武汉大学动力与机械工程学院, 技术科学研究院, 湖北武汉 430072

收稿日期:2025-06-24 接受日期:2025-09-05 出版日期:2026-01-18 发布日期:2026-01-05
通讯作者: 许狄,定明月
基金资助:
国家重点研发计划(2022YFA1504700);国家自然科学基金(22308266);国家自然科学基金(U21A20317);湖北省创新团队(2022CFA017);中国博士后科学基金(2021M702521);湖北省博士后创新研究岗位

Grain boundary engineering of CeO₂ induced electron redistribution for dimethyl carbonate synthesis from CO₂

Guoqiang Hou, Di Xu(), Haifeng Fan, Yangyang Li, Siyi Huang, Mingyue Ding()

The Institute of Technological Sciences, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, Hubei, China

Received:2025-06-24 Accepted:2025-09-05 Online:2026-01-18 Published:2026-01-05
Contact: Di Xu, Mingyue Ding
Supported by:
China National Key Research and Development Plan Project(2022YFA1504700);National Natural Science Foundation of China(22308266);National Natural Science Foundation of China(U21A20317);Innovative Groups in Hubei Province(2022CFA017);China Postdoctoral Science Foundation(2021M702521);Postdoctoral Innovative Research Post in Hubei Province

摘要/Abstract

摘要：

工业化进程加速了能源消费, 导致大气中CO₂等温室气体浓度持续升高. 2022年, 由不可再生能源的使用排放的CO₂达368亿吨, 远超自然固碳速率, 使得减排成为一项紧迫的环境问题. 因此, CO₂高效转化为高附加值化学品至关重要. 其中, 碳酸二甲酯(DMC)因其含有羰基、甲氧基等多种官能团, 可作为光气等剧毒物质的绿色替代品, 已广泛应用于医药、石油添加剂及电解质领域. 现有工业制备方法存在显著局限:传统光气法虽产率较高, 但存在剧毒物质使用风险; 酯交换法则受限于催化剂成本或反应安全性; 氧化羰基化法虽具有理论原子经济性优势, 但需苛刻反应条件且产物纯度受限. 相比之下, 以CO₂和甲醇直接合成DMC具有环境友好、原子经济性高及安全等优势, 能利用温室气体和煤化工下游产品, 学术与应用潜力巨大. 然而, 惰性的CO₂分子难活化, 如何促进关键中间体*CH₃OCOO的生成和转化以提升DMC产率, 是该反应的核心挑战.

本研究创新性地提出一种硼酸辅助再结晶策略, 通过添加4%硼酸成功构筑了富含晶界(GBs)缺陷的CeO₂空心纳米球催化剂(4%BCeO₂-GBs). 通过系统的结构表征与机理研究, 发现晶界缺陷的引入诱导了CeO₂电子结构的显著重构: 一方面, 电子从体相Ce离子向晶界界面迁移, 形成体相缺电子区与界面局域富电子区的协同体系; 另一方面, 晶界作为体相缺陷促进了单电子物种的生成. 这种独特的电子分布通过双路径提升催化性能: 在体相区域, Ce离子的电子缺失削弱了*CH₃O物种的吸附强度, 从而显著加速*CH₃O与CO₂耦合形成关键中间体CH₃OCOO的速率; 在界面区域, 富电子环境通过单电子氧物种增强CO₂的化学吸附, 进而有效降低了CH₃OCOO的解离能垒, 推动其高效转化为DMC. 催化性能测试结果表明, 在无脱水剂条件下, 4%BCeO₂-GBs的DMC产率达19.8 mmol/g, 具有显著的性能优势. 当引入脱水剂2-氰基吡啶后, DMC产率飙升至264.2 mmol/g(甲醇转化率7.12%), 较商业CeO₂提升了32倍.

综上, 本研究不仅首次阐明晶界缺陷通过电子重分布调控CH₃OCOO中间体行为的原子级机制, 更开创了“晶界工程”设计高效CO₂固定催化剂的设计思路.

关键词: 碳酸二甲酯合成, 二氧化铈催化剂, 晶界工程, 电子重分布, 反应中间体

Abstract:

Direct synthesis of dimethyl carbonate (DMC) from CO₂ is critical for achieving carbon neutrality, yet the sluggish formation and conversion of the key *CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields. Herein, we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO₂ hollow nanospheres, which serve as an efficient catalyst for CO₂ to DMC synthesis. The introduction of grain-boundary (GBs) induced the electron redistribution, which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface. This unique electronic landscape promoted reactive methoxy formation and stronger CO₂ adsorption, thereby enabling more efficient coupling of *CH₃O and *CO₂ to form the *CH₃OCOO. Concurrently, the enhanced CO₂ adsorption facilitated the dissociation of *CH₃OCOO and subsequent DMC formation. As a result, the 4%BCeO₂-GBs achieved an advantageous DMC yield of 19.8 mmol/g. In the assistance of dehydrating agent, the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12% methanol conversion, which was 32 times higher than commercial CeO₂. This study elucidated the intrinsic mechanisms governing *CH₃OCOO intermediate behavior and offers valuable guidance for CO₂ converting into high-value organic chemicals.

Key words: Dimethyl carbonate synthesis, CeO₂ catalyst, Grain boundary engineering, Electron redistribution, Reaction intermediates

侯国强, 许狄, 范海峰, 李洋洋, 黄思懿, 定明月. 晶界工程诱导二氧化铈电子重分布催化二氧化碳制碳酸二甲酯[J]. 催化学报, 2026, 80: 316-329.

Guoqiang Hou, Di Xu, Haifeng Fan, Yangyang Li, Siyi Huang, Mingyue Ding. Grain boundary engineering of CeO₂ induced electron redistribution for dimethyl carbonate synthesis from CO₂[J]. Chinese Journal of Catalysis, 2026, 80: 316-329.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64871-6

https://www.cjcatal.com/CN/Y2026/V80/I1/316

图/表 8

Scheme 1. Potential role of grain boundary in regulation of electronic structure of CeO2 and reactant adsorption in DMC synthesis from CO2 and methanol.

Fig. 1. The process of formation of CeO2 catalyst by dissolution-recrystallization. (a) TEM images of crystal growth process of Norm-CeO2, 4%BCeO2-GBs and 8%BCeO2 with increasing time from 90 to 200 min at 180 °C. (b) Schematic illustration for fabrication of 4%BCeO2-GBs hollow catalyst.

Fig. 2. Characterization of catalyst. The micro-morphological ofNorm-CeO2 (a), 2%BCeO2-GBs (b), 4%BCeO2-GBs (c), and 8%BCeO2 (d). (e) Rietveld refinement XRD pattern in the range of 5?80 and crystal structure of Norm-CeO2 and 4%BCeO2-GBs. HRTEM images and FFT images of Norm-CeO2 (f) and 4%BCeO2-GBs (g). (h1) Integrated pixel intensities of Norm-CeO2 from the Fig. 2(f). Integrated pixel intensities of GBs taken from the direction of arrow in blue (h2), red (h3), and green (h4). (i) HRTEM images image of 8%B/CeO2. (j) Raman spectra of Norm-CeO2 and 4%BCeO2-GBs at 1% power.

Fig. 3. The catalytic performance of CeO2 catalysts. (a) DMC yield of CeO2 catalysts at 140 °C. (b) DMC yield on 4%BCeO2-GBs at different temperatures. (c) Cycling stability of 4%BCeO2-GBs at 140 and 160 °C. (d) Comparison of the DMC yield with the reported metal oxide catalysts at similar conditions. Reaction conditions: 100 mg catalyst; 11.88 g MeOH; pure CO2; 3.5 MPa; 100?180 °C for 3 h. All data was collected by the average of three times results, the relative error less than 1.8%.

Fig. 4. Structural analysis of CeO2 catalysts. XPS spectra of Ce 3d (a) and O 1s (b) of Norm-CeO2 and 4%BCeO2-GBs and 8%BCeO2. (c) The electron-density distribution CeO2 catalysts containing GBs. (d) ESR spectra of Norm-CeO2 and 4%BCeO2-GBs. CO2-TPD (e) and in-situ DRIFTS of CO2 adsorption (f) of Norm-CeO2 and 4%BCeO2-GBs. (g) The correlation of base density (red line) and IR intensity of bidentate carbonate (blue line) with spin concentration. MeOH-TPD (h) and in-situ DRIFTS of MeOH adsorption (i) of Norm-CeO2 and 4%BCeO2-GBs.

Fig. 5. Reaction mechanism. DRIFTS spectra of pre-adsorbed with MeOH followed by passing CO2 at 140 °C and dynamic relative IR bands intensities of adsorption species for 4%BCeO2-GBs (a,b) and Norm-CeO2 (c,d). DRIFTS spectra of pre-adsorbed with CO2 20 min, Ar was introduced to show the *CO2 adsorption strength, followed by passing MeOH at 140 °C and dynamic relative IR bands intensities of adsorption species for 4%BCeO2-GBs (e,f) and Norm-CeO2 (g,h). The highest IR band intensity of species was defined as 100%.

Fig. 6. Reaction mechanism. DRIFTS spectra of pre-adsorbed with DMC followed by passing Ar at 160 °C and dynamic relative IR bands intensities of decomposed species for 4%BCeO2-GBs (a,b) and Norm-CeO2 (c,d). The highest IR band intensity of species was defined as 100%.

Scheme 2. Potential reaction mechanism for DMC synthesis from CO2 and methanol on 4%BCeO2-GBs.

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晶界工程诱导二氧化铈电子重分布催化二氧化碳制碳酸二甲酯

Grain boundary engineering of CeO₂ induced electron redistribution for dimethyl carbonate synthesis from CO₂

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晶界工程诱导二氧化铈电子重分布催化二氧化碳制碳酸二甲酯

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