铈锆固溶体Ce0.25Zr0.75O2光热协同催化CO2与甲醇合成DMC

doi:10.16085/j.issn.1000-6613.2023-0747

摘要/Abstract

摘要：

采用溶胶-凝胶法合成不同铈含量的ZrO₂催化剂，用于光热协同催化CO₂与甲醇直接合成碳酸二甲酯（DMC）。实验发现，光热催化的DMC产率明显高于热催化，且Ce_0.25Zr_0.75O₂具有最高DMC产率3.084mmol/g，是纯ZrO₂的1.9倍。XRD和TEM分析表明：Ce原子掺入ZrO₂晶格形成铈锆固溶体同时增加其表面氧空位浓度，提高吸附CO₂能力；固溶体的纳米尺寸减小、比表面积增大和介孔结构丰富，有利于CO₂扩散。能带结构和光吸收光谱表明：铈锆固溶体光响应范围拓宽且有效利用率提高；氧空位辅助窄带隙特征可促使光生载流子有效分离，允许更多光生电子和空穴参与CO₂及甲醇的活化，加之固溶体表面酸碱位点的协同作用，最终实现高效率高选择性合成DMC。最后，提出了铈锆固溶体光热催化CO₂与甲醇合成DMC的反应机理，为光协同热催化合成DMC的研究提供良好的理论基础和实验数据。

关键词: 二氧化碳, 碳酸二甲酯, 光热协同催化, 铈锆固溶体, 氧空位

Abstract:

ZrO₂ catalysts with different Ce contents were synthesized by sol-gel method and used for carrying out to achieve the photothermal catalytic direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol. Experimental results revealed that the DMC yield via photothermal catalysis was obviously higher than single thermal catalysis, and Ce_0.25Zr_0.75O₂ had the best effect with the DMC yield of 3.084mmol/g, which was 1.9 times that of pure ZrO₂. XRD and TEM analysis results showed that Ce atoms were doped into the crystal lattice of ZrO₂, which led to the formation of cerium-zirconium solid solution and the increasing concentration of surface oxygen vacancies, improving the CO₂ adsorption capacity. The solid solution had smaller nano size and larger specific surface area, and its formation of mesoporous structure was more conducive to CO₂ diffusion. The energy band structure and optical absorption spectra confirmed that the photoresponse of solid solution was widened and the light utilization efficiency was raised. Besides, with the assistance of oxygen vacancy in the narrow band gap prompts, the efficient separation of photo-generated carriers would provide more photo-generated electrons and held for activating methanol and CO₂, and combine with acid-base sites on the surface of solid solution, realizing the highly efficient synthesis and selectivity of DMC. Finally, the reaction mechanism of photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution was proposed, which should provide excellent theoretical basis and experimental data for the research and development on the photothermal catalytic synthesis of DMC.

Key words: carbon dioxide(CO₂), dimethyl crbonate(DMC), photothermal co-catalysis, ceria-zirconia solid solution, oxygen vacancies

中图分类号:

TQ032

郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.

ZHENG Qian, GUAN Xiushuai, JIN Shanbiao, ZHANG Changming, ZHANG Xiaochao. Photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 319-327.

图/表 9

图1 DMC产率随Ce含量的变化曲线

图2 ZrO2与Ce0.25Zr0.75O2的XRD谱图

图3 ZrO2与Ce0.25Zr0.75O2的XPS谱图

图4 ZrO2及Ce0.25Zr0.75O2的SEM图及HRTEM图

图5 ZrO2与Ce0.25Zr0.75O2的UV-vis DRS光谱图（a）、带隙图（b）、VB-XPS谱图（c）和PL谱图（d）

图6 ZrO2与Ce0.25Zr0.75O2的N2吸附/脱附等温线（a）、孔径分布曲线（b）及CO2吸附曲线（c）

图7 ZrO2与Ce0.25Zr0.75O2的CO2-TPD曲线（a）及EPR谱图（b）

图8 Ce0.25Zr0.75O2光热催化CO2与甲醇直接合成DMC反应机理

图9 Ce0.25Zr0.75O2的循环性能图（a）及反应前后催化剂XRD图（b）

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铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC

Photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution

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