Oxygen Vacancies in Pd/Pr-CeO2 Catalyst Regulate the Selectivity of CO Esterification to Dimethyl Carbonate

doi:10.6023/A25020035

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (7): 655-660.DOI: 10.6023/A25020035 Previous Articles Next Articles

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Pd/Pr-CeO₂催化剂载体氧空位调控CO酯化制碳酸二甲酯选择性

徐梦鑫^a^,^b, 杨智健^a, 孙径^a, 邹文强^a, 徐忠宁^a^,^*(), 郭国聪^a

^a 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002
^b 中国科学院大学材料科学与光电技术学院北京 100049

投稿日期:2025-02-02 发布日期:2025-07-28
基金资助:
国家重点研发计划项目(2021YFB3801600); 国家自然科学基金面上项目(22172171); 福建省自然科学基金(2022H0039); 榆林中科洁净能源创新研究院联合基金(2022010); 海西研究院自主部署项目(CXZX-2022-GH05)

Oxygen Vacancies in Pd/Pr-CeO₂ Catalyst Regulate the Selectivity of CO Esterification to Dimethyl Carbonate

Meng-Xin Xu^a^,^b, Zhi-Jian Yang^a, Jing Sun^a, Wen-Qiang Zou^a, Zhong-Ning Xu^a^,^*(), Guo-Cong Guo^a

^a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
^b College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-02-02 Published:2025-07-28
Contact: *E-mail: znxu@fjirsm.ac.cn
Supported by:
National Key R&D Program of China(2021YFB3801600); National Natural Science Foundation of China(22172171); Natural Science Foundation of Fujian Province(2022H0039); Grant YLU-DNL Fund(2022010); Program of Haixi Institute(CXZX-2022-GH05)

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Abstract

The resource characteristics of “oil-deficient, gas-deficient, and coal is relatively abundant” in China determine that coal-based CO esterification to dimethyl carbonate (DMC) is of great value. Pd(II)/NaY has been proved to be an effective catalyst for this reaction, but because the acidity of NaY molecular sieve causes partial decomposition of the raw material methyl nitrite, it is of great significance to develop non-molecular sieve catalysts. CeO₂ is a commonly used oxide support. Because of its weak acidity, the decomposition problem of methyl nitrite is almost non-existent, but the selectivity to DMC over Pd/CeO₂ catalyst is low. In order to improve the DMC selectivity, this work introduced different proportions of Pr into CeO₂ carrier, in order to increase the oxygen vacancy concentration of CeO₂, and then improve DMC selectivity. We synthesized Pd/Pr-CeO₂-2.5, Pd/Pr-CeO₂-5, Pd/Pr-CeO₂-7.5, and Pd/Pr-CeO₂-10 catalysts with different Pr doping ratios, and found that their DMC selectivity was significantly different. Pd/Pr-CeO₂-5 catalyst showed the best DMC selectivity (77%). To explore the reasons for this difference, we performed a series of characterizations. Inductively coupled plasma (ICP) and transmission electron microscopy (TEM) demonstrated the successful doping of Pr into the support. By Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis, combined with catalytic performance, it is found that the selectivity to DMC is proportional to the concentration of oxygen vacancy. Through the characterization of hydrogen programmed temperature reduction (H₂-TPR), it was found that the reduction temperature of Pd/Pr-CeO₂-5 catalyst is the highest, indicating that Pd/Pr-CeO₂-5 catalyst with the highest oxygen vacancy concentration also had the strongest metal-support interaction, which could stabilize Pd(II) active species. Therefore, the highest DMC selectivity is shown. The results of this work reveal the structure-activity relationship between the oxygen vacancy concentration of the oxide support and the selectivity of DMC, which has important guiding significance for the development of high-performance DMC catalysts in non-molecular sieve systems.

Key words: CeO₂, rare earth doping, oxygen vacancy, CO esterification, dimethyl carbonate

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Meng-Xin Xu, Zhi-Jian Yang, Jing Sun, Wen-Qiang Zou, Zhong-Ning Xu, Guo-Cong Guo. Oxygen Vacancies in Pd/Pr-CeO₂ Catalyst Regulate the Selectivity of CO Esterification to Dimethyl Carbonate[J]. Acta Chimica Sinica, 2025, 83(7): 655-660.

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Fig. & Tab. 7

Figure 1. The selectivities of DMC and DMO in the esterification of CO to DMC reaction with four catalysts (Reaction conditions: 200 mg of catalysts, 0.1 MPa, 120 ℃, space velocity of 2500 L•kgcat-1•h-1, V(CH3ONO)/V(CO)=2.4, reaction for 6 h)

Figure 2. XRD patterns of Pd/Pr-CeO2 catalysts

Figure 3. (a) TEM image and (b) HRTEM image of Pd/Pr-CeO2-2.5 catalyst; (c) TEM image and (d) HRTEM image of Pd/Pr-CeO2-5 catalyst; (e) TEM image and (f) HRTEM image of Pd/Pr-CeO2-7.5 catalyst; (g) TEM image and (h) HRTEM image of Pd/Pr-CeO2-10 catalyst

催化剂	w(Pd负载量)/%	w(Ce)/%	w(Pr)/%	Pd分散度/%
Pd/Pr-CeO₂-2.5	0.42	56.26	1.26	98.46
Pd/Pr-CeO₂-5	0.35	50.75	2.48	97.52
Pd/Pr-CeO₂-7.5	0.44	53.39	3.75	97.14
Pd/Pr-CeO₂-10	0.41	51.42	5.10	98.67

Table 1. Each metal mass fraction and Pd dispersion of Pd/Pr-CeO2 catalyst

Figure 4. (a) The Raman spectra of Pd/Pr-CeO2 catalysts at room temperature; (b) Ce 3d XPS spectra of Pd/Pr-CeO2 catalysts

Figure 5. H2-TPR images of (a) Pr-CeO2 support and (b) Pd/Pr-CeO2 catalysts

Figure 6. (a) XPS spectra of Pd 3d before the catalyst reaction and (b) XPS spectra of Pd 3d after the reaction

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Pd/Pr-CeO₂催化剂载体氧空位调控CO酯化制碳酸二甲酯选择性

Oxygen Vacancies in Pd/Pr-CeO₂ Catalyst Regulate the Selectivity of CO Esterification to Dimethyl Carbonate

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Pd/Pr-CeO2催化剂载体氧空位调控CO酯化制碳酸二甲酯选择性