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

doi:10.6023/A25020035

摘要/Abstract

我国“缺油少气煤炭相对丰富”的资源特点决定了煤基CO酯化制碳酸二甲酯(DMC)具有重要价值. Pd(II)/NaY已被证明是该反应的有效催化剂, 但由于NaY分子筛的酸性造成原料亚硝酸甲酯部分分解, 因此研发非分子筛体系的催化剂具有重要意义. CeO₂是一种常用的氧化物载体, 由于其酸性较弱, 原料亚硝酸甲酯分解问题几乎不存在, 然而Pd/CeO₂催化剂的DMC选择性却较低. 为了提升DMC选择性, 本工作在CeO₂载体中引入不同比例的Pr, 以期增大CeO₂的氧空位浓度, 进而提升DMC选择性. 合成了Pd/Pr-CeO₂-2.5, Pd/Pr-CeO₂-5, Pd/Pr-CeO₂-7.5, Pd/Pr-CeO₂-10四种不同Pr掺杂比例的催化剂, 发现其DMC选择性有显著差异, Pd/Pr-CeO₂-5催化剂表现出最佳的DMC选择性(77%). 通过拉曼光谱(Raman)和X-射线光电子能谱(XPS)分析, 结合催化性能, 发现DMC选择性与氧空位浓度成正比关系. 通过氢气程序升温还原(H₂-TPR)表征发现, Pd/Pr-CeO₂-5催化剂的还原温度最高, 说明具有最高氧空位浓度的Pd/Pr-CeO₂-5催化剂, 其金属-载体相互作用也最强, 可以稳定Pd(II)活性物种, 因而表现出最高的DMC选择性. 本工作的研究结果揭示了氧化物载体的氧空位浓度与DMC选择性之间的构-效关系, 对于研发非分子筛体系的高性能DMC催化剂具有重要指导意义.

关键词: CeO₂, 稀土掺杂, 氧空位, CO酯化反应, 碳酸二甲酯

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

引用此文

徐梦鑫, 杨智健, 孙径, 邹文强, 徐忠宁, 郭国聪. 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[J]. 化学学报, 2025, 83(7): 655-660.

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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图/表 7

图1. 四种催化剂在CO酯化制DMC反应中DMC和DMO的选择性 (反应条件: 200 mg催化剂, 0.1 MPa, 120 ℃, 空速为2500 L•kgcat-1•h-1, V(CH3ONO)/V(CO)=2.4, 反应时间6 h)

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)

图2. Pd/Pr-CeO2催化剂的XRD图谱

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

图3. (a) Pd/Pr-CeO2-2.5催化剂的TEM图像和(b) HRTEM图像; (c) Pd/Pr-CeO2-5催化剂的TEM图像和(d) HRTEM图像; (e) Pd/Pr-CeO2-7.5催化剂的TEM图像和(f) HRTEM图像; (g) Pd/Pr-CeO2-10催化剂的TEM图像和(h) HRTEM图像

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

表1. Pd/Pr-CeO2催化剂中各金属质量分数及Pd分散度

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

图4. (a) 室温下的Pd/Pr-CeO2催化剂的拉曼光谱; (b) Pd/Pr-CeO2催化剂的Ce 3d XPS谱图

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

图5. (a) Pr-CeO2载体和(b) Pd/Pr-CeO2催化剂的H2-TPR图像

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

图6. (a)催化剂反应前的Pd 3d XPS和(b)反应后Pd 3d XPS图谱

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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