Zn2+通过电子转移提升CO酯化反应Pd基催化剂性能

doi:10.6023/A23030074

化学学报 ›› 2023, Vol. 81 ›› Issue (7): 691-696.DOI: 10.6023/A23030074 上一篇下一篇

研究通讯

Zn²⁺通过电子转移提升CO酯化反应Pd基催化剂性能

刘洵^a^,^b, 江辉波^a, 荆凯强^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建福州 350002
b 中国科学院大学北京 100049

投稿日期:2023-03-10 发布日期:2023-05-17
基金资助:
国家重点研发计划项目(2021YFB3801600); 国家重点研发计划项目(2017YFA0700103); 国家重点研发计划项目(2018YFA0704500); 中国科学院战略性先导专项课题(XDA29030600); 国家自然科学基金(22172171); 福建省自然科学基金(2022H0039); 中科院洁净能源创新研究院-榆林学院联合基金(2022010)

Introduction of Zn²⁺ Promotes the Catalytic Performance of Pd-based Catalyst for CO Esterification Reaction via Electron Transfer

Xun Liu^a^,^b, Hui-Bo Jiang^a, Kai-Qiang Jing^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, Fujian 350002
b University of Chinese Academy of Sciences, Beijing 100049

Received:2023-03-10 Published:2023-05-17
Contact: *E-mail: znxu@fjirsm.ac.cn; gcguo@fjirsm.ac.cn
Supported by:
National Key Research and Development Program of China(2021YFB3801600); National Key Research and Development Program of China(2017YFA0700103); National Key Research and Development Program of China(2018YFA0704500); Strategic Priority Research Program of the Chinese Academy of Sciences(XDA29030600); National Natural Science Foundation of China(22172171); Natural Science Foundation of Fujian Province(2022H0039); Grant YLU-DNL Fund(2022010)

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1. Supporting Information-A23030074.pdf(696KB)

摘要/Abstract

煤制乙二醇是现代煤化工中的一个重要技术路线, 其中CO酯化反应合成草酸二甲酯(DMO)是关键步骤之一. 负载型Pd基催化剂可有效催化该反应, 但关于载体效应的研究相对较少. 本研究使用二维层状材料CoAl-LDH (layered double hydroxides)作为载体, 合成的Pd/CoAl-LDH催化剂在CO酯化制DMO反应中显示出51.5%的CO转化率. 进一步在载体中引入Zn²⁺合成Pd/ZnCoAl-LDH催化剂, 其CO转化率提高至61.8%. XPS (X-ray photoelectron spectroscopy)表征结果表明, Zn²⁺的引入促进了Pd活性物种与载体ZnCoAl-LDH之间部分电子转移, 从而使该催化剂表现出优异的活性. 原位红外实验表明, 载体中引入Zn²⁺使得CO吸附峰发生红移, 该结果进一步证实了Zn²⁺的引入增加了Pd活性位点的局域电子密度. 本研究通过结构设计增强催化剂载体的Lewis碱性, 从而提高催化剂的反应活性, 为进一步提升Pd基多相催化剂的性能提供了有益参考.

关键词: ZnCoAl-LDH, Lewis碱位点, 草酸二甲酯, 电子转移

Coal to ethylene glycol is a crucial route in modern coal chemical industry, and the CO esterification reaction, which synthesizes dimethyl oxalate (DMO), is a key step in this process. While supported Pd-based catalysts are effective for this reaction, research on support effect is limited. In this study, we employed a two-dimensional material CoAl-LDH (layered double hydroxides) as a catalytic support to investigate the support effect for the CO esterification reaction. We prepared various LDH supports with different Co/Al molar ratios and loaded Pd metal using the ALD (atomic layer deposition) method. The successful preparation of LDH carriers was confirmed by TEM (transmission electron microscopy), XRD (X-ray diffraction), and Fourier infrared spectroscopy characterizations. The catalysts were evaluated for their catalytic performance in the CO esterification to DMO reaction. Based on the results, the support with a Co/Al molar ratio of 1∶1 was chosen for further study, as it exhibited the highest Lewis basicity in CO₂-TPD (temperature programmed desorption) tests. We then prepared the Pd/ZnCoAl-LDH catalyst by doping Zn²⁺ into the selected CoAl-LDH support. Compared to the Pd/CoAl-LDH catalyst, the Pd/ZnCoAl-LDH catalyst exhibited better catalytic activity for the CO esterification to DMO reaction, with the conversion of CO increasing from 51.5% to 61.8%. XPS (X-ray photoelectron spectroscopy) characterization results indicated that the introduction of Zn²⁺ promoted electron transfer between the Pd active species and ZnCoAl-LDH, which is responsible for the higher activity of the Pd/ZnCoAl-LDH catalyst. In situ DRIRS (diffuse reflectance infrared spectroscopy) experiments demonstrated a red-shift in the adsorption peak of CO, which further confirmed the increase in electron density around the Pd active species. In addition, the 100 h stability test results showed that the introduction of Zn²⁺ can also enhance the stability of the catalyst. After 100 h of evaluation, the catalytic activity of Pd/CoAl-LDH catalyst decreased significantly, while the activity of Pd/ZnCoAl-LDH remained basically unchanged. This study focused on the structural design for promoting catalytic activity through enhanced Lewis-basicity, providing a reference for improving the performance of Pd-based heterogeneous catalysts.

Key words: ZnCoAl-LDH, Lewis base site, dimethyl oxalate, electron transfer

引用此文

刘洵, 江辉波, 荆凯强, 徐忠宁, 郭国聪. Zn²⁺通过电子转移提升CO酯化反应Pd基催化剂性能[J]. 化学学报, 2023, 81(7): 691-696.

Xun Liu, Hui-Bo Jiang, Kai-Qiang Jing, Zhong-Ning Xu, Guo-Cong Guo. Introduction of Zn²⁺ Promotes the Catalytic Performance of Pd-based Catalyst for CO Esterification Reaction via Electron Transfer[J]. Acta Chimica Sinica, 2023, 81(7): 691-696.

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图/表 7

图1. 不同钴铝比的Pd/CoAl-LDH催化剂性能图

Figure 1. Performance of Pd/CoAl-LDH catalysts with different cobalt to aluminum ratios

图2. Pd/ZnCoAl-LDH(1∶1)催化剂性能随温度变化的曲线图

Figure 2. Graph of Pd/ZnCoAl-LDH(1∶1) catalyst performance variation with temperature

图3. Pd/CoAl-LDH和Pd/ZnCoAl-LDH催化剂100 h性能评价图

Figure 3. 100 h evaluation performance graph of Pd/CoAl-LDH and Pd/ZnCoAl-LDH catalysts

图4. (a) Pd/ZnCoAl-LDH和(b) Pd/CoAl-LDH的透射电镜图像; (c) Pd/ZnCoAl-LDH的HAADF-STEM图像; (d) Pd/CoAl-LDH上Pd的EDX mapping图像; (e, f) Pd/ZnCoAl-LDH上Zn和Pd的EDX mapping图像

Figure 4. TEM images of (a) Pd/ZnCoAl-LDH and (b) Pd/CoAl-LDH; (c) HAADF-STEM image of Pd/ZnCoAl-LDH; (d) EDX mapping image of Pd on Pd/CoAl-LDH; (e, f) EDX mapping image of Zn and Pd on Pd/ZnCoAl-LDH

图5. 不同钴铝比CoAl-LDH载体和ZnCoAl-LDH载体的CO2-TPD图

Figure 5. CO2-TPD graph of Pd/CoAl-LDH and Pd/ZnCoAl-LDH catalysts with different cobalt to aluminum ratios

图6. Pd/ZnCoAl-LDH和Pd/CoAl-LDH的XPS图

Figure 6. XPS spectra of Pd/ZnCoAl-LDH and Pd/CoAl-LDH

图7. Pd/ZnCoAl-LDH和Pd/CoAl-LDH催化剂上CO原位漫反射红外光谱

Figure 7. In situ DRIRS of CO over Pd/ZnCoAl-LDH and Pd/CoAl-LDH catalysts

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Zn²⁺通过电子转移提升CO酯化反应Pd基催化剂性能

Introduction of Zn²⁺ Promotes the Catalytic Performance of Pd-based Catalyst for CO Esterification Reaction via Electron Transfer

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