PdZn Alloy Catalysts Modulating the Selectivity of CO Esterification Products: from Dimethyl Oxalate to Dimethyl Carbonate

doi:10.6023/A24110346

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (3): 206-211.DOI: 10.6023/A24110346 Previous Articles Next Articles

Communication

PdZn合金催化剂调控CO酯化产物选择性: 从草酸二甲酯到碳酸二甲酯

李翔宇^a^,^b, 李家凯^a^,^b, 林淑娟^a, 王明盛^a, 孙径^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 福州大学化学学院福州 350116

投稿日期:2024-11-14 发布日期:2025-02-05
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)

PdZn Alloy Catalysts Modulating the Selectivity of CO Esterification Products: from Dimethyl Oxalate to Dimethyl Carbonate

Xiang-Yu Li^a^,^b, Jia-Kai Li^a^,^b, Shu-Juan Lin^a, Ming-Sheng Wang^a, Jing Sun^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 Chemistry, Fuzhou University, Fuzhou 350116, China

Received:2024-11-14 Published:2025-02-05
Contact: ^*E-mail: jsun@fjirsm.ac.cn; 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 Institutes(CXZX-2022-GH05)

1. .pdf(4831KB)

Abstract

Currently, 10 million tons of coal to ethylene glycol (CTEG) plants have been built in China. Due to the poor market conditions of ethylene glycol, many plants are in a state of shutdown and are in urgent need of transformation. CO esterification in CTEG can produce two important ester chemicals, dimethyl oxalate (DMO) and dimethyl carbonate (DMC). Converting the product DMO into higher value-added DMC is one of the transition ideas. DMO can be converted to DMC by decarbonylation, but new reactors and catalysts are needed. It would be more economical and challenging to utilize CTEG plant to produce DMC directly by replacing the catalyst with a new one. Pd/α-Al₂O₃ is the traditional catalyst for DMO production. In this work, we proposed a PdZn alloying strategy to modulate the selectivity of CO esterification products, and realize the product selectivity change from DMO to DMC. Compared with Pd/α-Al₂O₃, the selectivity to DMO over PdZn(1:4)/α-Al₂O₃ was significantly decreased (85.8%→16.8%), and the DMC selectivity was increased remarkably (14.2%→83.2%). The formation of PdZn alloy was demonstrated by X-ray diffraction (XRD), transmission electron microscope (TEM), and other characterizations, X-ray photoelectron spectroscopy (XPS) results showed that the alloy formed between Zn and Pd significantly changed the electron density of the Pd component, and the Pd component was in an electron-deficient state, which was conducive to the improvement of the performance of the DMC reaction. In addition, the results of CO diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization showed that Zn can disperse Pd. With the increase of the second metal Zn content, the continuous Pd metal phase disappears, and an isolated single-atom alloy state may be formed, which inhibits the formation of the byproduct DMO. The present study not only provides a new way to regulate the selectivity of CO esterification products, but also provides an idea for the conversion of CTEG plants.

Key words: PdZn alloy, electron transfer, dimethyl carbonate, CO esterification reaction

Cite this article

Xiang-Yu Li, Jia-Kai Li, Shu-Juan Lin, Ming-Sheng Wang, Jing Sun, Zhong-Ning Xu, Guo-Cong Guo. PdZn Alloy Catalysts Modulating the Selectivity of CO Esterification Products: from Dimethyl Oxalate to Dimethyl Carbonate[J]. Acta Chimica Sinica, 2025, 83(3): 206-211.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

Figure 1. Product selectivity in CO esterification reaction of different catalysts. The selectivities were calculated based on CO, without considering the decomposition of MN. Reaction conditions: 200 mg catalyst, 120 ℃, 0.1 MPa, weight hour space velocity (WHSV)=2500 L?kgcat.?1?h?1, flow ratio of CO/MN/Ar/N2 is 19∶45∶3∶33

催化剂	Pd负载量^a/%	Zn负载量^a/%^a	分散度^b/%	CO转化率/%	DMC选择性/%
Pd	0.97	—	9.32	68.4	14.2
PdZn(1:1)	1.00	0.96	13.98	83.9	35.9
PdZn(1:2)	0.98	2.08	16.37	84.5	41.0
PdZn(1:4)	0.96	3.83	23.68	88.4	83.2

Table 1. Catalytic performance, metal loading and metal dispersion

Figure 2. (a) XRD patterns of Pd/α-Al2O3, PdZn(1:1)/α-Al2O3, PdZn(1:2)/α-Al2O3 and PdZn(1:4)/α-Al2O3. Brown vertical bars at the bottom denote the standard data for α-Al2O3 phase (PDF#50-1496); (b) partially zooming XRD spectra from 2θ=39°~43° of the above catalysts

Figure 3. H2-TPR profiles of calcined Pd/α-Al2O3, PdZn(1:1)/α-Al2O3, PdZn(1:2)/α-Al2O3 and PdZn(1:4)/α-Al2O3 catalysts

Figure 4. (a) TEM and (b) HRTEM images of PdZn(1:4)/α-Al2O3 catalyst; (c) HAADF-STEM image of PdZn(1:4)/α-Al2O3; (d~h) the corresponding elemental mapping of Al, O, Pd, Zn and Pd, Zn mixing

Figure 5. XPS spectra of Pd/α-Al2O3, PdZn(1:1)/α-Al2O3, PdZn(1:2)/ α-Al2O3 and PdZn(1:4)/α-Al2O3 samples

Figure 6. In situ CO-DRIFTS of Pd/α-Al2O3, PdZn(1:1)/α-Al2O3, PdZn(1:2)/α-Al2O3, PdZn(1:4)/α-Al2O3 and Zn/α-Al2O3 samples

References 29

[1]	Yin, Z.; Yan, B.; Wang, Z. Chem. Ent. Mgt. 2024, (13), 54 (in Chinese).
	(尹子帆, 闫炳旭, 王志强, 化工管理, 2024, (13), 54.)
[2]	Li, F.; Li, L. Chem. Ent. Mgt. 2021, (34), 25 (in Chinese).
	(李飞飞, 李丽君, 化工管理, 2021, (34), 25.)
[3]	Zhao, T.-J.; Chen, D.; Dai, Y.-C.; Yuan, W.-K.; Holmen, A. Ind. Eng. Chem. Res. 2004, 43, 4595.
[4]	Wang, S.; Li, W.; Dong, Y.; Zhao, Y.; Ma, X. Catal. Commun. 2015, 72, 43.
[5]	Peng, S.-Y.; Xu, Z.-N.; Chen, Q.-S.; Wang, Z.-Q.; Lv, D.-M.; Sun, J.; Chen, Y.; Guo, G.-C. ACS Catal. 2015, 5, 4410.
[6]	Tan, H.-Z.; Wang, Z.-Q.; Xu, Z.-N.; Sun, J.; Xu, Y.-P.; Chen, Q.-S.; Chen, Y.; Guo, G.-C. Catal. Today 2018, 316, 2.
[7]	Tundo, P.; Selva, M. Acc. Chem. Res. 2002, 35, 706.
[8]	Gu, B.; Liu, G.; Yin, K.; Zhang, J.; Xiang, H.; Wang, Y. Appl. Chem. Ind. 2023, 52, 1248 (in Chinese).
	(谷豹, 刘刚, 尹科科, 张嘉容, 项火芳, 王玉高, 应用化工, 2023, 52, 1248.)
[9]	Jv, N.; Li, C.; Li, F.; Xue, W.; Lv, J. New J. Chem. 2024, 48, 9062.
[10]	Li, G.-S. Ind. Catal. 2023, 31, 31 (in Chinese).
	(李贵生, 工业催化, 2023, 31, 31.) doi: 10.3969/j.issn.1008-1143.2023.03.004
[11]	Wang, Z.-Q.; Sun, J.; Xu, Z.-N.; Guo, G.-C. Nanoscale 2020, 12, 20131.
[12]	Lv, D.-M.; Xu, Z.-N.; Peng, S.-Y.; Wang, Z.-Q.; Chen, Q.-S.; Chen, Y.; Guo, G.-C. Catal. Sci. Technol. 2015, 5, 3333.
[13]	Wu, H.-Y.; Qin, Y.-Y.; Xiao, Y.-H.; Chen, J.-S.; Ye, R.; Guo, R.; Yao, Y.-G. Small 2023, 19, 2208238.
[14]	Peng, S.-Y.; Xu, Z.-N.; Chen, Q.-S.; Wang, Z.-Q.; Chen, Y.; Lv, D.-M.; Lu, G.; Guo, G.-C. Catal. Sci. Technol. 2014, 4, 1925.
[15]	Xu, Z.-N.; Sun, J.; Lin, C.-S.; Jiang, X.-M.; Chen, Q.-S.; Peng, S.-Y.; Wang, M.-S.; Guo, G.-C. ACS Catal. 2012, 3, 118.
[16]	Peng, S.-Y.; Xu, Z.-N.; Chen, Q.-S.; Chen, Y.-M.; Sun, J.; Wang, Z.-Q.; Wang, M.-S.; Guo, G.-C. Chem. Commun. 2013, 49, 5718.
[17]	Tan, H.-Z.; Wang, Z.-Q.; Xu, Z.-N.; Sun, J.; Chen, Z.-N.; Chen, Q.-S.; Chen, Y.; Guo, G.-C. Catal. Sci. Technol. 2017, 7, 3785.
[18]	Yamamoto, Y.; Matsuzaki, T.; Tanaka, S.; Nishihira, K.; Ohdan, K.; Nakamura, A.; Okamoto, Y. J. Chem. Soc., Faraday Trans. 1997, 93, 3721.
[19]	Hu, S.; Xie, C.; Xu, Y.-P.; Chen, X.; Gao, M.-L.; Wang, H.; Yang, W.; Xu, Z.-N.; Guo, G.-C.; Jiang, H.-L. Angew. Chem. Int. Ed. 2023, 62, e202311625.
[20]	Nakaya, Y.; Furukawa, S. Chem. Rev. 2023, 123, 5859.
[21]	Yin, Y.; Hu, B.; Li, X.; Zhou, X.; Hong, X.; Liu, G. Appl. Catal. B: Environ. 2018, 234, 143.
[22]	Furukawa, S.; Suzuki, R.; Komatsu, T. ACS Catal. 2016, 6, 5946.
[23]	Zhou, H.; Yang, X.; Li, L.; Liu, X.; Huang, Y.; Pan, X.; Wang, A.; Li, J.; Zhang, T. ACS Catal. 2016, 6, 1054.
[24]	Miyazaki, M.; Furukawa, S.; Takayama, T.; Yamazoe, S.; Komatsu, T. ACS Appl. Nano Mater. 2019, 2, 3307.
[25]	Chen, X.; Shi, C.; Wang, X.-B.; Li, W.-Y.; Liang, C. Commun. Chem. 2021, 4, 175.
[26]	Cheng, M.; Zhang, X.; Guo, Z.; Lv, P.; Xiong, R.; Wang, Z.; Zhou, Z.; Zhang, M. J. Colloid Interface Sci. 2021, 602, 459.
[27]	Rodriguez, J. A. J. Phys. Chem. 1994, 98, 5758.
[28]	Wang, H.; Luo, Q.; Liu, W.; Lin, Y.; Guan, Q.; Zheng, X.; Pan, H.; Zhu, J.; Sun, Z.; Wei, S.; Yang, J.; Lu, J. Nat. Commun. 2019, 10, 4998.
[29]	Tan, H.-Z.; Chen, Z.-N.; Xu, Z.-N.; Sun, J.; Wang, Z.-Q.; Si, R.; Zhuang, W.; Guo, G.-C. ACS Catal. 2019, 9, 3595.

PdZn合金催化剂调控CO酯化产物选择性: 从草酸二甲酯到碳酸二甲酯

PdZn Alloy Catalysts Modulating the Selectivity of CO Esterification Products: from Dimethyl Oxalate to Dimethyl Carbonate

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 29

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	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.
[2]	Chenfan Xie, Yu-Ping Xu, Ming-Liang Gao, Zhong-Ning Xu, Hai-Long Jiang. MOF-Stabilized Pd Single Sites for CO Esterification to Dimethyl Carbonate [J]. Acta Chimica Sinica, 2022, 80(7): 867-873.
[3]	Junmin Chen, Chengqian Cui, Hanlin Liu, Guodong Li. Study on the Selective Hydrogenation of Quinoline Catalyzed by Composites of Metal-Organic Framework and Pt Nanoparticles^※ [J]. Acta Chimica Sinica, 2022, 80(4): 467-475.
[4]	Yu Mohan, Cheng Yuanyuan, Liu Yajun. Mechanistic Study of Oxygenation Reaction in Firefly Bioluminescence [J]. Acta Chimica Sinica, 2020, 78(9): 989-993.
[5]	Jia Xiaoyan, Li Zhenhuan. Synthesis of N-Carboxy Alanine Anhydride from Alanine and Dimethyl Carbonate over NaZnPO₄ in One-pot [J]. Acta Chimica Sinica, 2020, 78(6): 540-546.
[6]	Qi Qige, Yang Chunfan, Xia Ye, Liu Kunhui, Su Hongmei. Photo-induced Electron Transfer between 4-Thiouracil and Tryptophan [J]. Acta Chimica Sinica, 2019, 77(6): 515-519.
[7]	Qiu Xuan, Shi Liang. Electrical Interplay between Microorganisms and Iron-bearing Minerals [J]. Acta Chim. Sinica, 2017, 75(6): 583-593.
[8]	Song Hao, Liu Xiaoyu, Qin Yong. Advances on Nitrogen-centered Radical Chemistry:A Photocatalytic N-H Bond Activation Approach [J]. Acta Chim. Sinica, 2017, 75(12): 1137-1149.
[9]	Yu Haibo, Li Hongling, Zhang Xinfu, Xiao Yi, Fang Peiju, Lv Chunjiao, Hou Wei. A Mitochondrial-Targetable and Turn-On Fluorescent Probe based on Nile Red and Monitoring for H₂S in Living Cells [J]. Acta Chim. Sinica, 2015, 73(5): 450-456.
[10]	Kang Hongliang, Liu Ruigang, Huang Yong. Synthesis of Ethyl Cellulose Grafted Poly(N-isopropylacrylamide) Copolymer and Its Micellization [J]. Acta Chimica Sinica, 2013, 71(01): 114-120.
[11]	Wang Feng, Liang Wen-Jing, Wang Wen-Guang, Chen Bin, Feng Ke, Zhang Li-Ping, Tung Chen-Ho, Wu Li-Zhu. Bis-terpyridine Os(Ⅱ) Complex Sensitized [FeFe] Hydrogenase Mimic Systems: Synthesis and Photophysical Study [J]. Acta Chimica Sinica, 2012, 70(22): 2306-2310.
[12]	Chai Yunfeng, Gan Shifeng, Pan Yuanjiang. A Mechanistic Study of Formation of Radical Anion from Fragmentation of Deprotonated N,2-Diphenylacetamide Derivatives in Electrospray Ionization Tandem Mass Spectrometry [J]. Acta Chimica Sinica, 2012, 70(17): 1805-1811.
[13]	DONG Jiang-Zhou, ZHAO Jun-Yan, CHAO Hui, CAO Ya-An. Band Structure and Photo-induced Charge Transfer in Surface-sensitized TiO₂-based Composite Films [J]. Acta Chimica Sinica, 2011, 69(23): 2781-2786.
[14]	JIN Ying-Xue, YUAN Wang, QU Feng-Yu, YIN Xiong-Can, WEI Shu-Quan, YUE Qun-Feng, TAN Guang-Hui. Photoinduced Single Electron Transfer Cyclization Reactions of N-(ω-Tributylstannylpolyethoxyether)phthalimides [J]. Acta Chimica Sinica, 2011, 69(20): 2407-2412.
[15]	DONG Yu-Pei, MOU Zhi-Gang, DU Yu-Kou, YANG Ping. Preparation, Electron Transfer and Photocatalysis of 4-(N,N-Diphenylamine) Benzyl Alcohol Functionalized Graphene [J]. Acta Chimica Sinica, 2011, 69(20): 2379-2384.