Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate

WANG Zhimiao1,2 ZHANG Hongqi1 ZHOU Lichao1 LI Fang1,2 XUE Wei1,2 WANG Yanji1,2

(1.Hebei Provincial Key Laboratory of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, China 300130)
(2.Tianjin Key Laboratory of Chemical Process Safety, Tianjin, China 300130)
【Knowledge Link】carbonylation

【Abstract】A Pd-Ce-O/SiO2 catalyst with Ce as an auxiliary was prepared by the microemulsion method for oxidative carbonylation of phenol to synthesize diphenyl carbonate (DPC). The activity evaluation results showed that the catalyst performance increases with the increase in the amount of Ce. When the Ce/Pd molar ratio is 10/1, the phenol conversion rate is 64.4%, and the DPC selectivity is 83.4%. The XRD results show that part of Ce4+ enters into the PdO crystal lattice, and thus the electrons of deactivated Pd can easily be transferred to Ce. So the Pd-Ce-O/SiO2 catalyst can be easily regenerated and shows better performance. According to the above mentioned results, Pd-O/CeO2 was designed and prepared for oxidative carbonylation of phenol. However, unlike Pd-Ce-O/SiO2, Pd-O/CeO2 shows poor catalytic performance. The phenol conversion and DPC selectivity are only 24.0% and 23.3% respectively. The characterization results show that PdO is the main species of Pd on the surface of Pd-Ce-O/SiO2, but there is more PdO2 on Pd-O/CeO2. Because Pd(Ⅱ) is the active site for oxidative carbonylation, Pd-O/CeO2 exhibits inferior activity to Pd-Ce-O/SiO2. In addition, in the Pd-O/CeO2 catalyst the surface Pd content is lower than those in other catalysts because of the strong interaction between Pd species and CeO2. That is one of the reasons for the poor activity of Pd-O/CeO2.

【Keywords】 diphenyl carbonate; oxidative carbonylation; heterogeneous reaction; catalyst; support; ceria;


【Funds】 National Natural Science Foundation of China (21776057) Natural Science Foundation of Tianjin (17JCYBJC20100, 18JCYBJC21500) Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Hebei Province (CL201605)

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(Translated by WANG YX)


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This Article


CN: 11-1946/TQ

Vol 70, No. 12, Pages 4625-4634+4920

December 2019


Article Outline



  • Introduction
  • 1 Experimental materials and methods
  • 2 Experimental results and discussion
  • 3 Conclusions
  • References