Regulation of Co2+ cations on the content of Brönsted acid site and oxygen vacancy of WOx to improve the epoxidation performance of 1-hexene

XING Xiang-ying; WANG Hui-xiang; WANG Lian-cheng; LÜ Bao-liang

doi:10.19906/j.cnki.JFCT.2022030

Volume 50 Issue 11

Nov. 2022

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Article Navigation > Journal of Fuel Chemistry and Technology > 2022 > 50(11): 1480-1490

XING Xiang-ying, WANG Hui-xiang, WANG Lian-cheng, LÜ Bao-liang. Regulation of Co2+ cations on the content of Brönsted acid site and oxygen vacancy of WOx to improve the epoxidation performance of 1-hexene[J]. Journal of Fuel Chemistry and Technology, 2022, 50(11): 1480-1490. doi: 10.19906/j.cnki.JFCT.2022030

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XING Xiang-ying, WANG Hui-xiang, WANG Lian-cheng, LÜ Bao-liang. Regulation of Co²⁺ cations on the content of Brönsted acid site and oxygen vacancy of WO_x to improve the epoxidation performance of 1-hexene[J]. Journal of Fuel Chemistry and Technology, 2022, 50(11): 1480-1490. doi: 10.19906/j.cnki.JFCT.2022030

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Regulation of Co²⁺ cations on the content of Brönsted acid site and oxygen vacancy of WO_x to improve the epoxidation performance of 1-hexene

doi: 10.19906/j.cnki.JFCT.2022030

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Natural Science Foundation of China (21972158), Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (2021017), Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2021-K10) and Natural Science Foundation of Shanxi Province (201901D211583) and Patent Conversion Foundation of Shanxi Province (202202093).

Received Date: 2022-03-10
Accepted Date: 2022-04-08
Rev Recd Date: 2022-04-06

Available Online: 2022-05-12

Publish Date: 2022-11-30

Abstract

Abstract

In this study, the Co-WO_x catalyst was successfully prepared by directly introducing Co²⁺ dopant in a dynamic solvothermal synthesis process, and the obtained Co-WO_x was used for the catalytic epoxidation of 1-hexene. The structures of WO_x before and after the doping were analyzed by XRD, SEM, TEM, Raman, XPS as well as in-situ NH₃-FTIR. The results show that the doping of Co²⁺ has not obvious effect on the crystal phase and main growth direction of WO_x, but can effectively reduce the content of Brönsted acid (B acid) site on the surface of WO_x catalyst and increase the content of oxygen vacancy at the same time. In the epoxidation reaction, the obtained Co-WO_x catalyst (Co/W = 0.1) can increase the selectivity of 1,2-epoxyhexane from 26.9% of pure WO_x to 55.7% with a 5.3% decrease in 1-hexene conversion. The improvement of Co-WO_x performance is mainly attributed to two aspects: (1) the reduction of B acid site on the surface of WO_x inhibits the ring opening hydrolysis of 1,2-epoxyhexane; (2) The increase of oxygen vacancies on the surface of WO_x promotes the activation of H₂O₂, ensuring that the conversion rate of 1-hexene does not decrease significantly, and an increase in the utilization of oxidant H₂O₂ by 13.5%. Combined with the characterization results and reaction data, the epoxidation mechanism of 1-hexene with W−O−OH as active intermediate is proposed.
- WO_x,
- Co doping,
- Brönsted acid site,
- oxygen vacancies,
- 1-hexene epoxidation

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References(54)

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