Dealuminated Beta zeolite reverses Ostwald ripening for durable copper nanoparticle catalysts

Author:

Liu Lujie1ORCID,Lu Jiaye2ORCID,Yang Yahui3,Ruettinger Wolfgang3ORCID,Gao Xinhua4ORCID,Wang Ming5,Lou Hao6,Wang Zhandong6ORCID,Liu Yifeng7,Tao Xin8,Li Lina8,Wang Yong9ORCID,Li Hangjie1ORCID,Zhou Hang1ORCID,Wang Chengtao1ORCID,Luo Qingsong1,Wu Huixin1,Zhang Kaidi1,Ma Jiabi5ORCID,Cao Xiaoming210ORCID,Wang Liang1ORCID,Xiao Feng-Shou111ORCID

Affiliation:

1. Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.

2. Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.

3. BASF Advanced Chemicals Co., Ltd., Shanghai 200137, China.

4. State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China.

5. Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.

6. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, China.

7. Department of Chemistry, Zhejiang University, Hangzhou 310027, China.

8. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China.

9. Center of Electron Microscopy and State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China.

10. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.

11. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China.

Abstract

Copper nanoparticle–based catalysts have been extensively applied in industry, but the nanoparticles tend to sinter into larger ones in the chemical atmospheres, which is detrimental to catalyst performance. In this work, we used dealuminated Beta zeolite to support copper nanoparticles (Cu/Beta-deAl) and showed that these particles become smaller in methanol vapor at 200°C, decreasing from ~5.6 to ~2.4 nanometers in diameter, which is opposite to the general sintering phenomenon. A reverse ripening process was discovered, whereby migratable copper sites activated by methanol were trapped by silanol nests and the copper species in the nests acted as new nucleation sites for the formation of small nanoparticles. This feature reversed the general sintering channel, resulting in robust catalysts for dimethyl oxalate hydrogenation performed with supported copper nanoparticles for use in industry.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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