Liu Lujie, Lu Jiaye, Yang Yahui, Ruettinger Wolfgang, Gao Xinhua, Wang Ming, Lou Hao, Wang Zhandong, Liu Yifeng, Tao Xin, Li Lina, Wang Yong, Li Hangjie, Zhou Hang, Wang Chengtao, Luo Qingsong, Wu Huixin, Zhang Kaidi, Ma Jiabi, Cao Xiaoming, Wang Liang, Xiao Feng-Shou
Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
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.
Science. 2024 Jan 5;383(6678):94-101. doi: 10.1126/science.adj1962. Epub 2023 Dec 21.
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.
基于铜纳米颗粒的催化剂已在工业中广泛应用,但在化学气氛中,这些纳米颗粒容易烧结成更大的颗粒,这对催化剂性能不利。在这项工作中,我们使用脱铝β沸石负载铜纳米颗粒(Cu/Beta-deAl),结果表明,在200°C的甲醇蒸汽中,这些颗粒会变小,直径从约5.6纳米减小到约2.4纳米,这与一般的烧结现象相反。我们发现了一个逆熟化过程,即被甲醇活化的可迁移铜位点被硅醇巢捕获,巢中的铜物种作为形成小纳米颗粒的新成核位点。这一特性逆转了一般的烧结通道,从而得到了用于工业草酸二甲酯加氢反应的、由负载型铜纳米颗粒构成的、性能稳定的催化剂。