Xiao Yuehua, Wang Yinjie, Wang Chengtao, Fang Wei, Liu Pei, Hui Yu, Li Hangjie, Zhou Hang, Xiao Feng-Shou
College of Chemical and Biological Engineering, State Key Laboratory of Chemical Engineering and Low-carbon Technology, Zhejiang University, Hangzhou 310058, China.
Ningbo Global Innovation Center, Zhejiang University, Ningbo 315100, China.
Chem Bio Eng. 2025 Jun 27;2(8):485-492. doi: 10.1021/cbe.5c00041. eCollection 2025 Aug 28.
Tungstate-based catalysts for olefin metathesis generally suffer from insufficient reaction rates, which require relatively high temperatures for the satisfied activities. This issue is mainly due to the shortage of active WO species related to intrinsic low adsorption and poor activation of olefin molecules. Herein, we found that the silanol nests in dealuminated Beta zeolite (DeAl-Beta) were favorable for high dispersion of tungsten species, forming active WO species on the zeolite, which was helpful for the adsorption and activation of olefin molecules, thus facilitating the generation of metallocycle intermediates. As a result, the propene yield in the metathesis of ethene and 1-butene over WO /DeAl-Beta was 2.3 times higher than that of the tungsten species supported on siliceous Beta zeolite with fewer silanol nests (WO /Si-Beta) under the equivalent conditions. A propene yield as high as >50% was achieved by optimizing the silanol nests in the WO /DeAl-Beta catalyst, outperforming those in the industrial silica supported tungsten species (W/SiO) catalysts reported previously.
用于烯烃复分解反应的钨酸盐基催化剂通常存在反应速率不足的问题，这需要相对较高的温度才能达到满意的活性。这个问题主要是由于与烯烃分子固有低吸附和差活化相关的活性WO 物种短缺。在此，我们发现脱铝β沸石（DeAl-Beta）中的硅醇巢有利于钨物种的高度分散，在沸石上形成活性WO 物种，这有助于烯烃分子的吸附和活化，从而促进金属环中间体的生成。结果，在等效条件下，WO /DeAl-Beta上乙烯与1-丁烯复分解反应中的丙烯产率比负载在硅醇巢较少的硅质β沸石（WO /Si-Beta）上的钨物种高出2.3倍。通过优化WO /DeAl-Beta催化剂中的硅醇巢，丙烯产率高达>50%，优于先前报道的工业二氧化硅负载钨物种（W/SiO）催化剂。
