12-Tungstophosphoric acid niched in Zr-based metal-organic framework:a stable and efficient catalyst for Friedel-Crafts acylation  

作　　者：Latif Ullah Guoying Zhao Zichen Xu Hongyan He Muhammad Usman Suojiang Zhang 

机构地区：[1]Beijing Key Laboratory of Ionic Liquids Clean Process,Key Laboratory of Green Process Engineering,State Key Laboratory of Multiphase Complex Systems,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]Center of Excellence in Nanotechnology,King Fahd University of Petroleum and Minerals,Dhahran 3126,Saudi Arabia

出　　处：《Science China Chemistry》2018年第4期402-411,共10页中国科学（化学英文版）

基　　金：supported by the National Key Research and Development Program of China(2016YFB0601303);the National Natural Science Foundation of China(51374193,21676278);Key Program of National Natural Science Foundation of China(9143420);Chinese Academy of Sciences,State Administration of Foreign Experts Affairs(CAS/SAFEA)International Partnership Program for Creative Research Teams(20140491518)

摘　　要：Heteropoly acids(HPA) are well known for their versatile solid acid catalysis in diverse chemical reactions, however they suffer from low surface area(<10 m^2/g) and leaching into the reactions media, which reduce their prospects as industrial catalyst.Herein, a novel hybrid material HPW@Zr-BTC,composed of 12-tungstophoric acid(HPW) and Zr^(Ⅳ)-benzene tri-carboxylate(Zr-BTC) metal-organic framework(MOF), was prepared via one-pot solvothermal method. Excellent HPW loading up to 32.3 wt% was achieved, and HPW@Zr-BTC composite proved to be highly stable, besides the crystalline morphology of Zr-BTC was intact. The catalytic activity of the hybrid composite was explored via Friedel-Crafts acylation of anisole with benzoyl chloride.The 28.2 wt% HPW@Zr-BTC showed excellent catalytic performance, with 99.4% anisole conversion and 97.6% yield(pmethoxybenzophenone) under solvent free conditions. Excellent retention of catalytic activity was achieved after at least five consecutive runs due to non-observable HPW leaching. The promising activity and stability of the catalyst forecasted its potential industrial applications.Heteropoly acids（HPA） are well known for their versatile solid acid catalysis in diverse chemical reactions, however they suffer from low surface area（〈10 m^2/g） and leaching into the reactions media, which reduce their prospects as industrial catalyst.Herein, a novel hybrid material HPW@Zr-BTC,composed of 12-tungstophoric acid（HPW） and Zr^Ⅳ-benzene tri-carboxylate（Zr-BTC） metal-organic framework（MOF）, was prepared via one-pot solvothermal method. Excellent HPW loading up to 32.3 wt% was achieved, and HPW@Zr-BTC composite proved to be highly stable, besides the crystalline morphology of Zr-BTC was intact. The catalytic activity of the hybrid composite was explored via Friedel-Crafts acylation of anisole with benzoyl chloride.The 28.2 wt% HPW@Zr-BTC showed excellent catalytic performance, with 99.4% anisole conversion and 97.6% yield（pmethoxybenzophenone） under solvent free conditions. Excellent retention of catalytic activity was achieved after at least five consecutive runs due to non-observable HPW leaching. The promising activity and stability of the catalyst forecasted its potential industrial applications.

关 键 词：dodeca-tungstophosphoric acid Zr-BTC metal-organic frameworks one-pot solvothermal synthesis HETEROGENEOUSCATALYSIS anisole acylation high temperature XRD 

分 类 号：O643.36[理学—物理化学]