三明治结构催化剂Ce-MOF@Pt@TpPa-COF的制备、表征与性能  

Preparation,characterization,and performance of sandwich-like structure catalyst Ce-MOF@Pt@TpPa-COF

作　　者：丛培澳 王荣耀 李春生[1] 陈国柱[1] CONG Peiao;WANG Rongyao;LI Chunsheng;CHEN Guozhu(School of Chemistry and Chemical Engineering,University of Jinan,Jinan 250022,China)

机构地区：[1]济南大学化学化工学院,山东济南250022

出　　处：《中国粉体技术》2025年第3期101-112,共12页China Powder Science and Technology

基　　金：国家自然科学基金项目,编号:21878121;山东省自然科学基金项目,编号:ZR202102230042,ZR2023MB103;济南大学2023年学科交叉会聚建设项目,编号:XKJC-202302。

摘　　要：【目的】为了提高肉桂醛加氢过程中制备苯丙醛的转化率和选择性,制备具有三明治结构的选择性催化加氢催化剂。【方法】采用溶剂热法合成金属有机框架(metal-organic framework,MOF)Ce-UiO-66-NH2(Ce-MOF)内核;利用胶体浸渍法将铂(Pt)金属纳米颗粒均匀地负载到Ce-MOF内核表面,制得Ce-MOF@Pt;通过溶剂热法将三醛基间苯三酚(2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde,Tp)和对苯二胺(p-phenylenediamine,Pa)构建共价有机框架(covalent organicframework,COF)壳层TpPa-COF,将壳层TpPa-COF通过共价键C—N连接到Ce-MOF上,制备以Ce-MOF为内核、以金属纳米颗粒(nanoparticles,NPs)Pt NPs为中间层、以TpPa-COF为壳层的具有三明治结构的复合催化剂Ce-MOF@Pt@TpPa-COF;制备催化剂TpPa-COF@Pt,对Ce-MOF@Pt、Ce-MOF@Pt@TpPa-COF、TpPa-COF@Pt的结构和性能进行比较,探讨3组催化剂在肉桂醛加氢制备苯丙醛过程中的转化率、选择性和稳定性。【结果】在反应时间为6 h的条件下,Ce-MOF@Pt、Ce-MOF@Pt@TpPa-COF、TpPa-COF@Pt对肉桂醛的转化率分别为92%、89%、99%,对目标产物苯丙醛的选择性分别为21%、50%、1%,对目标产物苯丙醛的产率分别为19%、45%、1%;与Ce-MOF@Pt、TpPa-COF@Pt相比,具有三明治结构的催化剂Ce-MOF@Pt@TpPa-COF具有更优秀的稳定性。【结论】在肉桂醛催化加氢过程中,Ce-MOF@Pt@TpPa-COF能够显著提高苯丙醛在多相催化加氢反应过程中的选择性和产率,并保持了更好的稳定性。Objective To improve the conversion rate and selectivity of phenylpropionaldehyde(HCAL)in cinnamaldehyde(CAL)hydrogenation,and to verify the effectiveness of covalent organic framework(COF)as a shell to improve the performance of heterogeneous catalytic hydrogenation,a selective catalytic hydrogenation catalyst with a sandwich-like structure is prepared.Methods A metal-organic framework(MOF),Ce-UiO-66-NH2(Ce-MOF),was synthesized as a core via solvothermal method.Using the colloidal impregnation method,platinum(Pt)metal nanoparticles(NPs)were uniformly loaded on the surface of the Ce-MOF core to obtain Ce-MOF@Pt.2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde(Tp)and p-phenylenediamine(Pa)were added via solvothermal method to construct a covalent organic framework(COF)shell,TpPa-COF.The shell was then covalently bonded to the Ce-MOF through a C-N bond to prepare the composite catalyst Ce-MOF@Pt@TpPa-COF with Ce-MOF as the core,Pt NPs as the intermediate layer,and TpPa-COF as the shell.Thecatalyst TpPa-COF@Pt was also prepared,and the the structures and performance of Ce-MOF@Pt,Ce-MOF@Pt@TpPa-COF,and TpPa-COF@Pt were compared regard-ing to the conversion rate,selectivity,and stability of the three catalyst groups during the hydrogenation of CAL to HCAL.Results and Discussion At a reaction time of 6 h,the conversion rates of CAL for Ce-MOF@Pt,Ce-MOF@Pt@TpPa-COF,and TpPa-COF@Pt were 92%,89%,and 99%,respectively.The selectivities for the target product HCAL were 21%,50%,and 1%,respectively.The yields of the target product HCAL were 19%,45%,and 1%,respectively.Compared to Ce-MOF@Pt and TpPa-COF@Pt,Ce-MOF@Pt@TpPa-COF effectively maintained activity and stability at high temperatures and exhib-ited stronger resistance to deactivation.Conclusion In the catalytic hydrogenation of CAL,Ce-MOF@Pt@TpPa-COF significantly improves the selectivity and yield of HCAL in heterogeneous catalytic hydrogenation reactions while maintaining better cyclic stability.The study provides insights into the research and applications of sandwich-li

关 键 词：三明治结构 金属有机框架 共价有机框架 肉桂醛 选择性加氢 

分 类 号：TB4[一般工业技术] O62[理学—有机化学] TQ032.4[理学—化学]