基于Cu-Fc配位聚合物衍生的Pt-Cu/Cu_xFe_yO@C催化1,4-丁炔二醇加氢性能研究

Study on Catalytic Hydrogenation Properties of 2-Butyne-1,4-diol over Pt-Cu/Cu_xFe_yO@C Derived from Cu-Fc Coordination Polymers

1,4-丁烯二醇是精细化工领域的重要中间体,有着广泛的应用.采用异丙醇还原氯铂酸制备Pt纳米颗粒,并通过浸渍法将其负载于1,1’-二茂铁二羧酸(Fc)与CuCl_2·2H_2O水热法合成的Cu-Fc配位聚合物,干燥焙烧后制备得到Pt-Cu/Cu_xFe_yO@C催化剂,利用XRD、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析仪(TG)、N_2吸附脱附仪等表征手段对所制备的催化剂进行表征,对比了催化剂焙烧前后加氢效果,并考察了催化剂与底物的物质的量之比对1,4-丁炔二醇加氢制备1,4-丁烯二醇的影响.结果表明,以焙烧后制备的5%Pt-Cu/Cu_xFe_yO@C催化剂,在n催化剂∶n原料=1∶2 000,温度为120℃,H_2压力为4 MPa,反应时间为30 min的条件下,加氢反应的转化率为100%,生成1,4-丁烯二醇选择性为96.1%.

2-butene-1,4-diol is a kind of important intermediate in the field of fine chemical engineering,which has a very wide range of applications. We prepared the Pt nano-particles by using the isopropanol as reductive agent to reduce the（hydro）chloroplatinic acid,and followed by using the impregnation method to load the prepared Pt nano-particles on the Cu-Fc coordination polymer,which synthetized by using 1,1＇-Ferrocenedicarboxylicacid and CuCl2· 2H2O under the condition of hydro-thermal.At last,vacuum was used to dry and calcine the Pt/Cu-Fc coordination polymer under the nitrogen atmosphere to get the catalysts of Pt-Cu/CuxFeyO@C,then the catalysts were characterized by some comprehensive technical approaches such as XRD, XPS, TEM, SEM, TG, Nitrogen adsorption instrument.We also compared the hydrogenation results of the catalysts before and after calcination, and investigated the effect of molar ratio of catalysts to substrate on the performance of hydrogenation 2-butyne-1,4-diol to 2-butylene-1,4-diol. The results show that using the 5%Pt-Cu/CuxFeyO@C as catalysts, the molar ratio of catalysts and substrate is 1：2 000, the temperature is 120℃, H2 pressure is 4 MPa, the reaction time is 30 min, 2-butyne-1,4-diol conversion of 100%, 2-butylene-1,4-diolselectivity is 96.1% respectively.