Fe(OH)x-Pt/BN催化剂上的巴豆醛加氢:Pt-Fe(OH)_(x)相互作用促进不饱和醇选择性  

Hydrogenation of crotonaldehyde over Fe(OH)_(x)-Pt/BN catalysts:Improved selectivity to unsaturated alcohol via Pt-Fe(OH)x interaction

作　　者：叶艳文 胡一鸣 贾爱平 李艳明 王瑜 鲁继青[1] Ye Yanwen;Hu Yiming;Jia Aiping;Li Yanming;Wang Yu;Lu Jiqing(College of Chemistry and Life Sciences,Zhejiang Normal University,Jinhua 321004,Zhejiang,China;Library and Information Center of Zhejiang Normal University,Jinhua 321004,Zhejiang,China)

机构地区：[1]浙江师范大学化学与生命科学学院,浙江金华321004 [2]浙江师范大学图文信息中心,浙江金华321004

出　　处：《工业催化》2022年第11期19-30,共12页Industrial Catalysis

基　　金：国家自然科学基金项目(21773212,21643007)。

摘　　要：测试了一系列Fe(OH)_(x)修饰的Pt/BN催化剂用于巴豆醛加氢的性能。与纯Pt/BN催化剂上巴豆醇的低选择性(小于5%)相比,Fe(OH)_(x)的修饰可显著增加巴豆醇的选择性。n(Fe)∶n(Pt)=0.1的催化剂(0.1FePt/BN)具有最佳性能,其在80℃液相中的巴豆醇生成速率为166.6μmol·g Pt^(-1)·s^(-1),选择性为72.7%,在70℃气相中的转换频率(TOF)为0.04278 s^(-1),选择性为80.5%。表征结果表明,Pt-Fe(OH)_(x)相互作用改变了Pt物种在Pt-Fe(OH)_(x)界面位点的电子特性,从而促进了吸附羰基的活化,提高了对不饱和醇的选择性。此外,动力学数据的定量分析表明,在70℃时,界面Pt位点的TOF为0.37753 s^(-1),比非界面Pt位点(0.56×10^(-3)s^(-1))高出三个数量级。A series of Fe(OH)_(x)-decorated Pt/BN catalysts were tested for hydrogenation of crotonaldehyde.Compared to the low selectivity to crotyl alcohol on bare Pt/BN(less than 5%),the Fe(OH)_(x) modification resulted in significant improvement in selectivity.The best performance was obtained on a catalyst with an Fe/Pt molar ratio of 0.1(0.1FePt/BN),which gave a crotyl alcohol formation rate of 166.6μmol·g_(Pt)^(-1)·s^(-1) at 80℃in liquid phase with a selectivity of 72.7%,and a turnover frequency(TOF)of 0.04278 s^(-1) at 70℃in gas phase with a selectivity of 80.5%.Various characterization results revealed that the Pt-Fe(OH)_(x) interaction altered electronic properties of the Pt species at the interfacial sites,which consequently facilitated the activation of adsorbed carbonyl group and thus the selectivity to unsaturated alcohol.Moreover,quantitative analysis of the kinetic data indicated that the TOF of the interfacial Pt site was 0.37753 s^(-1) at 70℃,which was three order of magnitude higher than that on the non-interfacial Pt site(0.56×10^(-3)s^(-1)).

关 键 词：催化化学 α β-不饱和醛 PT催化剂 Fe(OH)_(x)修饰 界面位点 反应机理 

分 类 号：TQ426.6[化学工程] O643.36[理学—物理化学]