Pd单原子和Pd纳米颗粒协同催化肉桂醛加氢制苯丙醛  

Synergistic catalysis of Pd single atoms and Pd nanoparticles for cinnamaldehyde hydrogenation to phenylpropanal

作　　者：任小敏 赵芋衡 马颖[2] 张啟霞 马军 刘岳峰 REN Xiaomin;ZHAO Yuheng;MA Ying;ZHANG Qixia;MA Jun;LIU Yuefeng(School of Environmental and Chemical Engineering,Dalian Jiaotong University,Dalian 116028,Liaoning,China;Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China;College of Chemistry and Chemical Engineering,Southwest Petroleum University,Chengdu 610500,Sichuan,China;School of Chemical Engineering,Sichuan University,Chengdu 610065,Sichuan,China)

机构地区：[1]大连交通大学环境与化学工程学院,辽宁大连116028 [2]中国科学院大连化学物理研究所,辽宁大连116023 [3]西南石油大学化学化工学院,四川成都610500 [4]四川大学化学工程学院,四川成都610065

出　　处：《低碳化学与化工》2025年第2期45-52,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22172161,22302027);大连市青年科技之星项目(2022RQ030);榆林中科洁净能源创新研究院人工智能科技专项(DNL-YLA202204)。

摘　　要：由于肉桂醛(CAL)分子中的两个不饱和化学键构成了复杂的共轭体系,CAL分子中的C==C和C==O键进行选择性加氢以生成所需产物是一项具有挑战性的工作。分别制备了Pd单原子、Pd纳米颗粒及Pd单原子和纳米颗粒共同负载在纳米金刚石(ND)的催化剂(分别为Pd_(1)/ND(w(Pd)=0.05%)、Pd_(NPs)/ND(w(Pd)=0.25%)和Pd_(1+NPs)/ND(w(Pd)=0.25%)),并研究了Pd的几何和电子结构对催化剂催化CAL加氢性能的影响。通过HR-TEM、XRD和XPS等方法对ND进行了表征。结果表明,ND是一种表面含有丰富氧官能团且具有单原子锚定位点的高结晶度及高表面能的载体。同时利用HADDF-STEM、AC-TEM和XPS等方法对Pd_(1+NPs)/ND的几何和电子结构进行了分析。结果表明,与Pd/C相比,Pd_(1+NPs)/ND具有更高的n(Pdδ+)/n(Pd0),进一步证实了Pd_(1+NPs)/ND上Pd单原子和Pd颗粒共存。在反应温度为40℃、H2压力为1 MPa和n(Pd)/n(CAL)为0.023%的条件下,分别考察了Pd_(1+NPs)/ND、Pd/C、Pd_(1)/ND和Pd_(NPs)/ND对CAL加氢反应的催化性能。结果表明,Pd_(1+NPs)/ND表现出远高于Pd/C的催化活性和苯丙醛(HCAL)选择性,Pd_(1)/ND和Pd_(NPs)/ND均表现出较低的催化活性。因此,在Pd_(1+NPs)/ND高效催化CAL加氢反应中,Pd单原子和Pd纳米颗粒之间存在协同效应。Due to the complex conjugated structure of the two unsaturated chemical bonds in cinnamaldehyde(CAL)molecules,the selective hydrogenation of C==C and C==O bonds in CAL to produce desired products is a challenging task.Pd single atoms,Pd nanoparticles and a combination of Pd single atoms and Pd nanoparticles supported on nanodiamonds(ND)were prepared(Pd_(1)/ND(w(Pd)=0.05%),Pd_(NPs)/ND(w(Pd)=0.25%)and Pd_(1+NPs)/ND(w(Pd)=0.25%),respectively).The influences of the geometric and electronic structures of Pd on catalytic performances of catalysts in CAL hydrogenation were studied.The ND was characterized by HR-TEM,XRD and XPS.The results show that ND is a kind of high-crystallinity and high-surface-energy support with abundant oxygen functional groups and single-atom anchoring sites.The geometric and electronic structures of Pd_(1+NPs)/ND were analyzed by HADDF-STEM,AC-TEM and XPS.The results show that compared to Pd/C,Pd_(1+NPs)/ND has higher n(Pdδ+)/n(Pd0),further confirming the coexistence of Pd single atoms and Pd nanoparticles.The catalytic performances of Pd_(1+NPs)/ND,Pd/C,Pd_(1)/ND and Pd_(NPs)/ND for CAL hydrogenation were investigated under the conditions of the temperature of 40℃,the H2 pressure of 1 MPa and n(Pd)/n(CAL)of 0.023%.The results show that Pd_(1+NPs)/ND exhibites much higher catalytic activity and hydrocinnamaldehyde(HCAL)selectivity than Pd/C.Pd_(1)/ND and Pd_(NPs)/ND show low catalytic activities.Therefore,there is a synergistic effect between Pd single atoms and Pd nanoparticles in the efficient catalytic CAL hydrogenation by Pd_(1+NPs)/ND.

关 键 词：Pd单原子 Pd纳米颗粒 纳米金刚石 肉桂醛加氢 协同催化 

分 类 号：TQ426[化学工程] O643.3[理学—物理化学]