双功能Pd/ZrHP催化剂的制备及其在苯酚选择性加氢反应中的应用  

Preparation and Application of the Bifunctional Pd/ZrHP Catalyst for Selective Hydrogenation of Phenol

作　　者：王紫璇 姜媛媛 周茹茹 陈平[1] 侯昭胤[1] WANG Zi-Xuan;JIANG Yuan-Yuan;ZHOU Ru-Ru;CHEN Ping;HOU Zhao-Yin(Department of Chemistry,Zhejiang University,Hangzhou 310028,China)

机构地区：[1]浙江大学化学系,杭州310028

出　　处：《无机化学学报》2022年第5期812-820,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家重点研发计划(No.2018YFB1501402)资助。

摘　　要：苯酚加氢制备环己酮是合成纤维(尼龙)生产过程中的重要环节。采用微波法快速合成了具有层状结构的固体酸(磷酸氢锆,ZrHP)和ZrHP负载的Pd催化剂,利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高倍透射电子显微镜(HRTEM)、氮气吸附-脱附、X射线光电子能谱(XPS)和程序升温脱附(TPD)技术对催化剂的结构、形貌和表面特性进行了详细的表征,并将其应用于苯酚选择性加氢制环己酮的反应中。研究发现:在温和条件(100℃,1.0 MPa H_(2))下,Pd/ZrHP比传统的氧化物(Al_(2)O_(3)、SiO_(2)、MgO)、分子筛(H‑Beta)、活性炭(XC‑72)负载的Pd催化剂具有更高的活性和稳定性,催化剂表面Pd原子的比活性最高可达612.2 h^(-1),并且经过5次循环使用后催化剂无明显失活。结合表征结果推断,金属中心Pd与ZrHP表面的酸性位点之间的协同作用可能是影响苯酚加氢产物停留在环己酮阶段的关键因素。Hydrogenation of phenol to cyclohexanone is a vital step in the production of synthetic fiber(nylon).In this work,a layered-structured solid acid(zirconium hydrogen phosphate,ZrHP)supported Pd catalyst was synthesized in a microwave method.The structure and property of Pd/ZrHP catalyst were characterized via X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),nitrogen adsorption-desorption,X-ray photoelectron spectroscopy(XPS),and temperature-programmed desorption(TPD)technologies.It was found that Pd/ZrHP catalyst exhibited better performance than the Pd-based catalysts supported by traditional oxide(Al_(2)O_(3),SiO_(2),MgO),molecular sieve(H-Beta),and active carbon(XC-72)under the mild condition(100℃,1.0 MPa H_(2)).The specific activity of the surface Pd atom in Pd/ZrHP reached 612.2 h^(-1),and it could be recycled five times without obvious deactivation.The synergistic effect between Pd metal and the acidic sites on ZrHP surface might be the main reason for the selective formation of cyclohexanone.

关 键 词：苯酚 环己酮 加氢 磷酸氢锆 PD 

分 类 号：O643.3[理学—物理化学]