Page 182 - 《精细化工》2023年第6期

第 40 卷第 6 期 精 细 化 工 Vol.40, No.6
20 23 年 6 月 FINE CHEMICALS June 2023

催化与分离提纯技术
高分散 Pd/Ni-A-CA 纳米催化剂催化喹啉加氢

*
*
崔坤成，李泓锟，雷 阳，袁果园，刘德蓉 ，熊 伟
（重庆科技学院 化学化工学院，重庆 401331）

摘要：以镍（Ni）为金属节点，腺嘌呤（A）和柠檬酸（CA）为有机配体，采用溶剂热法制备了非晶态金属有
机配合物 Ni-A-CA。将 PdCl 2 溶液浸渍于载体 Ni-A-CA 后用 NaBH 4 还原制得高分散的 Pd 纳米粒子（Pd NPs）
催化剂 Pd/Ni-A-CA。通过 SEM、TEM、XRD、FTIR、XPS、N 2 吸附-脱附对载体 Ni-A-CA〔n(Ni)∶n(A)∶n(CA)=
2∶1∶1.5〕和催化剂 3% Pd/Ni-A-CA（3%为 Pd 的理论负载量，以 Ni-A-CA 的质量计，下同）进行了表征。结
果表明，Pd NPs 高度分散在载体 Ni-A-CA 上，其粒径为(2.2±0.3) nm，且载体与 Pd NPs 之间存在的强相互作用
增强了催化剂的催化性能。在 90 ℃、2 MPa H 2 条件下，3% Pd/Ni-A-CA 催化喹啉加氢反应 70 min，喹啉转化
率为 99.0%，生成 1,2,3,4-四氢喹啉选择性>99%。
关键词：非晶态金属有机配合物；Ni-A-CA；Pd NPs；高分散；喹啉加氢；催化技术
中图分类号：O643.36；O626.323 文献标识码：A 文章编号：1003-5214 (2023) 06-1332-08

Highly dispersed Pd/Ni-A-CA nanocatalyst for catalytic

hydrogenation of quinoline

*
*
CUI Kuncheng, LI Hongkun, LEI Yang, YUAN Guoyuan, LIU Derong , XIONG Wei
（School of Chemistry and Chemical Engineering, Chongqing University of Science & Technology, Chongqing 401331,
China）

Abstract: Amorphous metal-organic compound (Ni-A-CA) was firstly synthesized from solvothermal
reaction of nickel (Ni), adenine (A) and citric acid (CA). Then, highly dispersed catalysts (Pd/Ni-A-CA)
were prepared by dispersing PdCl 2 on Ni-A-CA substrate and further reduction of PdCl 2 solution via freshly
prepared NaBH 4. Substrate Ni-A-CA [n(Ni)∶n(A)∶n(CA)=2∶1∶1.5] and catalyst 3% Pd/Ni-A-CA (3%
is the theoretical load of Pd, calculated by the mass of Ni-A-CA, the same below) were characterized by
SEM, TEM, XRD, FTIR, XPS, N 2 adsorption and desorption. The results showed that Pd NPs were highly
dispersed on the surface of Ni-A-CA substrate with a particle size of (2.2±0.3) nm, and the catalytic
performance of Pd/Ni-A-CA was enhanced by the strong interaction between the Pd NPs and the substrate.
Under reaction temperature of 90 ℃, reaction pressure of 2 MPa H 2, and rection time of 70 min, the
catalyst 3% Pd/Ni-A-CA led to a conversion rate of quinoline and selectivity of 1,2,3,4-tetrahydroquinoline
of 99.0% and > 99%, respectively.
Key words: amorphous metal-organic compounds; Ni-A-CA; Pd nanoparticles; high dispersion; quinoline
hydrogenation; catalytic technology

[4]
1,2,3,4-四氢喹啉（py-THQ）是一类重要的化工 中心发生配位作用，致使催化剂失活 。因此，研
原料，已广泛应用于制备药品、农药、染料、生物 究开发高效的喹啉选择性加氢催化剂具有重要的实
碱等 [1-3] 。喹啉选择性加氢制备 py-THQ 是一种最有 际意义。
前途的方法。但喹啉加氢反应通常具有较高的反应 负载型 Pd 纳米催化剂在催化喹啉加氢领域已
能垒，不易被加氢，且喹啉及其氢化物极易与活性 得到广泛应用 [5-7] 。金属纳米粒子的低配位位点和表

收稿日期：2022-08-23; 定用日期：2022-12-12; DOI: 10.13550/j.jxhg.20220782
作者简介：崔坤成（1996—），女，硕士生，E-mail：cui199619962021@163.com。联系人：刘德蓉（1969—），女，副教授，E-mail：
ldrxwxzj@163.com；熊 伟（1968—），男，教授，E-mail：xqxw_xx@163.com。