表面润湿性可控的碳纳米管负载钯催化剂及其在1,8-二硝基萘选择性加氢中的催化性能

doi:10.16085/j.issn.1000-6613.2019-0218

摘要/Abstract

摘要：

首先通过原子转移自由基聚合技术（atom transfer radical polymerization，ATRP）在碳纳米管（CNT）表面接枝聚N-异丙基丙烯酰胺（PNIPAM），成功制备出表面润湿性可控的复合载体（CNT-PNIPAM），并以其为载体制备Pd催化剂（Pd/CNT-PNIPAM）。采用红外光谱仪（FTIR）、热重仪（TGA）、有机元素分析仪（OEA）、差示量热仪（DSC）、X射线衍射仪（XRD）、透射电镜（TEM）和N₂吸附等手段对材料进行表征。制备的催化剂用于1,8-二硝基萘（1,8-DNN）选择性加氢反应，并研究表面化学对催化性能的影响。结果表明，CNT-PNIPAM的最低临界溶液温度（LCST）为37℃左右。利用温敏效应，CNT-PNIPAM在25℃（＜LCST）下负载Pd纳米颗粒，粒径为3.6nm±0.8nm。载体在低温下的亲水表面提高了Pd纳米颗粒在其上的分散。Pd/CNT-PNIPAM在120℃ （＞LCST）下表面润湿性发生转换。PNIPAM接枝引起催化剂表面化学性质的变化，进而使其对底物的吸附性能发生改变。Pd/CNT-PNIPAM上Pd颗粒的高度分散及其对1,8-DNN优良的吸附性能不仅使催化活性得以提高（反应速率常数k=2.1h^-1），而且对1,8-DAN的选择性也更高（完全反应时1,8-DAN选择性达98%）。

关键词: 润湿性可控表面, N-异丙基丙烯酰胺, 碳纳米管, 1,8-二硝基萘, 加氢

Abstract:

PNIPAM was successfully grafted on carbon nanotubes (CNT) by Atom Transfer Radical Polymerization (ATRP). The synthesized composite CNT-PNIPAM with wettability controllable surface was then used as support to prepare Pd catalyst (Pd/CNT-PNIPAM). The composite and its supported Pd catalyst were characterized by FTIR, TGA, OEA, DSC, XPS, XRD, TEM and N₂ adsorption. Further, the as-prepared catalysts were applied for selective hydrogenation of 1,8-dinitronaphthalene (1,8-DNN) and the effect of surface chemistry on the catalytic performance was studied. The results showed that CNT-PNIPAM had a lower critical solution temperature (LCST) about 37℃. It exhibited hydrophilic surface at room temperature that was helpful for the Pd dispersion. The Pd nanoparticles deposited had a small particle size of 3.6nm±0.8nm. When the temperature ascended to 120℃ (＞LCST), the surface wettability of Pd/CNT-PNIPAM transformed from hydrophilicity to hydrophobicity. The changes in the surface chemical properties after PNIPAM grafting further caused the changes in its adsorption performance to the substrates. Highly dispersed Pd nanoparticles on Pd/CNT-PNIPAM and its excellent adsorption performance to 1,8-DNN resulted in the enhanced catalytic activity (reaction rate constant k=2.1h^-1) and selectivity to 1,8-DAN (98% 1,8-DAN selectivity at nearly complete reaction).

Key words: wettability controllable surface, PNIPAM, carbon nanotubes, 1,8-dinitronaphthalene, hydrogenation

中图分类号:

TQ612.3

窦梦迪,丁雪洁,刘雯欣,张伟,鲁墨弘,李明时,朱劼. 表面润湿性可控的碳纳米管负载钯催化剂及其在1,8-二硝基萘选择性加氢中的催化性能[J]. 化工进展, 2020, 39(1): 181-189.

Mengdi DOU,Xuejie DING,Wenxin LIU,Wei ZHANG,Mohong LU,Mingshi LI,Jie ZHU. Carbon nanotubes supported palladium catalyst with wettability controllable surface and its catalytic performance in selective hydrogenation of 1,8-dinitronaphthalene[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 181-189.

图/表 15

图1 1,8-二硝基萘催化加氢反应路径

图2 CNT和CNT-PNIPAM的FTIR谱图

图3 CNT和CNT-PNIPAM的TGA曲线

表1 CNT材料有机元素分析

样品	C/%	H/%	N/%	PNIPAM/%
CNT	96.37	0.32	—	—
CNT-PNIPAM	77.45	2.45	2.73	31.0

图4 CNT和CNT-PNIPAM的孔径分布

表2 CNT改性前后的结构特性

样品	BET比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
CNT	217	0.71	13.1
CNT-A	221	0.77	14.5
CNT-PNIPAM	169	0.76	18.2

图5 CNT和CNT-PNIPAM在不同温度下不同溶剂中的分散性

图6 CNT和CNT-PNIPAM的DSC曲线

图7 Pd催化剂的TEM图

表3 Pd催化剂性质

样品	Pd负载量^①/%	Pd纳米颗粒粒径^②/nm	Pd分散度^③/%
Pd/CNT	1.02	10.7±3.0	12.1±3.5
Pd/CNT-A	0.96	4.6±0.8	26.2±3.6
Pd/CNT-PNIPAM	1.04	3.6±0.8	34.9±7.8

图8 CNT-PNIAM-Pd的XRD表征

图9 催化剂上Pd3d的XPS谱图

图10 不同Pd催化剂对1,8-二硝基萘选择性加氢反应的催化活性

图11 不同Pd催化剂对1,8-二氨基萘选择性对比图

表4 CNT-PNIPAM重复结果的催化性能

样品	转化率/%	选择性/%	收率/%
CNT-PNIPAM-R1	98.82	97.68	96.53
CNT-PNIPAM-R2	94.26	96.92	91.36
CNT-PNIPAM-R3	84.50	97.36	82.27

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