负载银纳米催化剂的聚多巴胺基微球的高效催化性能

doi:10.16085/j.issn.1000-6613.2019-0669

摘要/Abstract

摘要：

利用聚多巴胺（PDA）的还原性和黏附性，成功制备了分别负载银（Ag）纳米催化剂的聚N-异丙基丙烯酰胺-聚多巴胺（PN@PDA/Ag）核壳型微球、聚苯乙烯-聚多巴胺（PS@PDA/Ag）核壳型微球和聚多巴胺（PDA/Ag）均质型微球。系统研究了PN@PDA/Ag、PS@PDA/Ag和PDA/Ag微球的微观结构、化学组成及Ag纳米颗粒的分布情况，并考察了在模型催化反应中，还原剂硼氢化钠（NaBH₄）和反应物对硝基苯酚（4-NP）摩尔比对微球催化性能的影响。结果表明，3种微球均成功负载了Ag纳米催化剂，相比于两种核壳型微球，PDA/Ag微球负载Ag纳米催化剂的含量最多。随着NaBH₄和4-NP摩尔比的增加，PN@PDA/Ag、PS@PDA/Ag和PDA/Ag微球对4-NP的转化率逐渐增大。在考察的摩尔比下，PDA/Ag微球均表现出比PN@PDA/Ag和PS@PDA/Ag微球更优异的催化性能。当摩尔比为500∶1时，PN@PDA/Ag、PS@PDA/Ag和PDA/Ag微球的表观反应速率常数（k_app）值分别为0.21min^-1、0.35min^-1和1.78min^-1。PDA/Ag微球的k_app值远高于文献报道的PDA/Ag微球k_app的最大值0.35min^-1。研究结果将为高效催化微球的设计和制备提供理论指导和实验基础。

关键词: 催化剂载体, 催化, 纳米粒子, 银纳米颗粒, 聚多巴胺

Abstract:

Three silver (Ag) nanocatalysts loaded with core-shell poly(N-isopropylacrylamide)-polydopamine (PN@PDA/Ag) microspheres, core-shell polystyrene-polydopamine (PS@PDA/Ag) microspheres and homogeneous polydopamine (PDA/Ag) microspheres were successfully prepared by making use of the reducibility and adhesion of polydopamine (PDA). The microstructures, chemical compositions and the distribution of Ag nanoparticles of PN@PDA/Ag, PS@PDA/Ag and PDA/Ag microspheres were systematically studied. The effect of molar ratio of reductant sodium borohydride (NaBH₄) to reactant p-nitrophenol (4-NP) on the catalytic performance of the three microspheres were investigated. The results showed that Ag nanocatalysts were successfully loaded on all the three microspheres, and the amount of Ag nanocatalysts loaded on PDA/Ag microspheres was the highest. With the increase of the molar ratio of NaBH₄ to 4-NP, the conversions of 4-NP catalyzed by PN@PDA/Ag, PS@PDA/Ag and PDA/Ag microspheres all showed increasing trends. At all the molar ratios, PDA/Ag microspheres exhibited better catalytic performance than the other two microspheres. When the molar ratio was 500∶1, the apparent kinetic rate constants (k_app) of PN@PDA/Ag, PS@PDA/Ag and PDA/Ag microspheres were 0.21min^-1, 0.35min^-1 and 1.78min^-1, respectively. The k_app of as-prepared PDA/Ag microspheres was much higher than the maximum one of 0.35min^-1 reported in literature. The results could provide theoretical guidance and experimental basis for the design and preparation of efficient catalytic polymeric microspheres.

Key words: catalyst support, catalysis, nanoparticles, silver nanoparticles, polydopamine

中图分类号:

TQ426.65

郭石菲,谢锐,汪伟,巨晓洁,刘壮,褚良银. 负载银纳米催化剂的聚多巴胺基微球的高效催化性能[J]. 化工进展, 2020, 39(1): 166-173.

Shifei GUO,Rui XIE,Wei WANG,Xiaojie JU,Zhuang LIU,Liangyin CHU. Efficient catalytic performance of polydopamine-based microspheres loaded with silver nanocatalysts[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 166-173.

图/表 7

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微球	XPS测试的各元素质量分数/%				ICP-AES测试的Ag含量
微球	C	O	N	Ag	浓度/μg?mL^-1	质量分数/%
PN	72.85(70.59)	17.21(15.69)	9.94(13.72)	—	—	—
PS	100.00(100)	0.00	0.00	—	—	—
PDA	71.44(61.02)	22.43(27.12)	6.13(11.86)	—	—	—
PN@PDA	73.12	17.56	9.32	—	—	—
PS@PDA	77.76	18.81	3.43	—	—	—
PN@PDA/Ag	71.13	18.64	10.23	0.00	82.6	3.3
PS@PDA/Ag	74.00	23.82	1.09	1.09	15.6	0.6
PDA/Ag	68.31	22.57	2.61	6.51	244	9.8

微球	XPS测试的各元素质量分数/%				ICP-AES测试的Ag含量
微球	C	O	N	Ag	浓度/μg?mL^-1	质量分数/%
PN	72.85(70.59)	17.21(15.69)	9.94(13.72)	—	—	—
PS	100.00(100)	0.00	0.00	—	—	—
PDA	71.44(61.02)	22.43(27.12)	6.13(11.86)	—	—	—
PN@PDA	73.12	17.56	9.32	—	—	—
PS@PDA	77.76	18.81	3.43	—	—	—
PN@PDA/Ag	71.13	18.64	10.23	0.00	82.6	3.3
PS@PDA/Ag	74.00	23.82	1.09	1.09	15.6	0.6
PDA/Ag	68.31	22.57	2.61	6.51	244	9.8

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