Preparation and Catalytic Performance of Metal/Silica Nanosphere Catalysts

LI Yi-shao; SHEN Xiang-yu; ZHANG Shou-qun; ZHANG Song; WANG Mo-zhen; GE Xue-wu

doi:10.14028/j.cnki.1003-3726.2025.25.101

您当前的位置：

首页 >

文章列表页 >

Preparation and Catalytic Performance of Metal/Silica Nanosphere Catalysts

更新时间：2025-08-26

- Preparation and Catalytic Performance of Metal/Silica Nanosphere Catalysts
- Polymer Bulletin Vol. 38, Issue 9, Pages: 1385-1396(2025)
- 作者机构：
  
  精准智能化学全国重点实验室，中国科学技术大学高分子科学与工程系，合肥 230026
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.101
  CLC：
- Received：03 April 2025，
  
  Accepted：03 June 2025，
  
  Published Online：29 July 2025，
  
  Published：20 September 2025
- 稿件说明：
移动端阅览
LI Yi-shao, SHEN Xiang-yu, ZHANG Shou-qun, ZHANG Song, WANG Mo-zhen, GE Xue-wu. Preparation and Catalytic Performance of Metal/Silica Nanosphere Catalysts[J]. Polymer bulletin, 2025, 38(9): 1385-1396.
DOI：

LI Yi-shao, SHEN Xiang-yu, ZHANG Shou-qun, ZHANG Song, WANG Mo-zhen, GE Xue-wu. Preparation and Catalytic Performance of Metal/Silica Nanosphere Catalysts[J]. Polymer bulletin, 2025, 38(9): 1385-1396. DOI： 10.14028/j.cnki.1003-3726.2025.25.101.

摘要

高性能纳米金属催化剂的开发与能源转换和存储、环境保护以及工业应用的发展密切相关。本工作采用Stöber法制备了粒径为60 nm的单分散二

氧化硅纳米球，随后用

-缩水甘油醚氧丙基三甲氧基硅烷(KH560)对其进行改性，制备了一系列不同环氧基(EO)含量的改性二氧化硅纳米球(SiO

-EO)。进一步利用EO与Ag

离子的相互作用以及Ag

离子与乙醇的氧化还原反应，成功制备了表面均匀且稳定负载着6 nm银纳米粒子的二氧化硅(Ag/SiO

-EO)纳米球催化剂。研究了SiO

-EO纳米球上的EO含量与Ag/SiO

-EO复合纳米球的形貌和银负载量之间的关系，证明了EO比Si―OH更易与Ag

离子结合，这使得EO修饰的二氧化硅纳米球成为银纳米粒子的优良载体。并且载体纳米球上的EO含量决定了银纳米粒子的饱和负载量，因此通过精准调控EO和Ag

离子的相对数量，可以实现对银纳米粒子的精准高效负载。将Ag/SiO

-EO复合纳米球用于催化NaBH

还原亚甲基蓝(MB)的模型反应，结果表明所制备的复合纳米催化剂具有良好的催化活性和循环使用性。本工作不仅为纳米二氧化硅载体的环氧基功能化以及原位精准负载金属纳米粒子提供了理论和实践参考，还拓展了纳米二氧化硅载体的应用领域，为开发新型纳米金属催化体系和高性能环氧树脂复合材料提供了新思路。

Abstract

The development of high-performance nanometal catalysts is closely related to the development of energy conversion and storage

environmental protection

and industrial applications. In this work

monodisperse silica nanospheres with a particle size of 60 nm were precisely prepared by Stöber method

followed by the surface modification with 3-glycidoxypropyltrimethoxysilane (KH560) to obtain a series of epoxy (EO)-functionalized silica nanospheres (SiO

-EO) with different EO content. Based on the interaction between Ag

ions and EO groups and the redox reaction between EO and ethanol

silver nanoparticles with a size of 6 nm were uniformly and stably loaded on the SiO

-EO nanosphere carriers

resulting in the successful preparation of the novel Ag/SiO

-EO composite nanosphere catalyst. The dependence of the morphology and loading capacity of silver nanoparticles on Ag/SiO

-EO on the EO content of the SiO

-EO nanosphere carrier was studied. The result shows that EO has a stronger affinity toward Ag

ions than Si―OH groups

which makes the epoxy-functionalized silica nanospheres an excellent support for silver nanoparticles. Moreover

the EO content on the carrier nanospheres determines the loading capacity of silver nanoparticles. Therefore

stable and e

fficient loading of silver nanoparticles on SiO

-EO nanospheres can be achieved by precise regulation of the relative content of EO and Ag

ions. The Ag/SiO

-EO composite nanospheres were applied to the model reduction of methylene blue by NaBH

. The result shows that the prepared composite nanospheres exhibit excellent catalytic activity and recyclability. This work not only provides theoretical and practical references for the epoxy-functionalized nano-silica carriers and the in-situ precise loading of metal nanoparticles

but also expands the application fields of nano-silica carriers

providing novel strategies for developing advanced nanometal catalytic systems and high-performance epoxy resin composites.

关键词

Keywords

references

Hervés, P. ; Pérez-Lorenzo, M. ; Liz-Marzán, L. M. ; Dzubiella, J. ; Lu, Y. ; Ballauff, M . Catalysis by metallic nanoparticles in aqueous solution: model reactions . Chem. Soc. Rev. , 2012 , 41 ( 17 ), 5577 – 5587 .

Clarke, A. K. ; James, M. J. ; O’Brien, P. ; Taylor, R. J. K. ; Unsworth, W. P . Silica-supported silver nitrate as a highly active dearomatizing spirocyclization catalyst: synergistic alkyne activation by silver nanoparticles and silica . Angew. Chem. Int. Ed. , 2016 , 55 ( 44 ), 13798 – 13802 .

Wang, Y. ; Dong, B. B. ; Wang, Z. K. ; Cong, X. F. ; Bi, X. H . Silver-catalyzed reduction of quinolines in water . Org. Lett. , 2019 , 21 ( 10 ), 3631 – 3634 .

Kang, Y. P. ; Liu, R. M. ; Si, M. Z . Surface enhanced Raman scattering on self-assembled nano silver film prepared by electrolysis method . Chin. J. Chem. Phys. , 2009 , 22 ( 4 ), 435 – 439 .

Qiao, B. T. ; Liu, L. Q. ; Zhang, J. ; Deng, Y. Q . Preparation of highly effective ferric hydroxide supported noble metal catalysts for CO oxidations: from gold to palladium . J. Catal. , 2009 , 261 ( 2 ), 241 – 244 .

Yan, X. L. ; Li, S. ; Pan, Y. X. ; Xing, B. ; Li, R. F. ; Jang, B. W. L. ; Liu, X. G . Tunable Ag + ion release from Ag@C f or antibacterial and antifouling performances . RSC Adv. , 2015 , 5 ( 49 ), 39384 – 39391 .

Siamaki, A. R. ; El Rahman S Khder, A. ; Abdelsayed, V. ; El-Shall, M. S. ; Gupton, B. F . Microwave-assisted synthesis of palladium nanoparticles supported on graphene: a highly active and recyclable catalyst for carbon-carbon cross-coupling reactions . J. Catal. , 2011 , 279 ( 1 ), 1 – 11 .

Martínez-Edo, G. ; Balmori, A. ; Pontón, I. ; Martí del Rio, A. ; Sánchez-García, D . Functionalized ordered mesoporous silicas (MCM-41): synthesis and applications in catalysis . Catalysts , 2018 , 8 ( 12 ), 617 .

Jia, L. ; Pei, X. W. ; Zhou, F. ; Liu, W. M . Unconventional assembly of bimetallic Au–Ni Janus nanoparticles on chemically modified silica spheres . Chemistry , 2014 , 20 ( 7 ), 2065 – 2070 .

Li, X. J. ; Yang, S. S. ; Luan, Y. ; Wang, D. ; Du, X . Polydopamine modification on dendritic porous silica surface for efficient adhesion of functional nanoparticles . Colloids Surf. A Physicochem. Eng. Aspects , 2024 , 703 , 135439 .

Yang, J. C. ; Kim, S. H. ; Kwak, S. K. ; Song, H. K . Curvature-induced metal-support interaction of an islands-by-islands composite of platinum catalyst and carbon nano-onion for durable oxygen reduction . ACS Appl. Mater. Interfaces , 2017 , 9 ( 28 ), 23302 – 23308 .

Guo, K. ; Ding, Y. ; Luo, J. ; Gu, M. F. ; Yu, Z. X . NiCu bimetallic nanoparticles on silica support for catalytic hydrolysis of ammonia borane: composition-dependent activity and support size effect . ACS Appl. Energy Mater. , 2019 , 2 ( 8 ), 5851 – 5861 .

Zienkiewicz-Strzałka, M. ; Deryło-Marczewska, A. ; Kozakevych, R. B . Silica nanocomposites based on silver nanoparticles-functionalization and pH effect . Appl. Nanosci. , 2018 , 8 ( 7 ), 1649 – 1668 .

Zhang, J. X. ; Huang, G. W. ; Zhang, C. ; He, Q. H. ; Huang, C. ; Yang, X. ; Song, H. Y. ; Liang, Z. X. ; Du, L. ; Liao, S. J . Immobilization of highly active Pd nano-catalysts on functionalized mesoporous silica supports using mercapto groups as anchoring sites and their catalytic performance for phenol hydrogenation . Chin. J. Catal. , 2013 , 34 ( 8 ), 1519 – 1526 .

Dong, Z. P. ; Le, X. ; Li, X. L. ; Zhang, W. ; Dong, C. X. ; Ma, J. T . Silver nanoparticles immobilized on fibrous nano-silica as highly efficient and recyclable heterogeneous catalyst for reduction of 4-nitrophenol and 2-nitroaniline . Appl. Catal. B Environ. , 2014 , 158 , 129 – 135 .

Cao, W. ; Matharoo, G. S. ; Gulam Razul, M. S. ; Szabo, E. ; MacLeod, K. A. ; Joye, I. J. ; Pink, D. A . Quantifying sulfhydryl oxidation rates using Ellman's procedure . Physics of Fluids , 2025 , 37 ( 1 ), 017116 .

McKenzie, Z. ; Kendall, M. ; MacKay, R. M. ; Whitwell, H. ; Elgy, C. ; Ding, P. ; Mahajan, S. ; Morgan, C. ; Griffiths, M. ; Clark, H. ; Madsen, J . Surfactant protein A (SP-A) inhibits agglomeration and macrophage uptake of toxic amine modified nanoparticles . Nanotoxicology , 2015 , 9 ( 8 ), 952 – 962 .

Cao, X. Y. ; Wang, K. J. ; Mao, Q. F. ; Gu, Z. G. ; Wang, F . MCM-41-supported double metal cyanide nanocomposite catalyst for ring-opening polymerisation of propylene oxide . J. Nanopart. Res. , 2022 , 24 ( 3 ), 71 .

Wang, Q. ; Li, Q. Y. ; Wu, C. F . Construction of dual coordination networks in epoxidized butadiene-acrylonitrile rubber/CuSO 4 composites and mechanical behaviors . Polymer , 2020 , 207 , 122865 .

Sprenger, S . Nanosilica-toughened epoxy resins . Polymers , 2020 , 12 ( 8 ), 1777 .

Jeong, H. ; Jang, K. S . Catalysis of silver and bismuth in various epoxy resins . Polymers , 2024 , 16 ( 3 ), 439 .

Song, G. S. ; Lee, D. S. ; Kang, I . The effects of in situ -formed silver nanoparticles on the electrical properties of epoxy resin filled with silver nanowires . Polymers , 2016 , 8 ( 4 ), 157 .

Boumedienne, N. ; Faska, Y. ; Maaroufi, A. ; Pinto, G. ; Vicente, L. ; Benavente, R . Thermo-structural analysis and electrical conductivity behavior of epoxy/metals composites . J. Phys. Chem. Solids , 2017 , 104 , 185 – 191 .

胡延鹏 , 袁双龙 , 方斌 , 朱绪敏 , 杨向民 . 纳米铜/环氧树脂导热复合材料的制备、结构与性能 . 北京化工大学学报(自然科学版) , 2019 , 46 ( 6 ), 28 – 35 .

Yang, W. X. ; Zeng, K. ; Liu, J. X. ; Chen, L. C. ; Wang, M. Z. ; Zhuo, S. C. ; Ge, X. W . Fabrication of inverse-opal lysozyme-imprinted polydopamine/polypyrrole microspheres with near-infrared-light-controlled release property . J. Colloid Interface Sci. , 2019 , 548 , 37 – 47 .

Yang, W. X. ; Xu, G. Q. ; Shu, J. J. ; Wang, M. Z. ; Ge, X. W . Preparation and adsorption property of novel inverse-opal hierarchical porous N-doped carbon microspheres . Chin. Chem. Lett. , 2021 , 32 ( 2 ), 866 – 869 .

李德亮 , 徐翔民 , 张晟卯 , 吴志申 , 张治军 . 盐酸法测定 γ -氨丙基三乙氧基硅烷及其修饰的纳米二氧化硅表面氨基 . 分析科学学报 , 2007 , 23 ( 3 ), 323 – 326 .

相益信 , 沈显荣 , 高建纲 , 宋庆平 . 运用RAFT聚合方法在纳米二氧化硅表面接枝聚异戊二烯及其增强SBS . 高分子通报 , 2019 , ( 3 ), 43 – 50 .

江蒙 , 舒晶晶 , 金汉青 , 刘仪轩 , 汪谟贞 , 葛学武 . 中空介孔二氧化硅微球的辐射接枝改性及其在防腐涂料中的应用 . 辐射研究与辐射工艺学报 , 2019 , 37 ( 5 ), 050603 .

Zhao, W. J. ; Xiao, X. Y. ; Pan, G. M. ; Ye, Z. H . Fabrication of superhydrophobic cotton fabric treated with N -dodecyltrimethoxysilane/ zirconium oxychloride for highly efficient oil/water separation . J. Coat. Technol. Res. , 2020 , 17 ( 3 ), 657 – 668 .

Zhao, C. ; Ge, Z. Q. ; Jiang, Z. N. ; Yan, S. ; Shu, J. J. ; Wang, M. Z. ; Ge, X. W . Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template . Chin. Chem. Lett. , 2023 , 34 ( 4 ), 107499 .

Li, J. ; Ding, H. ; Zhang, H. Q. ; Guo, C. L. ; Hong, X. Y. ; Sun, L. Y. ; Ding, F. C . Superhydrophobic methylated silica Sol for effective oil-water separation . Materials , 2020 , 13 ( 4 ), 842 .

Cai, Y. C. ; Tan, F. T. ; Qiao, X. L. ; Wang, W. ; Chen, J. G. ; Qiu, X. L . Room-temperature synthesis of silica supported silver nanoparticles in basic ethanol solution and their antibacterial activity . RSC Adv. , 2016 , 6 ( 22 ), 18407 – 18412 .

Wang, T. ; Jiang, X. ; Mao, C. W . Influence of an adsorption layer and its evolvement on the formation of Ag . Langmuir , 2008 , 24 ( 24 ), 14042 – 14047 .

楼晨曦 , 陈怡蒙 , 叶芬霞 , 周琦 , 穆景山 . 二氧化碳辅助壳聚糖/银凝胶小球的制备及其催化性能的研究 . 高分子通报 , 2023 , ( 10 ), 1321 – 1329 .

Kuang, T. R. ; Deng, L. B. ; Shen, S. T. ; Deng, H. X. ; Shen, Z. S. ; Liu, Z. J. ; Zhao, Z. P. ; Chen, F. ; Zhong, M. Q . Nano-silver-modified polyphosphazene nanoparticles with different morphologies: design, synthesis, and evaluation of antibacterial activity . Chin. Chem. Lett. , 2023 , 34 ( 12 ), 108584 .

韩淼 , 李德荣 , 袁柳青 , 吕永博 , 葛黎明 , 李德富 , 穆畅道 . 双醛淀粉还原制备纳米银及其在胶原基抗菌敷料中的应用 . 高分子学报 , 2019 , 50 ( 4 ), 366 – 374 .

Guo, Y. F. ; Fu, X. N. ; Xie, Y. ; Zhu, L. ; Liu, R. J. ; Liu, L. X . Synthesis of Ag/ZnO nanocomposites with enhanced visible photocatalytic performance . Opt. Mater. , 2022 , 133 , 112980 .

Xie, Y. J. ; Yan, B. ; Xu, H. L. ; Chen, J. ; Liu, Q. X. ; Deng, Y. H. ; Zeng, H. B . Highly regenerable mussel-inspired Fe 3 O 4 @ polydopamine-Ag core-shell microspheres as catalyst and adsorbent for methylene blue removal . ACS Appl. Mater. Interfaces , 2014 , 6 ( 11 ), 8845 – 8852 .

Rad, A. S. ; Mirabi, A. ; Binaian, E. ; Tayebi, H . A review on glucose and hydrogen peroxide biosensor based on modified electrode included silver nanoparticles . Int. J. Electrochem. Sci. , 2011 , 6 ( 8 ), 3671 – 3683 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰