Preparation of Gold Nanoparticle/Perfused Silica Composite Microspheres and Evaluation of Their Catalytic Performance in the Reduction of 4-Nitrophenol

doi:10.12422/j.issn.1006-396X.2026.01.009

Abstract

Abstract:

Gold nanoparticles （Au NPs） exhibit great application potential in the reduction of aromatic nitro compound pollutants, owing to their nanoscale size effects and excellent catalytic properties. However, their tendency to aggregate has hindered practical applications. In this study, perfusion silica gel microspheres （PSM） with a hierarchical porous structure comprising macropores, mesopores, and perfusion pores were used as a support material. The surface of the PSM was first modified with thiol groups and then combined with gold nanoparticles to fabricate Au NPs/PSM composite microspheres. These composite microspheres were characterized by SEM, TEM, Raman spectroscopy and XRD. The catalytic performance of the Au NPs/PSM catalyst in reducing 4-nitrophenol to 4-aminophenol was investigated. The results showed that the composite microspheres retained their perfusion channels, and the Au NPs were uniformly distributed on the PSM surface. The average size of the Au NPs was approximately 4.8 nm, with a mass loading fraction of 2.72%. The Au NPs/PSM composite was employed as a catalyst for the reduction of 4-nitrophenol to 4-aminophenol. At 30 °C, the catalytic reaction followed first-order kinetics, with a rate constant of 0.103 min?1. The composite microspheres demonstrate excellent catalytic activity, good stability, and high recyclability.

Key words: Gold nanoparticles, Permeation silica microspheres, 4-nitrophenol, Catalytic reaction

摘要：

纳米金粒子（Au NPs）因其纳米尺寸效应和优异的催化性能，在催化芳硝基化合物的还原反应中具有广泛的应用前景，但易团聚的特性限制了其实际应用。以具有大孔、介孔和灌流孔的多级孔结构的灌流硅胶微球（PSM）为载体，对其表面进行巯基改性，并将改性后的PSM进一步与Au NPs复合，制备了纳米金/灌流硅胶复合微球（Au NPs/PSM）；采用SEM、TEM、拉曼光谱、XRD等手段，对复合微球进行了表征；考察了Au NPs/PSM催化剂将4-硝基苯酚还原为4-氨基苯酚的性能。结果表明，Au NPs/PSM保留了灌流孔道，Au NPs在PSM表面均匀分散，平均粒径约为4.8 nm，负载量（质量分数）为2.72%；在30 ℃的温度下，该催化反应符合一级反应动力学特征，动力学速率常数为0.103 min^-1；该复合微球表现出优异的催化活性、良好的稳定性和可循环使用性。

关键词: 纳米金粒子, 灌流硅胶微球, 4-硝基苯酚, 催化

CLC Number:

TQ426

Xiaoming SHEN, Shu QU, Junfang GUO. Preparation of Gold Nanoparticle/Perfused Silica Composite Microspheres and Evaluation of Their Catalytic Performance in the Reduction of 4-Nitrophenol[J]. Journal of Petrochemical Universities, 2026, 39(1): 75-82.

沈晓明, 屈舒, 郭俊芳. 纳米金/灌流硅胶复合微球的制备及催化还原4-硝基苯酚的性能研究[J]. 石油化工高等学校学报, 2026, 39(1): 75-82.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.01.009

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I1/75

Figures/Tables 13

Fig.1 UV spectra of the gold nanocolloid reaction system before and after the addition of NaBH4

Fig.2 TEM image of Au NPs/PSM nano-gold sol

Fig.3 SEM image of PSM

Fig.4 The nitrogen adsorption-desorption isotherm and bore diameter distribution of PSM

Fig.5 Infrared spectra of PSM, thiol-modified PSM and Au NPs/PSM

Fig.6 Raman spectra of thiol-modified PSM and Au NPs/PSM

Fig.7 XRD patterns of PSM and Au NPs/PSM and EDS pattern of Au NPs/PSM

Fig.8 SEM and TEM images of thiol-modified PSM and Au NPs/PSM

Fig.9 UV-vis spectra and linear fitting curve of 4-NP in sodium hydroxide solutions with different concentrations

Fig.10 Evaluation results of catalytic performance of Au NPs/PSM

Fig.11 Fitting curve of concentration versus time

Fig.12 The effect of cycle times on the performance of Au NPs/PSM

Fig.13 The effect of temperature on catalytic reduction reaction time

References 24

[1]	雒丽娜，陈常东，王芳芳. MXene@TiO₂/Co-MoS_2- xOy复合材料的制备及其光催化性能研究［J］. 石油化工高等学校学报， 2025， 38（1）： 74-80.
	LUO L N， CHEN C D， WANG F F. Preparation and photocatalytic properties of MXene@TiO₂/Co-MoS_2- xOy composites［J］. Journal of Petrochemical Universities， 2025， 38（1）： 74-80.
[2]	CARDOSO JUAREZ A O， IVAN OCAMPO LOPEZ E， KESARLA M K， et al. Advances in 4-nitrophenol detection and reduction methods and mechanisms： An updated review［J］. ACS Omega， 2024， 9（31）： 33335-33350.
[3]	MEHRINEJAD CHOOBARI S F， NEMATOLLAHZADEH A， BABOLAN N M. Inverse fluidized bed reactor enhanced with silver nanoparticle catalysts-embedded starch-based hydrogel for the sustainable conversion of 4-nitrophenol to 4-aminophenol［J］. Chemical Engineering Journal， 2025， 510： 161612.
[4]	YANG P， XU A D， XIA J， et al. Facile synthesis of highly catalytic activity Ni-Co-Pd-P composite for reduction of the p-nitrophenol［J］. Applied Catalysis A： General， 2014， 470： 89-96.
[5]	LIU Z N， LI B， ZHANG H C. Controllable assemblies of Au NPs/P₅A for enhanced catalytic reduction of 4-nitrophenol［J］. Polymers， 2024， 16（15）： 2104.
[6]	TEIMOURI M， KHOSRAVI-NEJAD F， ATTAR F， et al. Gold nanoparticles fabrication by plant extracts： Synthesis， characterization， degradation of 4-nitrophenol from industrial wastewater， and insecticidal activity——A review［J］. Journal of Cleaner Production， 2018， 184： 740-753.
[7]	张骁鑫，许雯，孙辉，等. 双金属催化剂在对硝基苯酚加氢还原中的研究进展［J］. 南京工业大学学报（自然科学版）， 2024， 46（5）： 479-489.
	ZHANG X X， XU W， SUN H， et al. Research progress on bimetallic catalysts in 4-nitrophenol hydrogenation reduction［J］. Journal of Nanjing University of Technology（Natural Science Edition）， 2024， 46（5）： 479-489.
[8]	常梦涵，路昊明，温沁雪. 改性聚氨酯载体用于军工废水处理［J］. 化工环保， 2025， 45（6）： 807-813.
	CHANG M H， LU H M， WEN Q X. Research on treatment of military wastewater using modified polyurethane carriers［J］. Environmental Protection of Chemical Industry， 2025， 45（6）： 807-813.
[9]	赵玲玉，赵可鑫，张秀玲，等. 氢等离子体制备Pd/GO-P催化材料及其催化还原对硝基苯酚性能［J］. 石油学报（石油加工）， 2023， 39（5）： 1059-1069.
	ZHAO L Y， ZHAO K X， ZHANG X L， et al. Hydrogen plasma synthesis of Pd/GO-P and its performance for catalytic reduction of p-nitrophenol［J］. Acta Petrolei Sinica （Petroleum Processing Section）， 2023， 39（5）： 1059-1069.
[10]	REN Z J， LI H H， LI J， et al. Green synthesis of reduced graphene oxide/chitosan/gold nanoparticles composites and their catalytic activity for reduction of 4-nitrophenol［J］. International Journal of Biological Macromolecules， 2023， 229： 732-745.
[11]	DARUICH DE SOUZA C， RIBEIRO NOGUEIRA B， ROSTELATO M E C M. Review of the methodologies used in the synthesis gold nanoparticles by chemical reduction［J］. Journal of Alloys and Compounds， 2019， 798： 714-740.
[12]	NAVEEN M H， KHAN R， BANG J H. Gold nanoclusters as electrocatalysts： Atomic level understanding from fundamentals to applications［J］. Chemistry of Materials， 2021， 33（19）： 7595-7612.
[13]	KE W， QIN X D， VAZQUEZ Y， et al. Direct characterization of interface sites in Au/TiO₂ catalysts prepared using atomic layer deposition［J］. Chem Catalysis， 2024， 4（5）： 100977.
[14]	SRAVAN KUMAR K B， WHITTAKER T N， PETERSON C， et al. Water poisons H₂ activation at the Au-TiO₂ interface by slowing proton and electron transfer between Au and titania［J］. Journal of the American Chemical Society， 2020， 142（12）： 5760-5772.
[15]	李欢欢，李瑾，王鹏飞，等. 还原氧化石墨烯负载纳米金催化还原4-硝基苯酚的性能研究［J］. 中国海洋大学学报（自然科学版）， 2025， 55（6）： 102-111.
	LI H H， LI J， WANG P F， et al. Immobilization of nanogold on reduced graphene oxide and the catalytic reduction of 4-nitrophenol［J］. Periodical of Ocean University of China， 2025， 55（6）： 102-111.
[16]	CHEN W R， LI B R， GAO G B， et al. Chiral supramolecular nanomaterials： From chirality transfer and amplification to regulation and applications［J］. Interdisciplinary Materials， 2023， 2（5）： 689-713.
[17]	施治国，冯钰锜. 新型快速分离介质灌流硅胶微球的合成及应用［J］. 分析化学， 2009， 37（5）： 695-697.
	SHI Z G， FENG Y Q. Synthesis of perforative silica microspheres and its application in fast separation［J］. Chinese Journal of Analytical Chemistry， 2009， 37（5）： 695-697.
[18]	代巧玲，孙佳新，贾燕子，等. 二氧化硅包覆核壳结构催化剂的制备与应用研究进展［J］. 石油炼制与化工， 2024， 55（3）： 148-153.
	DAI Q L， SUN J X， JIA Y Z， et al. Research progress on preparation and application of SiO₂ coated core-shell catalysts［J］. Petroleum Processing and Petrochemicals， 2024， 55（3）： 148-153.
[19]	朱燕超，冀银豪，赵春梅. 功能性二氧化硅微球的制备［J］. 当代化工， 2024， 53（8）： 1799-1803.
	ZHU Y C， JI Y H， ZHAO C M. Preparation of functional silica microspheres［J］. Contemporary Chemical Industry， 2024， 53（8）： 1799-1803.
[20]	HAISS W， THANH N T K， AVEYARD J， et al. Determination of size and concentration of gold nanoparticles from UV-vis spectra［J］. Analytical Chemistry， 2007， 79（11）： 4215-4221.
[21]	董前民，杨艳敏，梁培，等. 表面增强拉曼散射（SERS）衬底的研究及应用［J］. 光谱学与光谱分析， 2013， 33（6）： 1547-1552.
	DONG Q M， YANG Y M， LIANG P， et al. Research on the substrates of surface enhanced raman scattering （SERS） and their applications to biomedicine and environmental analysis［J］. Spectroscopy and Spectral Analysis， 2013， 33（6）： 1547-1552.
[22]	BURUNKOVA J， KOKENYESI S， CSARNOVICS I， et al. Influence of gold nanoparticles on the photo-polymerization processes and structure in acrylate nanocomposites［J］. European Polymer Journal， 2015， 64： 189-195.
[23]	SHIN K S， CHOI J Y， PARK C S， et al. Facile synthesis and catalytic application of silver-deposited magnetic nanoparticles［J］. Catalysis Letters， 2009， 133（1）： 1-7.
[24]	杨棽垚，杨二龙，戚志林，等. 基于反应分子动力学的超临界多元热流体发生规律及物性变化特征［J］. 东北石油大学学报， 2024， 48（6）： 98-108.
	YANG C Y， YANG E L， QI Z L， et al. Generation and variation characteristics of supercritical multicomponent thermal fluids based on reaction molecular dynamics simulation［J］. Journal of Northeast Petroleum University， 2024， 48（6）： 98-108.