硅钛杂化介孔球负载金纳米粒子及其催化性能调控

doi:10.15541/jim20210261

无机材料学报 ›› 2022, Vol. 37 ›› Issue (4): 404-412.DOI: 10.15541/jim20210261

硅钛杂化介孔球负载金纳米粒子及其催化性能调控

马慧¹(), 陶疆辉¹, 王艳妮¹, 韩玉¹, 王亚斌¹^,²(), 丁秀萍³()

1.延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 延安 716000
2.西北工业大学化学与化工学院, 西安710129
3.中国科学院青海盐湖研究所, 中国科学院盐湖资源综合高效利用重点实验室, 西宁 810008

收稿日期:2021-04-20 修回日期:2021-07-11 出版日期:2022-04-20 网络出版日期:2021-07-12
通讯作者: 王亚斌, 副教授. E-mail: ybw_bingerbingo@126.com;
丁秀萍, 副研究员. E-mail: dingxp@isl.ac.cn
作者简介:马慧(1996-), 女, 硕士研究生. E-mail: mh08201@163.com
基金资助:
国家自然科学基金(52063029);陕西省自然科学基础研究计划资助项目(2019JQ-104);国家大学生创新创业训练计划项目(S202010719001)

Gold Nanoparticles Supported on Silica & Titania Hybrid Mesoporous Spheres and Their Catalytic Performance Regulation

MA Hui¹(), TAO Jianghui¹, WANG Yanni¹, HAN Yu¹, WANG Yabin¹^,²(), DING Xiuping³()

1. Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry and Chemical Engineering, Yan’an University, Yan’an 716000, China
2. School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710129, China
3. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China

Received:2021-04-20 Revised:2021-07-11 Published:2022-04-20 Online:2021-07-12
Contact: WANG Yabin, associate professor. E-mail: ybw_bingerbingo@126.com;
DING Xiuping, associate professor. E-mail: dingxp@isl.ac.cn
About author:MA Hui (1996-), female, Master candidate. E-mail: mh08201@163.com
Supported by:
National Natural Science Foundation of China(52063029);Natural Science Basic Research Plan in Shaanxi Province of China(2019JQ-104);National Training Program of Innovation and Entrepreneurship for Undergraduates(S202010719001)

摘要/Abstract

摘要：

以能源开发(如光解水制氢)及环境保护(如有机物降解)应用为目标, 负载型贵金属催化剂在设计、制备及理论研究方面已取得了长足的发展。本工作以具有特异形貌及结构的树枝状二氧化硅纳米球载体为基础, 通过溶胶-凝胶法在其孔道引入二氧化钛纳米颗粒形成硅钛杂化结构。通过有机改性技术, 在树枝状硅钛杂化纳米球表面接枝氨基官能团。然后, 通过浸渍法和硼氢化钠还原手段, 在杂化纳米球孔道负载超细金纳米粒子。不同手段表征结果显示实验成功制备了树枝状硅钛杂化纳米球负载金纳米颗粒复合材料。在模拟太阳光下, 所得催化剂光解水产氢量及速率为69.08 μmol·g^-1和13.82 μmol·g^-1·h^-1, 约为对比样催化剂(树枝状二氧化硅纳米球负载金纳米粒子)的7倍。在无光条件下, 其降解对硝基苯酚的表观动力学常数为6.540×10^-3 s^-1, 约为对比样的17倍(0.372×10^-3 s^-1)。由此可见, 设计合成的新型催化剂展现出优越的多功能催化活性。

关键词: 树枝状纳米球, 硅钛杂化结构, 金纳米粒子, 光解水制氢, 对硝基苯酚还原

Abstract:

In order to exploit energy sources (like photocatalytic water splitting for hydrogen production) and protect environment (like organics degradation), supported noble metal catalysts have made considerable progress in terms of design, fabrication, and theory. Herein, based on the specific morphology and structure of dendritic mesoporous silica nanospheres (DMSNs), TiO₂ nanoparticles (NPs) were introduced into the channels via Sol-Gel method, developing dendritic mesoporous silica&titania nanospheres (DMSTNs). Then, amino groups (-NH₂) were grafted onto DMSTNs surfaces by organic modification technology. Finally, ultrasmall gold (Au) NPs were anchored onto the as-prepared DMSTNs-NH₂ through impregnation method and sodium borohydride (NaBH₄) reduction. DMSTNs supported Au NPs catalysts could be successfully constructed, as verified by different methods. Under simulated sunlight for splitting water, the amount of produced H₂ by the brand-new catalysts and the corresponding rate are 69.08 µmol·g^-1 and 13.82 µmol·g^-1·h^-1, respectively, roughly. seven times of that of the contrast sample (DMSNs supported Au NPs). Without light irradiation, the apparent kinetic constant of p-nitrophenol reduction by the as-prepared catalysts is 6.540×10^-3s^-1, about 17 times higher than that of the reference (0.372×10^-3 s^-1). ln conclusion, DMSTNs supported Au NPs exhibit good multifunctional catalytic activity.

Key words: dendritic nanospheres, silica&titania hybrid, gold nanoparticles, photocatalytic water splitting for hydrogen production, p-nitrophenol reduction

中图分类号:

TQ127

马慧, 陶疆辉, 王艳妮, 韩玉, 王亚斌, 丁秀萍. 硅钛杂化介孔球负载金纳米粒子及其催化性能调控[J]. 无机材料学报, 2022, 37(4): 404-412.

MA Hui, TAO Jianghui, WANG Yanni, HAN Yu, WANG Yabin, DING Xiuping. Gold Nanoparticles Supported on Silica & Titania Hybrid Mesoporous Spheres and Their Catalytic Performance Regulation[J]. Journal of Inorganic Materials, 2022, 37(4): 404-412.

图/表 9

图1 DMSNs与DMSTNs负载金纳米粒子催化剂的制备流程示意图

Fig. 1 Schematic diagram of constructing DMSNs- and DMSTNs-based supported Au NPs catalysts

图2 DMSNs (a)、DMSTNs (b)、DMSNs-NH2 (c)、DMSTNs-NH2 (d)、DMSNs-NH2-Au (e)和DMSTNs-NH2-Au (f)的SEM照片

Fig. 2 SEM images of DMSNs (a), DMSTNs (b), DMSNs-NH2 (c), DMSTNs-NH2 (d), DMSNs-NH2-Au (e), and DMSTNs-NH2-Au (f)

图3 DMSNs、DMSTNs、DMSNs-NH2和DMSTNs-NH2的傅里叶转换红外光谱图

Fig. 3 FT-IR spectra of DMSNs, DMSTNs, DMSNs-NH2, and DMSTNs-NH2

图4 DMSTNs、DMSNs-NH2和DMSTNs-NH2的XPS全谱扫描

Fig. 4 XPS survey scan of DMSTNs, DMSNs-NH2, and DMSNs-NH2

图5 DMSNs (a)、DMSTNs (b)、DMSNs-NH2 (c)、DMSTNs-NH2 (d)、DMSNs-NH2-Au (e)、DMSTNs-NH2-Au (f)的透射电镜照片, DMSNs-NH2-Au (g)和DMSTNs-NH2-Au (h)的透射电镜-元素分布图

Fig.5 TEM images of DMSNs (a), DMSTNs (b), DMSNs-NH2 (c), DMSTNs-NH2 (d), DMSNs-NH2-Au (e), and DMSTNs-NH2-Au (f), and TEM-mapping images of DMSNs-NH2-Au (g) and DMSTNs-NH2-Au (h)

图6 DMSNs、DMSTNs、DMSNs-NH2-Au和DMSTNs-NH2-Au的XRD图谱(a), 紫外-可见漫反射光谱图(b)和光致发光谱图(c)

Fig. 6 XRD patterns (a), UV-Vis-DRS spectra (b) and PL spectra (c) of DMSNs, DMSTNs, DMSNs-NH2-Au, and DMSTNs-NH2-Au

图7 DMSNs、DMSTNs、DMSNs-NH2-Au和DMSTNs-NH2-Au在模拟太阳光下的氢产量(a)及速率(b); DMSTNs-NH2-Au 的光解水产氢循环性能(c); DMSTNs-NH2-Au经过5次催化循环后的透射电镜照片(插图为高角环形暗场成像)(d)

Fig. 7 H2 production amount as a function of irradiation time (a) and the corresponding production rates (b) of DMSNs, DMSTNs, DMSNs-NH2-Au, and DMSTNs-NH2-Au, cycling tests of DMSTNs-NH2-Au for H2 production (c), and TEM image of DMSTNs-NH2-Au sample experienced five cycles, with inset showing the high-angle annular dark-field imaging (d)

图8 对硝基苯酚、对硝基苯酚钠和对氨基苯酚的紫外可见漫反射光谱(a), 不同样品(含有硼氢化钠的对硝基苯酚溶液作为空白试样(b)、加入DMSNs(c)、DMSTNs(d)、DMSNs-NH2-Au(e)和DMSTNs-NH2-Au(f))的紫外吸收变化, DMSNs-NH2-Au和DMSTNs-NH2-Au的转化率(g)及准一级模拟方程(h), DMSTNs-NH2-Au循环降解性能(i), DMSTNs-NH2-Au经过10次催化循环后的SEM形貌(j)及元素分布图(k), 任意4个经过10次催化循环的DMSTNs-NH2-Au单体球能谱测试标定区域(l)

Fig. 8 Characteristic ultraviolet absorption peaks of p-nitrophenol, p-nitrophenolate, and p-aminophenol (a), Ultraviolet absorption spectra of different samples, including p-nitrophenol+NaBH4 as the blank sample (b), with the addition of DMSNs (c), DMSTNs (d), DMSNs-NH2-Au (e), and DMSTNs-NH2-Au (f), the conversion (g) and pseudo first-order linear equation (h) of DMSNs-NH2-Au, and DMSTNs-NH2-Au, and cycling tests of DMSTNs-NH2-Au for p-nitrophenol reduction (i), SEM images (j) and energy dispersive spectroscopy (EDS) mappings (k) of DMSTNs-NH2-Au sample experienced ten cycles. EDS measurement of random four DMSTNs-NH2-Au individuals (l)

图9 DMSTNs-NH2-Au 在(a)模拟太阳光条件下光解水制氢和(b)无光照条件下还原对硝基苯酚的催化机理

Fig. 9 Schematic illustration of possible photocatalytic mechanisms for DMSTNs-NH2-Au to split water under simulated sunlight (a) and ordinary catalytic reduction of p-nitrophenol without light irritation (b)

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硅钛杂化介孔球负载金纳米粒子及其催化性能调控

Gold Nanoparticles Supported on Silica & Titania Hybrid Mesoporous Spheres and Their Catalytic Performance Regulation

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