超声吸附制备均匀分散在SBA-15的S2O82--Fe2O3纳米粒子:增强S2O82--Fe2O3本体催化活性

doi:10.1016/S1872-2067(17)63007-9

催化学报 ›› 2018, Vol. 39 ›› Issue (5): 955-963.DOI: 10.1016/S1872-2067(17)63007-9

超声吸附制备均匀分散在SBA-15的S₂O₈^2--Fe₂O₃纳米粒子:增强S₂O₈^2--Fe₂O₃本体催化活性

楚庆岩^a,b, 陈静^a, 侯文华^c, 余昊轩^d, 王平^a,d, 刘睿^a, 宋广亮^a, 朱红军^a, 赵萍萍^d

a 南京工业大学化学与分子工程学院, 江苏南京 211816;
b 中国石化齐鲁分公司研究院, 山东淄博 255400;
c 南京大学化学化工学院介观化学教育部重点实验室, 江苏南京 210023;
d 山东理工大学化工学院, 山东淄博 255049

收稿日期:2017-11-23 修回日期:2017-12-29 出版日期:2018-05-18 发布日期:2018-04-19
通讯作者: 侯文华
基金资助:
国家重点研究发展计划项目（2016YFB0301703）；江苏省产学研前瞻性联合研究项目（BY2016005-06）；国家自然科学基金（21506118）.

Enhancement of catalytic activity by homo-dispersing S₂O₈^2--Fe₂O₃ nanoparticles on SBA-15 through ultrasonic adsorption

Qingyan Chu^a,b, Jing Chen^a, Wenhua Hou^c, Haoxuan Yu^d, Ping Wang^a,d, Rui Liu^a, Guangliang Song^a, Hongjun Zhu^a, Pingping Zhao^d

a College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China;
b Research institute of QILU petrochemical company, SINOPEC, Zibo 255400, Shandong, China;
c Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China;
d School of Chemical Engineering, Shandong University of Technology, Zibo 255049, Shandong, China

Received:2017-11-23 Revised:2017-12-29 Online:2018-05-18 Published:2018-04-19
Contact: 10.1016/S1872-2067(17)63007-9
Supported by:
This work was supported by the National Key Research and Development Program of China (2016YFB0301703), the Joint Innovation and Research Funding-prospective Joint Research Projects (BY2016005-06), and the National Natural Science Foundation of China (21506118).

摘要/Abstract

摘要：

酸催化剂在化学反应和化工生产中具有重要的作用.传统无机酸，如H₂SO₄，H₃PO₄和对甲苯磺酸等具有较高的催化活性，但是存在污染大、设备腐蚀严重以及催化剂不能重复使用等问题.固体酸具有酸性强、易分离、环境友好以及稳定性和重复使用性好等特点因而近年来越来越引起人们的关注.其中，SO₄^2--M_xO_y固体超强酸（如SO₄^2--ZrO₂，SO₄^2--TiO₂和SO₄^2--SnO₂等）因具有很好的催化性能而备受关注.相比SO₄^2--M_xO_y，S₂O₈^2--M_xO_y具有更强的酸性和稳定性而成为研究的重点.如何克服固体超强酸本体的低比表面积和孔容，增加其比表面积和催化活性是固体超强酸研究的热点.超声吸附法可保证所制介孔固体酸活性组分均匀分散，以及大的比表面积和更多的酸性位点.因此采用超声吸附法制备了一种新型介孔固体酸S₂O₈^2--Fe₂O₃/SBA-15.相比S₂O₈^2--Fe₂O₃本体、B酸和文献报道催化剂，负载30% Fe₂O₃的S₂O₈^2--Fe₂O₃/SBA-15在环氧苯乙烷甲醇醇解的探针反应中显示出很高的催化活性，反应收率为100%.S₂O₈^2--Fe₂O₃纳米粒子的纳米效应和SBA-15介孔结构的协同作用使S₂O₈^2--Fe₂O₃/SBA-15具有高催化活性.
相比S₂O₈^2--Fe₂O₃本体，采用超声分散技术制备的S₂O₈^2--Fe₂O₃/SBA-15固体超强酸具有典型的介孔结构、大的比表面积和孔容，并且表面富含酸性位点.并且吡啶红外分析S₂O₈^2--Fe₂O₃/SBA-15表面富含L酸和B酸.环氧苯乙烷甲醇醇解探针反应表明，Fe₂O₃负载量为30%时，S₂O₈^2--Fe₂O₃/SBA-15的催化活性最高，优于S₂O₈^2--Fe₂O₃本体和已报道的布朗酸和路易斯酸等催化剂，将醇底物拓展（ROHs，R=C₂H₅-C₄H₉），S₂O₈^2--Fe₂O₃/SBA-15的催化活性也优于S₂O₈^2--Fe₂O₃本体.同时，S₂O₈^2--Fe₂O₃/SBA-15具有很好的重复使用性能，连续使用七次，反应收率在84.1%以上.总之，具有高催化活性、好的稳定性和经济性的S₂O₈^2--Fe₂O₃/SBA-15具有广阔的应用前景.

关键词: 介孔固体酸, 纳米粒子, 纳米效应, S₂O₈^2--Fe₂O₃/SBA-15, 酸性位, 超声分散, 醇解

Abstract:

Mesoporous superacids S₂O₈^2--Fe₂O₃/SBA-15 (SFS) with active nanoparticles are prepared by ultrasonic adsorption method. This method is adopted to ensure a homo-dispersed nanoparticle active phase, large specific surface area and many acidic sites. Compared with bulk S₂O₈^2--Fe₂O₃, Brönsted acid catalysts and other reported catalysts, SFS with an Fe₂O₃ loading of 30% (SFS-30) exhibits an outstanding activity in the probe reaction of alcoholysis of styrene oxide by methanol with 100% yield. Moreover, SFS-30 also shows a more excellent catalytic performance than bulk S₂O₈^2--Fe₂O₃ towards the alcoholysis of other ROHs (R=C₂H₅-C₄H₉). Lewis and Brönsted acid sites on the SFS-30 surfaces are confirmed by pyridine adsorbed infrared spectra. The highly efficient catalytic activity of SFS-30 may be attributed to the synergistic effect from the nano-effect of S₂O₈^2--Fe₂O₃ nanoparticles and the mesostructure of SBA-15. Finally, SFS-30 shows a good catalytic reusability, providing an 84.1% yield after seven catalytic cycles.

Key words: Mesoporous superacid, Nanoparticle, Nano effect, S₂O₈^2--Fe₂O₃/SBA-15, Acidic site, Ultrasonic adsorption, Alcoholysis

楚庆岩, 陈静, 侯文华, 余昊轩, 王平, 刘睿, 宋广亮, 朱红军, 赵萍萍. 超声吸附制备均匀分散在SBA-15的S₂O₈^2--Fe₂O₃纳米粒子:增强S₂O₈^2--Fe₂O₃本体催化活性[J]. 催化学报, 2018, 39(5): 955-963.

Qingyan Chu, Jing Chen, Wenhua Hou, Haoxuan Yu, Ping Wang, Rui Liu, Guangliang Song, Hongjun Zhu, Pingping Zhao. Enhancement of catalytic activity by homo-dispersing S₂O₈^2--Fe₂O₃ nanoparticles on SBA-15 through ultrasonic adsorption[J]. Chinese Journal of Catalysis, 2018, 39(5): 955-963.

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超声吸附制备均匀分散在SBA-15的S₂O₈^2--Fe₂O₃纳米粒子:增强S₂O₈^2--Fe₂O₃本体催化活性

Enhancement of catalytic activity by homo-dispersing S₂O₈^2--Fe₂O₃ nanoparticles on SBA-15 through ultrasonic adsorption

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