活性炭催化苯一步羟基化制备苯酚

doi:10.1016/S1872-2067(11)60444-0

摘要/Abstract

摘要： 将市售活性炭经过硝酸、过氧化氢及不同温度进行处理后用于苯的羟基化反应, 并研究了活性炭催化苯羟基化反应机理. 用 Boehm 滴定, N₂吸附-脱附及 X 射线光电子能谱对活性炭进行了表征. 结果表明, 反应体系的 pH 对催化剂活性具有重要的影响, 活性炭对苯的吸附受表面含氧基团含量的影响. 模型化合物反应结果表明, 活性炭表面的酚羟基和羰基是反应的活性位, 两者可相互转化, 并在一定的 pH 条件下达到平衡, 该转化使得 H2O2 活化为羟基自由基, 进而与苯反应生成苯酚. 在苯羟基化反应中, 活性炭表现出良好且稳定的催化性能, 苯酚收率可达 14.4%.

关键词: 活性炭, 苯, 羟基化, 含氧基团, 模型化合物, 苯酚

Abstract: Phenol is widely used in industry. The hydroxylation of benzene to phenol can meet the increasing requirement for phenol and green chemistry. Commercial wood-based activated carbon was treated by different methods, including oxidation by nitric acid and hydrogen peroxide and thermal treatment at different temperatures, and used as the catalyst for the hydroxylation of benzene to phenol in acetonitrile using H₂O₂ as oxidant. The mechanism of the hydroxylation was also investigated. The activated carbon samples were ch aracterized by Boehm titration, nitrogen adsorption, and X-ray photoelectron spectroscopy. The pH had a significant effect on the phenol yield. The effect of benzene adsorption was also investigated. Several model compounds with oxygen groups were used as catalysts for the hydroxylation of benzene. The reaction between phenolic hydroxyl and quinone on the surface of activated carbon was responsible for the hydroxylation of benzene to phenol when it activated H₂O₂ to form the hydroxyl radical. Activated carbon was an efficient and stable catalyst and a maximum phenol yield of 14.4% was obtained under the optimal reaction conditions.

Key words: activated carbon, benzene hydroxylation, oxygen group, model compound, mechanism

徐加泉, 刘慧慧, 杨瑞光, 李桂英, 胡常伟. 活性炭催化苯一步羟基化制备苯酚[J]. 催化学报, 2012, 33(10): 1622-1630.

XU Jia-Quan, LIU Hui-Hui, YANG Rui-Guang, LI Gui-Ying, HU Chang-Wei. Hydroxylation of Benzene by Activated Carbon Catalyst[J]. Chinese Journal of Catalysis, 2012, 33(10): 1622-1630.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(11)60444-0

https://www.cjcatal.com/CN/Y2012/V33/I10/1622

参考文献

1 Niwa S I, Eswaramoorthy M, Nair J, Raj A, Itoh N, Shoji H, Namba T, Mizukami F. Science, 2002, 295: 105
2 Zhang F M, Chen X, Zhuang J, Xiao Q, Zhong Y J, Zhu W D. Catal Sci Technol, 2011, 1: 1250
3 Yuranov I, Bulushev D A, Renken A, Kiwi-Minsker L. Appl Catal A, 2007, 319: 128
4 Tani M, Sakamoto T, Mita S, Sakaguchi S, Ishii Y. Angew Chem, Int Ed, 2005, 44: 2586
5 Dittmeyer R, Bortolotto L. Appl Catal A, 2011, 391: 311
6 陈佳琦, 高爽, 李军, 吕迎. 催化学报(Chen J Q, Gao Sh, Li J, Lv Y. Chin J Catal), 2011, 32: 1446
7 Chammingkwan P, Hoelderich W F, Mongkhonsi T, Kanchanawanichakul P. Appl Catal A, 2009, 352: 1
8 Abbo H S, Titinchi S J J. Appl Catal A, 2009, 356: 167
9 Zhang J, Tang Y, Li G Y, Hu C W. Appl Catal A, 2005, 278: 251
10 Song S Q, Yang H X, Rao R C, Liu H D, Zhang A M. Appl Catal A, 2010, 375: 265
11 Song S Q, Jiang S J, Rao R C, Yang H X, Zhang A M. Appl Catal A, 2011, 401: 215
12 Choi J S, Kim T H, Choo K Y, Sung J S, Saidutta M B, Ryu S O, Song S D, Ramachandra B, Rhee Y W. Appl Catal A, 2005, 290: 1
13 Zhong Y K, Li G Y, Zhu L F, Yan Y, Wu G, Hu C W. J Mol Catal A, 2007, 272: 169
14 Chen C H, Xu J Q, Jin M M, Li G Y, Hu C W. Chin J Chem Phys, 2011, 24: 358
15 Rodríguez-Reinoso F. Carbon, 1998, 36: 159
16 陈晨, 林性怡, 于政锡, 陈晓晖, 郑起, 魏可镁. 石油化工(Chen Ch, Lin X Y, Yu Zh X, Chen X H, Zheng Q, Wei K M. Petrochem Technol), 2004, 33: 1024
17 Song W, Li Y, Guo X H, Li J, Huang X M, Shen W J. J Mol Catal A, 2010, 328: 53
18 Yu G X, Lu S X, Chen H, Zhu Z N. Carbon, 2005, 43: 2285
19 Pereira M F R, Órfão J J M, Figueiredo J L. Appl Catal A, 1999, 184: 153
20 Georgi A, Kopinke F D. Appl Catal B, 2005, 58: 9
21 Ono Y, Matsumura T, Kitajima N, Fukuzumi S I. J Phys Chem, 1977, 81: 1307
22 Donnet J B. Carbon, 1968, 6: 161
23 Boehm H P. Carbon, 1994, 32: 759
24 Takaoka M, Yokokawa H, Takeda N. Appl Catal B, 2007, 74: 179
25 Guo B, Zhu L F, Hu X K, Zhang Q, Tong D M, Li G Y, Hu C W. Catal Sci Technol, 2011, 1: 1060
26 Boehm H P. In: Eley D D, Herman P, Weisz P B eds. Ad-vances in Catalysis. New York: Academic Press, 1966. 179
27 Goertzen S L, Thériault K D, Oickle A M, Tarasuk A C, An-dreas H A. Carbon, 2010, 48: 1252
28 Oickle A M, Goertzen S L, Hopper K R, Abdalla Y O, An-dreas H A. Carbon, 2010, 48: 3313
29 Boehm H P, Diehl E, Heck W. Proceedings of the 2nd London Carbon and Graphite Conference. London, UK, 1965. 369
30 Brunauer S, Deming L S, Deming W E, Teller E. J Am Chem Soc, 1940, 62: 1723
31 朱赛, 何欣雅, 赵亮, 李惠萍. 化学通报(Zhu S, He X Y, Zhao L, Li H P. Chemistry), 2010, 3: 284
32 Moreno-Castilla C, López-Ramón M V, Carrasco-Mar??n F. Carbon, 2000, 38: 1995
33 Zerda T W, Yuan X, Moore S M, Leon y Leon C A. Carbon, 1999, 37: 1999
34 Figueiredo J L, Pereira M F R, Freitas M M A, Órfão J J M. Carbon, 1999, 37: 1379
35 贾建国, 李闯, 朱春来, 肖春英, 徐东, 闫欣, 梁长海. 炭素技术(Jia J G, Li Ch, Zhu Ch L, Xiao Ch Y, Xu D, Yan X, Liang Ch H. Carbon Techniques), 2009, 28(6): 11
36 Zielke U, Hüttinger K J, Hoffman W P. Carbon, 1996, 34: 983
37 Moreno-Castilla C, Carrasco-Marín F, Mueden A. Carbon, 1997, 35: 1619
38 Larsen E C, Walton J H. J Phys Chem, 1940, 44: 70
39 León y León C A, Radovic L R. In: Thrower P A ed. Chemis-try and Physics of Carbon. New York: Marcel Dekker, 1994. 213
40 Biniak S, Szymański G, Siedlewski J, Swiatkowski A. Car-bon, 1997, 35: 1799
41 Serp P, Figueiredo J L. Carbon Materials for Catalysis. New Jersey: Wiley, 2009. 177
42 Wibowo N, Setyadhi L, Wibowo D, Setiawan J, Ismadji S. J Hazard Mater, 2007, 146: 237
43 Van der Zee F P, Bisschops I A E, Lettinga G, Field J A. Environ Sci Technol, 2003, 37: 402
44 Diez L, Livertoux M H, Stark A A, Wellman-Rousseau M, Leroy P. J Chromatogr B, 2001, 763: 185

[1]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[2]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[3]	孟帅奇, 李忠玉, 张鹏, Francisca Contreras, 季宇, Ulrich Schwaneberg. 深度学习指导的热裂褐藻角质酶工程用于促进PET解聚[J]. 催化学报, 2023, 50(7): 229-238.
[4]	Mengistu Tulu Gonfa, 申升, 陈浪, 胡彪, 周威, 白张君, 区泽堂, 尹双凤. 光催化苯制苯酚的研究进展[J]. 催化学报, 2023, 49(6): 16-41.
[5]	夏思源, 李奇远, 张仕楠, 许冬, 林秀, 孙露菡, 许景三, 陈接胜, 李国栋, 李新昊. Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用[J]. 催化学报, 2023, 49(6): 180-187.
[6]	马多征, 李相呈, 刘闯, Caroline Versluis, 叶迎春, 王振东, Eelco T. C. Vogt, Bert M. Weckhuysen, 杨为民. SCM-36分子筛纳米片用于乙烯和2,5-二甲基呋喃转化制可再生对二甲苯[J]. 催化学报, 2023, 47(4): 200-213.
[7]	李倩, 刘䶮, 李灿. 钯催化不对称烯丙基化/去对称化反应合成无保护基的2-喹啉酮骨架环状氨基酸[J]. 催化学报, 2023, 47(4): 222-228.
[8]	张志普, 卢珊珊, 张兵, 史艳梅. 揭示硫掺杂的碳材料在水电氧化过程中活性苯醌基团及惰性硫残留物的形成[J]. 催化学报, 2023, 47(4): 129-137.
[9]	苏凯艺, 张超锋, 王业红, 张健, 郭强, 高著衍, 王峰. 利用N-羟基邻苯二甲酰亚胺研究可见光照射下Nb₂O₅中高度扭曲的NbO₆单元作为电子转移位点[J]. 催化学报, 2022, 43(7): 1894-1905.
[10]	刘清港, 马俊国, 陈晨. 纳米催化剂的理性设计与精准调控[J]. 催化学报, 2022, 43(4): 898-912.
[11]	韩孝琴, 左佳昌, 温丹璐, 袁友珠. ZnZrO_x-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯[J]. 催化学报, 2022, 43(4): 1156-1164.
[12]	Muhammad Tayyab, 刘玉洁, 敏世雄, Rana Muhammad Irfan, 朱乔虹, 周亮, 雷菊英, 张金龙. 无贵金属光催化剂VC/CdS纳米线将苯甲醇选择性氧化为苯甲醛并产氢[J]. 催化学报, 2022, 43(4): 1165-1175.
[13]	范召博, 郭鑫, 杨梦雪, 靳治良. 机械法制备石墨二炔并耦合CdSe纳米粒子高效光催化制氢[J]. 催化学报, 2022, 43(10): 2708-2719.
[14]	魏英聪, 张琪琪, 周颖, 马雄风, 王乐乐, 王严杰, 洒荣建, 龙金林, 付贤智, 员汝胜. 非贵金属等离子共振增强MoO_3-_x基S型异质结光催化苯甲醇氧化同步产氢和苯甲醛[J]. 催化学报, 2022, 43(10): 2665-2677.
[15]	俞浩然, 刘丹旭, 王恒屹, 于海爽, 闫青云, 嵇家辉, 张金龙, 邢明阳. CoP助催化光芬顿中单线态氧协同表面吸附羟基自由基降解苯酚[J]. 催化学报, 2022, 43(10): 2678-2689.