H6PMo9V3O40/SiO2催化剂催化酚类化合物选择性硝化

doi:10.3724/SP.J.1095.2014.30261

摘要/Abstract

摘要： 为创建洁净高效的酚类化合物硝化工艺，以杂多酸H6PMo9V3O40(PMAV3)为活性组分，硅胶为载体，浸渍法制备了负载型催化剂PMAV3/SiO2，采用红外光谱、X射线衍射谱、N2吸附-脱附法及TG-DSC分析等测试技术对该催化剂的结构及热稳定性进行了表征；考察了该催化剂对多种酚类化合物硝化反应的催化性能。结果显示，该催化剂对多种酚类化合物的硝化反应具有很强的催化活性和区域选择性，产率为83.7%～94.5%，其中苯酚、邻甲酚、邻氯苯酚和邻氟苯酚以邻位硝化产物居多，水杨酸的对位硝化产物占绝对优势；负载催化剂的织构性质与载体相近，但随负载量增加，比表面积逐渐降低；PMAV3/SiO2的热稳定性好于本体PMAV3。催化剂回收容易，重复使用5次，活性基本不变。

关键词: 催化剂, 杂多酸, H6PMo9V3O40, 硅胶, 硝, 酚类化合物

Abstract: To establish a clean and efficient nitration process of phenolic compounds, heteropolyacid H6PMo9V3O40(PMAV3) and chromatographic silica gel were respectively chosen as active component and carrier for the preparation of a series of supported catalysts(PMAV3/SiO2) via the conventional impregnation method. The catalysts were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD)，N2 adsorption-desorption and thermogravimetry-differential scanning calorimetry(TG-DSC). The catalytic performance of catalysts was evaluated for the nitration of phenols. The results reveals that PMAV3/SiO2 exhibits excellent catalytic activity and regioselectivity for the nitration of phenols, the nitration yield is in the range of 83.7%～94.5%. For salicylic acid, the para-selectivity is nearly 100%, but for phenol, 2-methylphenol, 2-chlorophenol and 2-fluorphenol, the ortho-selectivity is observed. The textural properties of PMAV3/SiO2 are close to that of PMAV3, but BET of the supported catalysts is decreased with the rise of PMAV3 loading. PMAV3/SiO2 shows better thermal stability than PMAV3. The catalyst can be recovered easily and reused for five times without noticeable drop in activity.

Key words: catalyst, heteropolyacid, H6PMo9V3O40, silica gel, nitration, phenolic compound

中图分类号:

吴锦明, 施磊, 沈爱宝, 汤艳峰, 陆天虹. H₆PMo₉V₃O₄₀/SiO₂催化剂催化酚类化合物选择性硝化[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30261.

WU Jinming1, SHI Lei1, SHEN Aibao1*, TANG Yanfeng1, LU Tianhong2,3. Selective Nitration of Phenols via H₆PMo₉V₃O₄₀/SiO₂ catalysts[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30261.

参考文献

[1] Olah G A,Malhotra R,Narang S C. Nitration Methods and Mechanism[M]. New York:VCH Press,1989:5-15.

[2] Zaldivar J M,Molgab E,Alos M A,et al. Aromatic Nitrations by Mixed Acid. Fast Liquid-Liquid Reaction Regime[J]. Chem Eng Process,1996,35(2):91-105.

[3] Mellor J M,Mittoo S,Parkes R,et al. Improved Nitrations Using Metal Nitrate-Sulfuric Acid Systems[J]. Tetrahedron,2000,56(40):8019-8024.

[4] Selvam J J P,Suresh V,Rajesh K,et al. Highly Efficient Nitration of Phenolic Compounds by Zirconyl Nitrate[J]. Tetrahedron Lett,2006,47(15):2507-2509.

[5] Anuradha V,Srinivas P V,Aparna P,et al. p-Toluenesulfonic Acid Catalyzed Regiospecific Nitration of Phenols with Metal Nitrates[J]. Tetrahedron Lett,2006,47(28):4933-4935.

[6] Pourali A R,Fatemi F. Selective Nitration of Phenols Using Bismuth Subnitrate/Charcoal in the Presence of Trichloroisocyanuric Acid under Aprotic Conditions[J]. Chinese Chem Lett,2010,21(11):1283-1286.

[7] Nowrouzi N,Jonaghani M Z. Nitration of Aromatic Compounds under Neutral Conditions Using the Ph2PCl/I2/AgNO3 Reagent System[J]. Tetrahedron Lett,2011,52(39):5081-5082.

[8] Wang P C,Lu M. Regioselectivity Nitration of Aromatics with N2O5 in PEG-based Dicationic Ionic Liquid[J]. Tetrahedron Lett,2011,52(13):1452-1455.

[9] Ma X M,Li B D,Chen L,et al. Selective Nitration of Aromatic Compounds Catalyzed by H beta Zeolite Using N2O5[J]. Chinese Chem Lett,2012,23(7):809-812.

[10] Parida K M,Rath D. Studies on MCM-41:Effect of Sulfate on Nitration of Phenol[J]. J Mol Catal A:Chem,2006,258(1/2):381-387.

[11] Khder A S,Ahmed A I. Nitration of Phenol over Nanosized Tungsten Oxide Supported on Sulfated SnO2 as a Solid Acid Catalyst[J]. Appl Catal A,2009,354(1/2):153-160.

[12] Kemdeo S M,Sapkal V S,Chaudhari G N. TiO2-SiO2 Mixed Oxide Supported MoO3 Catalyst:Physicochemical Characterization and Activities in Nitration of Phenol[J]. J Mol Catal A:Chem,2010,323(1/2):70-77.

[13] Timofeeva M N. Acid Catalysis by Heteropoly Acids[J]. Appl Catal A,2003,256(1/2):19-35.

[14] Shaabani A,Behnam M,Rezayan A H. Tungstophosphoric Acid (H3PW12O40) Catalyzed Oxidation of Organic Compounds with NaBrO3[J]. Catal Commun,2009,10(7):1074-1078.

[15] Rafiee E,Joshaghani M,Tork F,et al. Esterification of Mandelic Acid Catalyzed by Heteropoly Acid[J]. J Mol Catal A:Chem,2008,283(1/2):1-4.

[16] Feng S J,Zhang L,Ren Y H,et al. Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide over Cesium Salts of Keggin-type Heteropoly Acids[J]. Acta Chim Sin,2012,70(22):2316-2322.

[17] Mallick S,Parida K M. Selective Nitration of Phenol over Silicotungstic Acid Supported Zirconia[J]. Catal Commun,2007,8(10):1487-1492.

[18] Kumar A S H,Rao K T V,Upendar K,et al. Nitration of Methyl 5-Nitrosalicylate Catalyzed by H6PMoV3O40 Supported on Silica Gel[J]. Catal Commun,2012,18:37-40

[19] WU Jinming,SHEN Aibao. Synthesis of Methyl 5-Nitrosalicylate Catalyzed by H6PMoV3O40 Supported on Silica Gel[J]. Fine Chem,2011,28(6):603-605(in Chinese).

吴锦明，沈爱宝. 硅胶负载H6PMo9V3O40催化制备5-硝基水杨酸甲酯[J]. 精细化工,2011,28(6):603-605.

[20] WU Jinming,TANG Yanfeng,SHEN Aibao. Synthesis of 5-Nitrosalicylaldehyde Catalyzed by H6PMo9V3O40 Supported on Silica Gel[J]. Chinese J Appl Chem,2012,29(5):545-550(in Chinese).

吴锦明,汤艳峰,沈爱宝. 硅胶负载H6PMo9V3O40催化合成5-硝基水杨醛[J]. 应用化学,2012,29(5):545-550.

[21] PEI Supeng,YUE Bin,CHENG Jifang,et al. Selective Oxidation of Methane on SBA-15 Supported P-Mo-V Oxide Catalysts[J]. Acta Chim Sin,2008,66(8):902-908(in Chinese).

裴素朋,岳斌,程记芳,等. 负载型 P-Mo-V/SBA-15催化剂上的甲烷选择氧化反应[J]. 化学学报,2008,66(8):902-908.

[22] Rodrigues J A R,Filho A P O,Moran P J S,et al. Regioselectivity of the Nitration of Phenol by Acetyl Nitrate Adsorbed on Silica Gel[J]. Tetrahedron,1999,22(55):6733-6738.

[23] HE Yigong,LI Fen,WANG Peng,et al. Adsorption, Acidity and Physico-chemical Properties of Heteropolyacid Catalysts[J]. Pet Process Petrochem,1996,27(8):12-16(in Chinese).

何奕工，李奋，王蓬，等. 杂多酸催化剂的吸附、酸性和物化性质[J]. 石油炼制与化工,1996,27(8):12-16.

[24] QIAN Hua,LIU Dabin,YE Zhiwen. Selective Nitration of Chlorobenzene with N2O5 Assisted by Heteropolyacids[J]. Chiense J Appl Chem,2009,26(6):676-680(in Chinese).

钱华，刘大斌，叶志文. 负载杂多酸催化下N2O5对氯苯的选择性硝化[J]. 应用化学,2009,26(6):676-680.

H₆PMo₉V₃O₄₀/SiO₂催化剂催化酚类化合物选择性硝化

Selective Nitration of Phenols via H₆PMo₉V₃O₄₀/SiO₂ catalysts

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张毅城, 查飞, 唐小华, 常玥, 田海锋, 郭效军. 非均相催化制备有机过氧化物的研究进展[J]. 应用化学, 2023, 40(6): 769-788.
[2]	于宜辰, 张雨宸, 张耀远, 吴芹, 史大昕, 陈康成, 黎汉生. 本体金属氧化物在丙烷无氧脱氢中的研究进展[J]. 应用化学, 2023, 40(6): 789-805.
[3]	李佳铮, 何述钟. 天然产物Polygalolides的全合成研究进展[J]. 应用化学, 2023, 40(5): 615-624.
[4]	伍凡, 田贺元, 刘鹏, 孙立伟, 张一波, 杨向光. 高氧空位尖晶石型锰基催化剂用于低温NH₃-SCR反应[J]. 应用化学, 2023, 40(5): 697-707.
[5]	李冰, 刘军辉, 宋亚坤, 李想, 郭旭明, 熊健. 金属-有机骨架材料在催化氨硼烷水解释氢中的研究进展[J]. 应用化学, 2023, 40(3): 329-340.
[6]	耿佳美, 马素芳, 刘文, 刁海鹏, 武志芳, 李思进. 肝靶向荧光探针用于HepG2细胞中ONOO^-的特异性检测[J]. 应用化学, 2023, 40(3): 441-448.
[7]	王路飞, 甄蒙蒙, 沈伯雄. 贫电解液下电催化剂对调控锂硫电池性能的研究进展[J]. 应用化学, 2023, 40(2): 188-209.
[8]	李玉凰, 卢泽毅, 袁红梅, 王刚, 张成江. 酰腙键聚合物凝胶的制备及其在硝基呋喃类药物分析中的应用[J]. 应用化学, 2023, 40(1): 100-108.
[9]	曹蓉, 夏杰桢, 廖漫华, 赵路超, 赵晨, 吴琪. 单原子催化剂在电化学合成氨中的理论研究进展[J]. 应用化学, 2023, 40(1): 9-23.
[10]	张丹, 尚润梅, 赵振涛, 李君华, 邢锦娟. V/Ce-Al₂O₃催化甲醇选择性氧化制备二甲氧基甲烷[J]. 应用化学, 2022, 39(9): 1429-1436.
[11]	王显, 杨小龙, 马荣鹏, 刘长鹏, 葛君杰, 邢巍. 单原子分散的Ir-N-C燃料电池阳极抗中毒催化剂[J]. 应用化学, 2022, 39(8): 1202-1208.
[12]	刘也, 郭少波, 梁艳莉, 葛红光, 马剑琪, 刘智峰, 刘波. 核壳型纳米复合材料CuFe₂O₄@NH₂@Pt的制备及催化性能[J]. 应用化学, 2022, 39(8): 1237-1245.
[13]	张超. 单原子催化剂电催化还原二氧化碳研究进展[J]. 应用化学, 2022, 39(6): 871-887.
[14]	李世帅, 刘佳奇, 王佳一, 杨江峰. 多级孔Beta沸石合成研究进展[J]. 应用化学, 2022, 39(6): 912-926.
[15]	王岩, 张树聪, 汪兴坤, 刘志承, 王焕磊, 黄明华. 电解海水析氢反应过渡金属基催化剂的研究进展[J]. 应用化学, 2022, 39(6): 927-940.