Citation: Xinli Yang, Liming Qiao, Weilin Dai. One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde[J]. Chinese Journal of Catalysis, ;2015, 36(11): 1875-1885. doi: 10.1016/S1872-2067(15)60972-X shu

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

Xinli Yang ^a,, ,
Liming Qiao ^a ,
Weilin Dai ^b,,

1.
a School of Chemistry & Chemical Engineering, Henan University of Technology, Zhengzhou 450001, Henan, China;

Corresponding author: Xinli Yang, Weilin Dai,
Received Date: 15 July 2015
Available Online: 10 September 2015
Fund Project: 河南工业大学自然科学基础研究重点培育计划(2013JCYJ09) (2013JCYJ09) 河南省省属高校基本科研业务费专项资金(2014YWQQ13) (2014YWQQ13) 国家自然科学基金(20903035, 21373054). (20903035, 21373054)

A hierarchical microporous-mesoporous metal-organic framework of HKUST-1(Cu)-encapsulated phosphotungstic acid (HPW) material, referred to as HPWs@Meso-HKUST-1, is prepared by a one-pot synthesis method using cetyltrimethylammonium bromide as the supramolecular template. The addition of HPWs to the synthesis mixture of hierarchical porous HKUST-1 results in the direct encapsulation of HPWs inside the mesopores of the HKUST-1 structure, with a homogeneous distribution over the HKUST-1 crystals, which is confirmed by XRD, FT-IR, N₂ adsorption, UV-Vis DRS, and TEM. FT-IR-CO adsorption experiments indicated that additional Lewis acid sites were present in the HPWs@Meso-HKUST-1 sample. The novel heterogeneous catalyst demonstrates excellent catalytic performance for the selective oxidation of cyclopentene (CPE) to glutaraldehyde (GA) using tert-butyl hydroperoxide and acetonitrile (MeCN) as the oxidant and solvent, respectively. The high activity of the catalyst is attributed to the mesostructure of the catalyst and the nature and appropriate abundance of the HPWs—being highly dispersed with the addition of Lewis sites. After a reaction for 36 h, the 30% wt% HPWs@Meso-HKUST-1 catalyst exhibits a CPE conversion of 92.5% and a high GA yield of 73%. Furthermore, the HPWs@Meso-HKUST-1 material is sufficiently stable to prevent the leaching of HPWs, and behaves as a true heterogeneous catalyst that can be repeatedly recycled without sustaining a loss of activity and selectivity in the selective oxidation of CPE.
- Metal-organic frameworks,
- HKUST-1,
- Phosphotungstic acids,
- Cyclopentene,
- Glutaraldehyde
1. [1]
  [1] Kozhevnikov I V. Chem Rev, 1998, 98: 171
2. [2]
  [2] Inumaru K, Ishihara T, Kamiya Y, Okuhara T, Yamanaka S. Angew Chem Int Ed, 2007, 46: 7625
3. [3]
  [3] Bigi F, Corradini A, Quarantelli C, Sartori G. J Catal, 2007, 250: 222
4. [4]
  [4] Khder A E R S. Appl Catal A, 2008, 343: 109
5. [5]
  [5] Schwegler M A, Vinke P, van der Eijk M, van Bekkum H. Appl Catal A, 1992, 80: 41
6. [6]
  [6] Dupont P, Védrine J C, Paumard E, Hecquet G, Lefebvre F. Appl Catal A, 1995, 129 : 217
7. [7]
  [7] Nomiya K, Murasaki H, Miwa M. Polyhedron, 1986, 5: 1031
8. [8]
  [8] Kozhevnikov I V, Kloetstra K R, Sinnema A, Zandbergen H W, van Bekkum H. J Mol Catal A, 1996, 114: 287
9. [9]
  [9] Yuan C Y, Chen J. Chin J Catal (袁程远, 陈静. 催化学报), 2011, 32: 1191
10. [10]
  [10] Khder A E R S, Khder, Hassan H M A, El-Shall M S. Appl Catal A, 2012, 411-412: 77
11. [11]
  [11] Ferey G. Chem Soc Rev, 2008, 37: 191
12. [12]
  [12] Long J R, Yaghi O M. Chem Soc Rev, 2009, 38: 1213
13. [13]
  [13] Dhakshinamoorthy A, Garcia H. Chem Soc Rev, 2012, 41: 5262
14. [14]
  [14] Prestipino C, Regli L, Vitillo J G, Bonino F, Damin A, Lamberti C, Zecchina A, Solari P L, Kongshaug K O, Bordiga S. Chem Mater, 2006, 18: 1337
15. [15]
  [15] Chui S S Y, Lo S M F, Charmant J P H, Orpen A G, Williams I D. Science, 1999, 283: 1148
16. [16]
  [16] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81
17. [17]
  [17] Alaerts L, Séguin E, Poelman H, Thibault-Starzyk F, Jacobs P A, De Vos D E. Chem Eur J, 2006, 12: 7353
18. [18]
  [18] Dhakshinamoorthy A, Alvaro M, Garcia H. J Catal, 2009, 267: 1
19. [19]
  [19] Wu Y, Qiu L G, Wang W, Li Z Q, Xu T, Wu Z Y, Jiang X. Trans Met Chem, 2009, 34: 263
20. [20]
  [20] Brown K, Zolezzi S, Aguirre P, Venegas-Yazigi D, Paredes-Garcia V, Baggio R, Novak M A, Spodine E. Dalton Trans, 2009: 1422
21. [21]
  [21] Marx S, Kleist W, Baiker A. J Catal, 2011, 281: 76
22. [22]
  [22] Sun C Y, Liu S X, Liang D D, Shao K Z, Ren Y H, Su Z M. J Am Chem Soc, 2009, 131: 1883
23. [23]
  [23] Janssens N, Wee L H, Bajpe S, Breynaert E, Kirschhock C E A, Martens J A. Chem Sci, 2012, 3: 1847
24. [24]
  [24] Song J, Luo Z, Britt D K, Furukawa H, Yaghi O M, Hardcastle K I, Hill C L. J Am Chem Soc, 2011, 133: 16839
25. [25]
  [25] Yang H, Li J, Wang L Y, Dai W, Lü Y, Gao S. Catal Commun, 2013, 35: 101
26. [26]
  [26] Wee L H, Janssens N, Bajpe S R, Kirschhock C E A, Martens J A. Catal Today, 2011, 171: 275
27. [27]
  [27] Klein N, Senkovska I, Gedrich K, Stoeck U, Henschel A, Mueller U, Kaskel S. Angew Chem Int Ed, 2009, 48: 9954
28. [28]
  [28] Fang Q R, Makal T A, Young M D, Zhou H C. Comments Inorg Chem, 2010, 31: 165
29. [29]
  [29] Xuan W M, Zhu C F, Liu Y, Cui Y. Chem Soc Rev, 2012, 41: 1677
30. [30]
  [30] Song L F, Zhang J, Sun L X, Xu F, Li F, Zhang H Z, Si X L, Jiao C L, Li Z B, Liu S, Liu Y L, Zhou H Y, Sun D L, Du Y, Cao Z, Gabelica Z. Energy Environ Sci, 2012, 5: 7508
31. [31]
  [31] Qiu L G, Xu T, Li Z Q, Wang W, Wu Y, Jiang X, Tian X Y, Zhang L D. Angew Chem Int Ed, 2008, 47: 9487
32. [32]
  [32] Furukawa H, Nakamura T, Inagaki H, Nishikawa E, Imai C, Misono M. Chem Lett, 1988: 877
33. [33]
  [33] Furukawa H, Nishikawa E, Koyama T. JP Patent 62029546. 1987
34. [34]
  [34] Deng J F, Xu X H, Chen H Y, Jiang A R. Tetrahedron, 1992, 48: 3503
35. [35]
  [35] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81
36. [36]
  [36] Yuan D Q, Lu W G, Zhao D, Zhou H C. Adv Mater, 2011, 23: 3723
37. [37]
  [37] Chen H, Dai W L, Deng J F, Fan K N. Catal Lett, 2002, 81: 131
38. [38]
  [38] Dai W L, Chen H, Cao Y, Li H X, Xie S H, Fan K N. Chem Commun, 2003: 892
39. [39]
  [39] Gregg S J, Sing K S W. Adsorption, Surface Area and Porosity. London: Academic Press, 1997. 111
40. [40]
  [40] Sun L B, Li J R, Park J, Zhou H C. J Am Chem Soc, 2012, 134: 126
41. [41]
  [41] Wee L H, Wiktor C, Turner S, Vanderlinden W, Janssens N, Bajpe S R, Houthoofd K, Van Tendeloo G, De Feyter S, Kirschhock C E A, Martens J A. J Am Chem Soc, 2012, 134: 10911
42. [42]
  [42] Pauly T R, Liu Y, Pinnavaia T J, Billinge S J L, Rieker T P. J Am Chem Soc, 1999, 121: 8835
43. [43]
  [43] Férey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J, Surblé S, Margiolaki I. Science, 2005, 309: 2040
44. [44]
  [44] Rao K M, Gobetto R, Iannibello A, Zecchina A. J Catal, 1989, 119: 512
45. [45]
  [45] Damyanova S, Dimitrov L, Mariscal R, Fierro J L G, Petrov L, Sobrados I. Appl Catal A, 2003, 256: 183
46. [46]
  [46] Zang Y D, Shi J, Zhao X M, Kong L C, Zhang F M, Zhong Y J. Reac Kinet Mech Catal, 2013, 109: 77
47. [47]
  [47] Wee L H, Bonino F, Lamberti C, Bordiga S, Martens J A. Green Chem, 2014, 16: 1351
48. [48]
  [48] Vimont A, Goupil J M, Lavalley J C, Daturi M, Surblé S, Serre C, Millange F, Férey G, Audebrand N. J Am Chem Soc, 2006, 128: 3218
49. [49]
  [49] Youn M H, Kim H, Jung J C, Song I K, Barteau K P, Barteau M A. J Mol Catal A, 2005, 241: 227
50. [50]
  [50] Juan-Alcañiz J, Ramos-Fernandez E V, Lafont U, Gascon J, Kapteijn F. J Catal, 2010, 269: 229
51. [51]
  [51] Duncan D C, Chambers R C, Hecht E, Hill C L. J Am Chem Soc, 1995, 117: 681
52. [52]
  [52] Hu X F, Lu Y K, Dai F N, Liu C G, Liu Y Q. Microporous Mesoporous Mater, 2013, 170: 36
1. [1]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
2. [2]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢. Acta Physico-Chimica Sinica, 2025, 41(1): 2308032-. doi: 10.3866/PKU.WHXB202308032
3. [3]
  Ran HUO , Zhaohui ZHANG , Xi SU , Long CHEN . Research progress on multivariate two dimensional conjugated metal organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2063-2074. doi: 10.11862/CJIC.20240195
4. [4]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
5. [5]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
6. [6]
  Yongzhi LI , Han ZHANG , Gangding WANG , Yanwei SUI , Lei HOU , Yaoyu WANG . A two-dimensional metal-organic framework for the determination of nitrofurantoin and nitrofurazone in aqueous solution. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 245-253. doi: 10.11862/CJIC.20240307
7. [7]
  Yueyue WEI , Xuehua SUN , Hongmei CHAI , Wanqiao BAI , Yixia REN , Loujun GAO , Gangqiang ZHANG , Jun ZHANG . Two Ln-Co (Ln=Eu, Sm) metal-organic frameworks: Structures, magnetism, and fluorescent sensing sulfasalazine and glutaraldehyde. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2475-2485. doi: 10.11862/CJIC.20240193
8. [8]
  Aiai WANG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress of bimetallic organic framework in tumor diagnosis and treatment. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1825-1839. doi: 10.11862/CJIC.20240225
9. [9]
  Bin HE , Hao ZHANG , Lin XU , Yanghe LIU , Feifan LANG , Jiandong PANG . Recent progress in multicomponent zirconium?based metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2041-2062. doi: 10.11862/CJIC.20240161
10. [10]
  Yinwu Su , Xuanwen Zheng , Jianghui Du , Boda Li , Tao Wang , Zhiyan Huang . Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment. University Chemistry, 2024, 39(5): 307-314. doi: 10.3866/PKU.DXHX202311092
11. [11]
  Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan . 铂单原子功能化的二维Al-TCPP金属-有机框架纳米片用于增强光动力抗菌治疗. Acta Physico-Chimica Sinica, 2025, 41(5): 100046-. doi: 10.1016/j.actphy.2025.100046
12. [12]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
13. [13]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
14. [14]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
15. [15]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
16. [16]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
17. [17]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
18. [18]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
19. [19]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
20. [20]
  Mengzhen JIANG , Qian WANG , Junfeng BAI . Research progress on low-cost ligand-based metal-organic frameworks for carbon dioxide capture from industrial flue gas. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 1-13. doi: 10.11862/CJIC.20240355

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1929)
HTML views(360)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142