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
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