Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation

doi:10.12066/j.issn.1007-2861.1903

Abstract

Abstract:

Cu/ZnO/MCM-41 catalyst was prepared via a double-solvent impregnation method, and its catalytic performance of CO$_{2}$ hydrogenation to methanol was investigated. The water-ethylene glycol double solvent formed by adding an appropriate amount of ethylene glycol to the metal nitrate aqueous solution in the impregnation process promoted metal ions into the channels of MCM-41 support, resulting in the formation of metal particles with very small size. Metal particles were uniformly embedded in MCM-41 channels. The relatively low reduction temperature indicated highly dispersed active sites with strong interaction between Cu and ZnO. Cu/ZnO/MCM-41 catalysts prepared with the method had stable catalytic performance in hydrogenation of CO$_{2}$ to methanol. By adjusting loading to control the particle size of Cu, the methanol selectivity and yield could reach 64.3% and 32.8 g$\cdot$(kgcat)$^{-1 }\cdot$h$^{-1}$. Therefore the double-solvent impregnation method can effectively limit migration and sintering of active components with optimized particle size, so as to obtain catalysts with highly dispersed active sites and stable catalytic performance.

Key words: double-solvent impregnation method, Cu/ZnO/MCM-41, catalyst, CO$_{2}$ hydrogenation, methano

CLC Number:

O643.3

ZHANG Chen, LIAO Peiyi, SHI Zhibiao, SUN Jian, WANG Hui. Preparation of Cu/ZnO/MCM-41 catalyst with double-solvent impregnation method and catalytic performance in methanol synthesis by CO$_{\textbf{2}}$ hydrogenation[J]. Journal of Shanghai University（Natural Science Edition）, 2019, 25(1): 109-119.

Figures/Tables 10

Fig. 1

Table 1

Fig. 2

Fig. 3

Table 2

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

References 24

[1]	Liu P, Qin R, Gang F , et al. Surface coordination chemistry of metal nanomaterials[J]. Journal of the American Chemical Society, 2017,139(6):2122-2131.
[2]	Moulijn J A, Diepen A E V, Kapteijn F , et al. Catalyst deactivation: is it predictable?: what to do?[J]. Applied Catalysis A: General, 2001,212(1/2):3-16.
[3]	Prieto G, Concepcion P, Martinez A , et al. New insights into the role of the electronic properties of oxide promoters in Rh-catalyzed selective synjournal of oxygenates from synjournal gas[J]. Journal of Catalysis, 2011,280(2):274-288.
[4]	Lopez H M, Cies J M, Trasobares S , et al. Imaging nanostructural modifications induced by electronic metal support interaction effects at Au/Cerium-based oxide nanointerfaces[J]. ACS Nano, 2012,6(8):6812-6820.
[5]	Torres G H M, Bitter J H, Davidian T , et al. Iron particle size effects for direct production of lower olefins from synjournal gas[J]. Journal of the American Chemical Society, 2012,134(39):16207-16215.
[6]	Cao A, Veser G . Exceptional high-temperature stability through distillation-like self-stabilization in bimetallic nanoparticles[J]. Nature Materials, 2010,9(1):75-81.
[7]	Wang Y, van de Vyver S, Sharma K , et al. Insights into the stability of gold nanoparticles supported on metal oxides for the base-free oxidation of glucose to gluconic acid[J]. Green Chemistry, 2014,16(2):719-726.
[8]	Li F, Yi X D, Fang W P , et al. Effect of organic nickel precursor on the reduction performance and hydrogenation activity of Ni/Al$_{2}$O$_{3}$ catalysts[J]. Catalysis Letters, 2009,130(3/4):335-340.
[9]	Nares R, Ramirez J, Gutierrez A A , et al. Characterization and hydrogenation activity of Ni/Si(Al)-MCM-41 catalysts prepared by deposition-precipitation[J]. Industrial and Engineering Chemistry Research, 2009,48(3):1154-1162.
[10]	Bartholomew C H, Pannell R B, Butler J L , et al. Support and crystallite size effects in CO hydrogenation on nickel[J]. Journal of Catalysis, 1980,65(2):335-347.
[11]	Lu J, Fu B, Kung M C , et al. Coking- and sintering-resistant palladium catalysts achieved through atomic layer deposition[J]. Science, 2012,335(6073):1205-1208.
[12]	Prieto G, Zecevic J, Jovana F , et al. Towards stable catalysts by controlling collective properties of supported metal nanoparticles[J]. Nature Materials, 2013,12(1):34-39.
[13]	Richardson J T . Pore size effects on sintering of Ni/Al$_{2}$O$_{3}$ catalysts[J]. Journal of Catalysis, 1986,98(2):457-467.
[14]	Sun J, Ma D, Zhang H , et al. Toward monodispersed silver nanoparticles with unusual thermal stability[J]. Journal of the American Chemical Society, 2006,128(49):15756-15764.
[15]	Chen J F, Zhang Y R, Tan L , et al. A simple method for preparing the highly dispersed supported Co$_{3}$O$_{4}$ on silica support[J]. Industrial and Engineering Chemistry Research, 2011,50(7):4212-4215.
[16]	Ho S W, Su Y S . Effects of ethanol impregnation on the properties of silica-supported cobalt catalysts[J]. Journal of Catalysis, 1997,44(6):591-596.
[17]	Behrens M, Studt F, Kasatkin I . The active site of methanol synjournal over Cu/ZnO/Al$_{2}$O$_{3}$ industrial catalysts[J]. Science, 2012,336:893-897.
[18]	Rasmussen D B, Janssens T V W, Temel B . The energies of formation and mobilities of Cu surface species on Cu and ZnO in methanol and water gas shift atmospheres studied byDFT[J]. Journal of Catalysis, 2012,293(1):205-214.
[19]	Karelovic A, Ruiz P . The role of copper particle size in low pressure methanol synjournal via CO$_{2}$ hydrogenation over Cu/ZnO catalysts[J]. Catalysis Science and Technology, 2015,5(2):869-881.
[20]	Kresge C T, Leonowicz M E, Roth W J , et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992,359(6397):710-712.
[21]	Bore M T, Pham H N, Roth W J , et al. The role of pore size and structure on the thermal stability of gold nanoparticles within mesoporous Silica[J]. The Journal of Physical Chemistry B, 2005,109(7):2873-2880.
[22]	Lei H, Nie R F, Wu G Q , et al. Hydrogenation of CO$_{2 }$ to CH$_{3}$OH over Cu/ZnO catalysts with different ZnO morphology[J]. Fuel, 2015,154:161-166.
[23]	Arena F, Mezzatesta G, Zafarana G , et al. How oxide carriers control the catalytic functionality of the Cu-ZnO system in the hydrogenation of CO$_{2}$ to methanol[J]. Catalysis Today, 2013,210(7):39-46.
[24]	Prieto G, Shakeri M, de Jong K P , et al. Quantitative relationship between support porosity and the stability of pore-confined metal nanoparticles studied on CuZnO/SiO$_{2}$ methanol synjournal catalysts[J]. ACS Nano, 2014,8(3):2522-2531.