Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation
【Abstract】In this work, the effect of support materials on the kinetic behaviors of indium-based catalysts in carbon dioxide hydrogenation was studied. A series of supported indium-based catalysts were prepared and tested. Only group ⅣB metal (Ti, Zr and Hf) oxide supported indium-based catalysts have substantial catalytic activity. Particularly, In1/HfO2 and In1/ZrO2 catalysts show high methanol selectivity, while In1/TiO2 mainly catalyzes the reverse water-gas shift reaction. The steady-state kinetics, in-situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed experiments indicate that the key surface reaction intermediates over In1/HfO2 and In1/ZrO2 are formate and methoxy species, and methanol is produced via stepwise hydrogenation of the surface formate. In1/HfO2 possesses the strongest hydrogen splitting and hydrogenation ability, thus favoring methanol synthesis. Over In1/TiO2, no significant surface carbonaceous species is detected under reaction conditions. The improved CO production might be related to the interfacial oxygen defects facilitating the redox cycle and decomposition of formate intermediate.
【Keywords】 carbon dioxide; catalysts; kinetics; methanol synthesis; in-situ DRIFTS; temperature-programmed experiments;
(Translated by WANG YX)
 Mcfarlan A. Techno-economic assessment of pathways for electricity generation in northern remote communities in Canada using methanol and dimethyl ether to replace diesel [J]. Renew. Sust. Energ. Rev., 2018, 90: 863–876.
 Yang P P, Sun Q, Zhang Y L, et al. Research progress of the role of CO2 in methanol synthesis [J]. Chem. Ind. Eng. Prog., 2018, 37(S1): 94–101 (in Chinese).
 Ipatieff V, Monroe G. Synthesis of methanol from carbon dioxide and hydrogen over copper–alumina catalysts. Mechanism of reaction [J]. J. Am. Chem. Soc., 1945, 67(12): 2168–2171.
 Joo O S, Jung K D, Jung Y S. CAMERE process for methanol synthesis from CO2 hydrogenation [J]. Stud. Surf. Sci. Catal., 2004, 153: 67–72.
 Li Q X, Wang Z B, Lou S J, et al. Research progress in methanol production from carbon dioxide hydrogenation [J]. Modern Chemical Industry, 2019, (5): 19–23 (in Chinese).
 Bao J, Yang G H, Yoneyama Y, et al. Significant advances in C1 catalysis: highly efficient catalysts and catalytic reactions [J]. ACS Catal., 2019, 9(4): 3026–3053.
 Kattel S, Liu P, Chen J G. Tuning selectivity of CO2 hydrogenation reactions at the metal/oxide interface [J]. J. Am. Chem. Soc., 2017, 139(29): 9739–9754.
 Arena F, Mezzatesta G, Zafarana G, et al. Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in the synthesis of methanol via CO2 hydrogenation [J]. J. Catal., 2013, 300: 141–151.
 Angelo L, Kobl K, Tejada L M M, et al. Study of CuZnMOx oxides (M = Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO2 into methanol [J]. C. R. Chim., 2015, 18(3): 250–260.
 Zhan H J, Li F, Xin C L, et al. Performance of the La–Mn–Zn–Cu–O based perovskite precursors for methanol synthesis from CO2 hydrogenation [J]. Catal. Lett., 2015, 145(5): 1177–1185.
 Wu J, Saito M, Takeuchi M, et al. The stability of Cu/ZnO-based catalysts in methanol synthesis from a CO2-rich feed and from a CO-rich Feed [J]. Appl. Catal. A Gen., 2001, 218(1): 235–240.
 Qu J, Zhou X, Xu F, et al. Shape effect of Pd-promoted Ga2O3 nanocatalysts for methanol synthesis by CO2 hydrogenation [J]. J. Phys. Chem. C, 2014, 118(42): 24452–24466.
 Jiang X, Koizumi N, Guo X, et al. Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol [J]. Appl. Catal. B Environ., 2015, 170/171: 173–185.
 Wang J, Li G, Li Z, et al. A highly selective and stable ZnO–ZrO2 solid solution catalyst for CO2 hydrogenation to methanol [J]. Sci. Adv., 2017, 3(10): e1701290.
 Martin O, Mart N A J, Mondelli C, et al. Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation [J]. Angew. Chem. Int. Ed., 2016, 55(21): 6261–6265.
 Sun K, Fan Z, Ye J, et al. Hydrogenation of CO2 to methanol over In2O3 catalyst [J]. J. CO2 Util., 2015, 12: 1–6.
 Gao P, Li S, Bu X, et al. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst [J]. Nat. Chem., 2017, 9: 1019–1024.
 Gao P, Dang S, Li S, et al. Direct production of lower olefins from CO2 conversion via bifunctional catalysis [J]. ACS Catal., 2018, 8(1): 571–578.
 Su J, Wang D, Wang Y, et al. Direct conversion of syngas into light olefins over zirconium-doped indium(Ⅲ) oxide and SAPO-34 bifunctional catalysts: design of oxide component and construction of reaction network [J]. ChemCatChem, 2018, 10(7): 1536–1541.
 Zhang M, Dou M, Yu Y. DFT study of CO2 conversion on InZr3 (110) surface [J]. PCCP, 2017, 19(42): 28917–28927.
 Zhang M, Dou M, Yu Y. Theoretical study of the promotional effect of ZrO2 on In2O3 catalyzed methanol synthesis from CO2 hydrogenation [J]. Appl. Surf. Sci., 2018, 433 (Suppl. C): 780–789.
 Ye J, Liu C, Ge Q. DFT study of CO2 adsorption and hydrogenation on the In2O3 surface [J]. J. Phys. Chem. C, 2012, 116(14): 7817–7825.
 Ye J, Liu C, Mei D, et al. Active oxygen vacancy site for methanol synthesis from CO2 hydrogenation on In2O3 (110): a DFT study [J]. ACS Catal., 2013, 3(6): 1296–1306.
 Gervasini A, Perdigon-Melon J A, Guimon C, et al. An in-depth study of supported In2O3 catalysts for the selective catalytic reduction of NOx: the influence of the oxide support [J]. J. Phys. Chem. B, 2006, 110(1): 240–249.
 Chen M, Xu J, Cao Y, et al. Dehydrogenation of propane over In2O3–Al2O3 mixed oxide in the presence of carbon dioxide [J]. J. Catal., 2010, 272(1): 101–108.
 Mikhaylov R V, Nikitin K V, Glazkova N I, et al. Temperature programmed desorption of CO2, formed by CO photooxidation on TiO2 surface [J]. J. Photoch. Photobio. A, 2018, 360: 255–261.
 Rotzinger F P, Kesselman--Truttmann J M, Hug S J, et al. Structure and vibrational spectrum of formate and acetate adsorbed from aqueous solution onto the TiO2 rutile (110) surface [J]. J. Phys. Chem. B, 2004, 108(16): 5004–5017.
 Coronado J M, Kataoka S, Tejedor–Tejedor I, et al. Dynamic phenomena during the photocatalytic oxidation of ethanol and acetone over nanocrystalline TiO2: simultaneous FTIR analysis of gas and surface species [J]. J. Catal., 2003, 219(1): 219–230.
 Larmier K, Liao W C, Tada S, et al. CO2 to methanol hydrogenation on zirconia–supported copper nanoparticles: reaction intermediates and the role of the metal–support interface [J]. Angew. Chem. Int. Ed., 2017, 56(9): 2318–2323.
 Kattel S, Yan B H, Yang Y X, et al. Optimizing binding energies of key intermediates for CO2 hydrogenation to methanol over oxide-supported copper [J]. J. Am. Chem. Soc., 2016, 138(38): 12440–12450.
 Fisher I A, Bell A T. In-situ infrared study of methanol synthesis from H2/CO2 over Cu/SiO2 and Cu/ZrO2/SiO2 [J]. J. Catal., 1997, 172(1): 222–237.
 Fisher I A, Woo H C, Bell A T. Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2 [J]. Catal. Lett., 1997, 44(1): 11–17.
 Ouyang F, Kondo J N, Maruya K I, et al. Site conversion of methoxy species on ZrO2 [J]. J. Phys. Chem. B, 1997, 101(25): 4867–4869.
 Paulino P N, Salim V M M, Resende N S. Zn–Cu promoted TiO2 photocatalyst for CO2 reduction with H2O under UV light [J]. Appl. Catal. B Environ., 2016, 185: 362–370.
 Kim S S, Lee H H, Hong S C. The Effect of the morphological characteristics of TiO2 supports on the reverse water-gas shift reaction over Pt/TiO2 catalysts [J]. Appl. Catal. B Environ., 2012, 119/120: 100–108.
 Chen X, Su X, Duan H, et al. Catalytic performance of the Pt/TiO2 catalysts in reverse water gas shift reaction: controlled product selectivity and a mechanism study [J]. Catal. Today, 2017, 281: 312–318.