Preparation, characterization and catalytic performance of Cu nanowire catalyst for CO₂ hydrogenation

Abstract

Pure Cu nanowires as catalyst were prepared by electrochemical deposition and were used in CO₂ hydrogenation to methanol. The active sites of the Cu based catalyst were discussed. The performance and structural development of the catalyst were observed during CO₂ hydrogenation. A mechanism for the deactivation of the catalyst was discussed. The key factors that affect the deactivation of the catalyst were found. Cu nanowire sample was characterized by SEM, EDS, XRD, and BET. The results show that Cu nanowires have very high sintering resistance and catalytic stability. This helps to develop high performance catalysts. The changes in the grain size, SEM morphology and catalytic properties of the sample during CO₂ hydrogenation show that the migration of the Cu atoms on the surface of the Cu nanowires can occur. Continuous migration of Cu atoms and sintering of Cu grains can lead to flow blockage in gas channels. The gas channel flow blockage or the sintering of Cu grains can lead to deactivation of the catalyst. However, the shape of catalytic performance curve indicates that the main reason for the deactivation of the catalyst is the gas channel flow blockage.

Keywords

CO₂ hydrogenation / methanol / Cu nanowire / migration / sintering / flow blockage

References

[1] RenH, XuC-h, ZhaoH-y, WangY-x, LiuJ, LiuJ-ying. Methanol synthesis from CO₂ hydrogenation over Cu/γ-Al₂O₃ catalysts modified by ZnO, ZrO₂ and MgO [J]. Journal of Industrial and Engineering Chemistry, 2015, 28: 261-267

[2] LiC-m, YuanX-d, FujimotoK. Development of highly stable catalyst for methanol synthesis from carbon dioxide [J]. Applied Catalysis A: General, 2014, 469: 306-311

[3] GaoP, ZhongL-s, ZhangL-n, WangH, ZhaoN, WeiW, SunY-han. Yttrium oxide modified Cu/ZnO/Al₂O₃ catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol [J]. Catalysis Science & Technology, 2015, 5(9): 4365-4377

[4] LiZ-x, Naw, WangH, GaoW-gui. Direct syntheses of Cu-Zn-Zr/SBA-15 mesoporous catalysts for CO₂ hydrogenation to methanol [J]. Chemical Journal of Chinese Universities, 2014, 35(12): 2616-2623

[5] NatesakhawatS, LekseJ W, BaltrusJ P, OhodnickiP RJr, HowardB H, DengX-y, MatrangaC. Active sites and structure–activity relationships of copper-based catalysts for carbon dioxide hydrogenation to methanol [J]. ACS Catalysis, 2012, 2(8): 1667-1676

[6] BaltesC, VukojevićS, SchüthF. Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al₂O₃ catalysts for methanol synthesis [J]. Journal of Catalysis, 2008, 258(2): 334-344

[7] SaitoM, MurataK. Development of high performance Cu/ZnO-based catalysts for methanol synthesis and the water-gas shift reaction [J]. Catalysis Surveys from Asia, 2004, 8(4): 285-294

[8] ToyirJ, MilouaR, ElkadriN E, NawdaliM, ToufikH, MilouaF, SaitoM. Sustainable process for the production of methanol from CO₂ and H₂ using Cu/ZnO-based multicomponent catalyst [J]. Physics Procedia, 2009, 2(3): 1075-1079

[9] AhouariH, SoualahA, ValantA L, PinardL, MagnouxP, PouillouxY. Methanol synthesis from CO₂ hydrogenation over copper based catalysts [J]. Reaction Kinetics Mechanisms and Catalysis, 2013, 110(1): 131-145

[10] GaoP, LiF, ZhaoN, WangH, WeiW, SunY-han. Preparation of Cu/Zn/Al/(Zr)/(Y) catalysts from hydrotalcite-like precursors and their catalytic performance for the hydrogenation of CO₂ to methanol [J]. Acta Physico-Chimica Sinica, 2014, 30(6): 1155-1162

[11] ArenaF, BarberaK, ItalianoG, BonuraG, SpadaroL, FrusteriF. Synthesis, characterization and activity pattern of Cu–ZnO/ZrO₂ catalysts in the hydrogenation of carbon dioxide to methanol [J]. Journal of Catalysis, 2007, 249: 185-194

[12] TwiggM V, SpencerM S. Deactivation of supported copper metal catalysts for hydrogenation reactions [J]. Applied Catalysis A: General, 2001, 212: 161-174

[13] KangS H, BaeJ W, PrasadP S S, OhJ H, JunK W, SongS L, MinK S. Influence of Ga addition on the methanol synthesis activity of Cu/ZnO catalyst in the presence and absence of alumina [J]. Journal of Industrial and Engineering Chemistry, 2009, 15(5): 665-669

[14] WangS-jianComprehensive utilization technology of natural gas [M], 2003, Beijing, Chemical Industry Press

[15] HuangZ-taoIndustrial catalyst handbook [M], 2004, Beijing, Chemical Industry Press: 660663

[16] FujitaniT, NakamuraI, UchijimaT, NakamuraJ. The kinetics and mechanism of methanol synthesis by hydrogenation of CO₂ over a Zn-deposited Cu( 111 ) surface [J]. Surface Science, 1997, 383: 285-298

[17] ChoiY, FutagamiK, FujitaniT, NakamuraJ. The role of ZnO in Cu/ZnO methanol synthesis catalysts— morphology effect or active site model? [J]. Applied Catalysis A: General, 2001, 208(1): 163-167

[18] BehrensM, StudtF, KasatkinI, KühlS, HäveckerM, Abild-PedersenF, ZanderS, GirgsdiesF, KurrP, KniepB L, TovarM, FischerR W, NørskovJ K, SchlöglR. The active site of methanol synthesis over Cu/ZnO/Al₂O₃ industrial catalysts [J]. Science, 2012, 336(6083): 893-897

[19] QianB-zhang. Hope of CO₂ for efficient methanol synthesis [N]. China Chemical Industry News, 2014

[20] LiZ, FanH, ZhangH-y, LiuYan. Influence of microwave irradiation on precursor microstructure and catalytic performance of Cu/ZnO/Al₂O₃ for slurry methanol synthesis [J]. Chinese Journal of Catalysis, 2010, 31(4): 471-478

[21] LiZ, LiuY, HeZ, FanH, ZhengH-yan. Effects of Cu/Zn on the structure and activity of CuO/ZnO/Al₂O₃ catalysts prepared under microwave irradiation in aging process [J]. Acta Chimica Sinica, 2011, 69(5): 570-576

[22] LinS-d, TangH-d, LuZ-b, LiuC-l, CenY-q, LiuH-zhang. Influence of precipitation methods on precursors and properties of Cu-based catalyst for methanol synthesis [J]. Chinese Journal of Catalysis, 2010, 31(10): 1257-1262

[23] WangD-s, TanY-s, HanY-z, TsubakiN. Effect of CO₂ on stability of Cu-based catalyst for dimethyl ether synthesis in slurry phase [J]. Chinese Journal of Catalysis, 2008, 29(1): 63-68

[24] ArenaF, ItalianoG, BarberaK, BonuraG, SpadaroL, FrusteriF. Basic evidences for methanol synthesis catalyst design [J]. Catalysis Today, 2009, 143: 80-85

[25] LeiH, NieR-f, WuG-q, HouZ-yin. Hydrogenation of CO₂ to CH₃OH over Cu/ZnO catalysts with different ZnO morphology [J]. Fuel, 2015, 154: 161-166

[26] ErtlG, KnözingerH, SchüthF, WeitkampJHandbook of heterogeneous catalysis [M]. 2nd ed, 2008, Weinheim, Wiley-VCH: 9798

[27] ToyirJ, SaitoM, YamauchiI, LuoS-c, WuJ-g, TakaharaI, TakeuchiM. Development of high performance Raney Cu-based catalysts for methanol synthesis from CO₂ and H2 [J]. Catalysis Today, 1998, 45(1): 245-250

[28] ChuWeiCatalyst engineering [M], 2006, Chengdu, Sichuan University Press: 107

[29] ZhangY-l, LiY-longManufacture and aapplication of industrial catalysts [M], 2008, Beijing, Chemical Industry Press

[30] YanX, ShuJ-j, KongY-huaNovel integrated methanol process and energy saving [M], 2009, Beijing, Chemical Industry Press

[31] NatesakhawatS, OhodnickiP RJr, HowardB H, LekseJ W, BaltrusJ P, MatrangaC. Adsorption and deactivation characteristics of Cu/ZnO-based catalysts for methanol synthesis from carbon dioxide [J]. Topics in Catalysis, 2013, 56(18): 1752-1763

[32] AnX, RenF, LiJ-l, WangJ-fu. A highly active Cu/ZnO/Al₂O₃ nanofiber catalyst for methanol synthesis through CO₂ and CO hydrogenation [J]. Chinese Journal of Catalysis, 2005, 26(9): 729-730

[33] AnX, LiJ-l, ZuoY-z, ZhangQ, WangD-z, WangJ-fu. A Cu/Zn/Al/Zr fibrous catalyst that is an improved CO₂ hydrogenation to methanol catalyst [J]. Catalysis Letters, 2007, 118(3): 264-269

[34] WangG-n, ChenL-m, GuoY-y, FuM-l, WuJ-l, HuangB-c, YeD-qi. Effect of chromium doping on the catalytic behavior of Cu/ZrO₂/CNTs-NH2 for the synthesis of methanol from carbon dioxide hydrogenation [J]. Acta Physico-Chimica Sinica, 2014, 30(5): 923-931

[35] RazaliN A M, LeeK T, BhatiaS, MohamedA R. Heterogeneous catalysts for production of chemicals using carbon dioxide as raw material: A review [J]. Renewable and Sustainable Energy Reviews, 2012, 16: 4951-4964

[36] SameiE, TaghizadehM, BahmaniM. Enhancement of stability and activity of Cu/ZnO/Al₂O₃ catalysts by colloidal silica and metal oxides additives for methanol synthesis from a CO₂-rich feed [J]. Fuel Processing Technology, 2012, 96: 128-133

[37] FichtlM B, SchlerethD, JacobsenN, KasatkinI, SchumannJ, BehrensM A, SchlöglR, HinrichsenO. Kinetics of deactivation on Cu/ZnO/Al₂O₃ methanol synthesis catalysts [J]. Applied Catalysis A: General, 2015, 502: 262-270

[38] QuJ, ZhouX-w, XuF, GongX-q, TsangS C E. Shape effect of Pd-promoted Ga₂O₃ nanocatalysts for methanol synthesis by CO₂ hydrogenation [J]. The Journal of Physical Chemistry C, 2014, 118: 24452-24466

[39] ChowdhuryT, CaseyD P, RohanJ F. Additive influence on Cu nanotube electrodeposition in anodised aluminium oxide templates [J]. Electrochemistry Communications, 2009, 11: 1203-1206

[40] SongM-p, HeZ-hangBasic chemistry experiment and technology [M], 2008, Beijing, Chemical Industry Press

[41] KhalilA, HashaikehR, JouiadM. Synthesis and morphology analysis of electrospun copper nanowires [J]. Journal of Materials Science, 2014, 49(8): 3052-3065

[42] BansodeA, TidonaB, von RohrP R, UrakawaA. Impact of K and Ba promoters on CO₂ hydrogenation over Cu/Al₂O₃ catalysts at high pressure [J]. Catalysis Science & Technology, 2013, 3: 767-778

[43] ZhaoY-f, YangY, MimsC, PedenC H F, LiJ, MeiD-hai. Insight into methanol synthesis from CO₂ hydrogenation on Cu(111): Complex reaction network and the effects of H₂O [J]. Journal of Catalysis, 2011, 281(2): 199-211

[44] RasmussenD B, JanssensT V W, TemelB, BligaardT, HinnemannB, HelvegS, SehestedJ. The energies of formation and mobilities of Cu surface species on Cu and ZnO in methanol and water gas shift atmospheres studied by DFT [J]. Journal of Catalysis, 2012, 293: 205-214

[45] KondoS, IshikawaT, AbeIAdsorption science [M]. 2nd ed, 2006, Beijing, Chemical Industry, Press

[46] YuQ-c, DengY, WangF, FengY-b, YangB, XuB-q, LiuD-chun. Comparison of desulfurization kinetics of copper oxide sorbent [J]. Journal of Central South University, 2015, 22(08): 2902-2908

[47] ZhangX-y, WangM-h, WebleyP A, XiaoP, WangF-l, TaoY-z, ZhaiY-chun. Preparation and performance of catalyst for CO₂ hydrogenation [J]. Journal of Materials and Metallurgy, 2016, 15(4): 272-276