Abstract
Hydrogenation of CO2 to methanol over heterogeneous catalysts usually requires hash conditions. Various heterogeneous catalysts based on Cu, Pd, Ni, Ag, Au, In, and other metals have been recently developed and investigated. Cu doped by other metals or metal oxides are the preferred selection. Besides metal itself, catalyst morphology, which is generally influenced by the method of preparation and calcination, is crucial for reaction conversion and selectivity. The relationship between catalyst characteristics and catalyst performance is discussed.
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References
Liu X-M, Lu GQ, Yan Z-F, Beltramini J (2003) Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2. Ind Eng Chem Res 42(25):6518–6530. doi:10.1021/ie020979s
Wang W, Wang S, Ma X, Gong J (2011) Recent advances in catalytic hydrogenation of carbon dioxide. Chem Soc Rev 40(7):3703–3727. doi:10.1039/c1cs15008a
Jadhav SG, Vaidya PD, Bhanage BM, Joshi JB (2014) Catalytic carbon dioxide hydrogenation to methanol: a review of recent studies. Chem Eng Res Des 92(11):2557–2567. doi:10.1016/j.cherd.2014.03.005
Ali KA, Abdullah AZ, Mohamed AR (2015) Recent development in catalytic technologies for methanol synthesis from renewable sources: a critical review. Renew Sustain Energy Rev 44:508–518. doi:10.1016/j.rser.2015.01.010
Yang C, Ma Z, Zhao N, Wei W, Hu T, Sun Y (2006) Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst. Catal Today 115(1–4):222–227. doi:10.1016/j.cattod.2006.02.077
Zhang Y, Fei J, Yu Y, Zheng X (2006) Methanol synthesis from CO2 hydrogenation over Cu based catalyst supported on zirconia modified γ-Al2O3. Energy Convers Manage 47(18–19):3360–3367. doi:10.1016/j.enconman.2006.01.010
Raudaskoski R, Niemelä MV, Keiski RL (2007) The effect of ageing time on co-precipitated Cu/ZnO/ZrO2 catalysts used in methanol synthesis from CO2 and H2. Top Catal 45(1–4):57–60. doi:10.1007/s11244-007-0240-9
An X, Li J, Zuo Y, Zhang Q, Wang D, Wang J (2007) A Cu/Zn/Al/Zr fibrous catalyst that is an improved CO2 hydrogenation to methanol catalyst. Catal Lett 118(3–4):264–269. doi:10.1007/s10562-007-9182-x
Arena F, Barbera K, Italiano G, Bonura G, Spadaro L, Frusteri F (2007) Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol. J Catal 249(2):185–194. doi:10.1016/j.jcat.2007.04.003
Zhang Y, Fei J, Yu Y, Zheng X (2007) Study of CO2 hydrogenation to methanol over Cu-V/γ-Al2O3 catalyst. J Nat Gas Chem 16(1):12–15. doi:10.1016/s1003-9953(07)60019-x
Liu Y, Zhang Y, Wang T, Tsubaki N (2007) Efficient conversion of carbon dioxide to methanol using copper catalyst by a new low-temperature hydrogenation process. Chem Lett 36(9):1182–1183. doi:10.1246/cl.2007.1182
Arena F, Italiano G, Barbera K, Bordiga S, Bonura G, Spadaro L, Frusteri F (2008) Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH. Appl Catal A Gen 350(1):16–23. doi:10.1016/j.apcata.2008.07.028
Guo X, Mao D, Wang S, Wu G, Lu G (2009) Combustion synthesis of CuO–ZnO–ZrO2 catalysts for the hydrogenation of carbon dioxide to methanol. Catal Commun 10(13):1661–1664. doi:10.1016/j.catcom.2009.05.004
Guo X, Mao D, Lu G, Wang S, Wu G (2010) Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation. J Catal 271(2):178–185. doi:10.1016/j.jcat.2010.01.009
H-d Zhuang, S-f Bai, X-m Liu, Z-f Yan (2010) Structure and performance of Cu/ZrO2 catalyst for the synthesis of methanol from CO2 hydrogenation. J Fuel Chem Tech 38(4):462–467. doi:10.1016/s1872-5813(10)60041-2
Wang X, Zhang H, Li W (2010) In situ IR studies on the mechanism of methanol synthesis from CO/H2 and CO2/H2 over Cu-ZnO-Al2O3 catalyst. Korean J Chem Eng 27(4):1093–1098. doi:10.1007/s11814-010-0176-9
Maniecki TP, Mierczyński P, Jóźwiak WK (2010) Copper-supported catalysts in methanol synthesis and water gas shift reaction. Kinet Catal 51(6):843–848. doi:10.1134/s0023158410060108
Guo X, Mao D, Lu G, Wang S, Wu G (2011) CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared via a route of solid-state reaction. Catal Commun 12(12):1095–1098. doi:10.1016/j.catcom.2011.03.033
Wang D, Zhao J, Song H, Chou L (2011) Characterization and performance of Cu/ZnO/Al2O3 catalysts prepared via decomposition of M(Cu, Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H2 and CO2. J Nat Gas Chem 20(6):629–634. doi:10.1016/s1003-9953(10)60246-0
Guo X, Mao D, Lu G, Wang S, Wu G (2011) The influence of La doping on the catalytic behavior of Cu/ZrO2 for methanol synthesis from CO2 hydrogenation. J Mol Catal A Chem 345(1–2):60–68. doi:10.1016/j.molcata.2011.05.019
Mierczynski P, Maniecki TP, Maniukiewicz W, Jozwiak WK (2011) Cu/Cr2O3·3Al2O3 and Au–Cu/Cr2O3·3Al2O3 catalysts for methanol synthesis and water gas shift reactions. React Kinet Mech Catal 104(1):139–148. doi:10.1007/s11144-011-0336-x
Bonura G, Arena F, Mezzatesta G, Cannilla C, Spadaro L, Frusteri F (2011) Role of the ceria promoter and carrier on the functionality of Cu-based catalysts in the CO2-to-methanol hydrogenation reaction. Catal Today 171(1):251–256. doi:10.1016/j.cattod.2011.04.038
Zhang L, Zhang Y, Chen S (2012) Effect of promoter SiO2, TiO2 or SiO2-TiO2 on the performance of CuO-ZnO-Al2O3 catalyst for methanol synthesis from CO2 hydrogenation. Appl Catal A Gen 415–416:118–123. doi:10.1016/j.apcata.2011.12.013
Karelovic A, Bargibant A, Fernández C, Ruiz P (2012) Effect of the structural and morphological properties of Cu/ZnO catalysts prepared by citrate method on their activity toward methanol synthesis from CO2 and H2 under mild reaction conditions. Catal Today 197(1):109–118. doi:10.1016/j.cattod.2012.07.029
Gao P, Li F, Zhao N, Xiao F, Wei W, Zhong L, Sun Y (2013) Influence of modifier (Mn, La, Ce, Zr and Y) on the performance of Cu/Zn/Al catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol. Appl Catal A Gen 468:442–452. doi:10.1016/j.apcata.2013.09.026
Arena F, Mezzatesta G, Zafarana G, Trunfio G, Frusteri F, Spadaro L (2013) Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in the synthesis of methanol via CO2 hydrogenation. J Catal 300:141–151. doi:10.1016/j.jcat.2012.12.019
Ladera R, Pérez-Alonso FJ, González-Carballo JM, Ojeda M, Rojas S, Fierro JLG (2013) Catalytic valorization of CO2 via methanol synthesis with Ga-promoted Cu–ZnO–ZrO2 catalysts. Appl Catal B Environ 142–143:241–248. doi:10.1016/j.apcatb.2013.05.019
Bansode A, Urakawa A (2014) Towards full one-pass conversion of carbon dioxide to methanol and methanol-derived products. J Catal 309:66–70. doi:10.1016/j.jcat.2013.09.005
Din IU, Shaharun MS, Subbarao D, Naeem A (2014) Synthesis, characterization and activity pattern of carbon nanofibres based Cu-ZrO2 catalyst in the hydrogenation of carbon dioxide to methanol. Adv Mater Res 925:349–353. doi:10.4028/www.scientific.net/AMR.925.349
Gao P, Zhong L, Zhang L, Wang H, Zhao N, Wei W, Sun Y (2015) Yttrium oxide modified Cu/ZnO/Al2O3 catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol. Catal Sci Technol 5(9):4365–4377. doi:10.1039/c5cy00372e
Chen Y, Choi S, Thompson LT (2015) Low-temperature CO2 hydrogenation to liquid products via a heterogeneous cascade catalytic system. ACS Catal 5(3):1717–1725. doi:10.1021/cs501656x
Ren H, Xu C-H, Zhao H-Y, Wang Y-X, Liu J, Liu J-Y (2015) Methanol synthesis from CO2 hydrogenation over Cu/γ-Al2O3 catalysts modified by ZnO, ZrO2 and MgO. J Ind Eng Chem 28:261–267. doi:10.1016/j.jiec.2015.03.001
Lei H, Nie R, Wu G, Hou Z (2015) Hydrogenation of CO2 to CH3OH over Cu/ZnO catalysts with different ZnO morphology. Fuel 154:161–166. doi:10.1016/j.fuel.2015.03.052
Xiao J, Mao D, Guo X, Yu J (2015) Effect of TiO2, ZrO2, and TiO2–ZrO2 on the performance of CuO–ZnO catalyst for CO2 hydrogenation to methanol. Appl Surf Sci 338:146–153. doi:10.1016/j.apsusc.2015.02.122
Witoon T, Bumrungsalee S, Chareonpanich M, Limtrakul J (2015) Effect of hierarchical meso–macroporous alumina-supported copper catalyst for methanol synthesis from CO2 hydrogenation. Energy Convers Manage 103:886–894. doi:10.1016/j.enconman.2015.07.033
Li L, Mao D, Yu J, Guo X (2015) Highly selective hydrogenation of CO2 to methanol over CuO–ZnO–ZrO2 catalysts prepared by a surfactant-assisted co-precipitation method. J Power Sources 279:394–404. doi:10.1016/j.jpowsour.2014.12.142
Cai W, de la Piscina PR, Toyir J, Homs N (2015) CO2 hydrogenation to methanol over CuZnGa catalysts prepared using microwave-assisted methods. Catal Today 242:193–199. doi:10.1016/j.cattod.2014.06.012
Gao P, Xie R, Wang H, Zhong L, Xia L, Zhang Z, Wei W, Sun Y (2015) Cu/Zn/Al/Zr catalysts via phase-pure hydrotalcite-like compounds for methanol synthesis from carbon dioxide. J CO2 Util 11:41–48. doi:10.1016/j.jcou.2014.12.008
Kunkes EL, Studt F, Abild-Pedersen F, Schlögl R, Behrens M (2015) Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not? J Catal 328:43–48. doi:10.1016/j.jcat.2014.12.016
Tisseraud C, Comminges C, Belin T, Ahouari H, Soualah A, Pouilloux Y, Le Valant A (2015) The Cu–ZnO synergy in methanol synthesis from CO2, part 2: origin of the methanol and CO selectivities explained by experimental studies and a sphere contact quantification model in randomly packed binary mixtures on Cu–ZnO coprecipitate catalysts. J Catal 330:533–544. doi:10.1016/j.jcat.2015.04.035
Yang H, Gao P, Zhang C, Zhong L, Li X, Wang S, Wang H, Wei W, Sun Y (2016) Core–shell structured Cu@m-SiO2 and Cu/ZnO@m-SiO2 catalysts for methanol synthesis from CO2 hydrogenation. Catal Commun 84:56–60. doi:10.1016/j.catcom.2016.06.010
Posada-Pérez S, RamÃrez PJ, Gutiérrez RA, Stacchiola DJ, Viñes F, Liu P, Illas F, Rodriguez JA (2016) The conversion of CO2 to methanol on orthorhombic β-Mo2C and Cu/β-Mo2C catalysts: mechanism for admetal induced change in the selectivity and activity. Catal Sci Technol 6(18):6766–6777. doi:10.1039/c5cy02143j
Chen Y, Choi S, Thompson LT (2016) Low temperature CO2 hydrogenation to alcohols and hydrocarbons over Mo2C supported metal catalysts. J Catal 343:147–156. doi:10.1016/j.jcat.2016.01.016
Ro I, Liu Y, Ball MR, Jackson DHK, Chada JP, Sener C, Kuech TF, Madon RJ, Huber GW, Dumesic JA (2016) Role of the Cu-ZrO2 interfacial sites for conversion of ethanol to ethyl acetate and synthesis of methanol from CO2 and H2. ACS Catal 6(10):7040–7050. doi:10.1021/acscatal.6b01805
da Silva RJ, Pimentel AF, Monteiro RS, Mota CJA (2016) Synthesis of methanol and dimethyl ether from the CO2 hydrogenation over Cu·ZnO supported on Al2O3 and Nb2O5. J CO2 Util 15:83–88. doi:10.1016/j.jcou.2016.01.006
Kiss AA, Pragt JJ, Vos HJ, Bargeman G, de Groot MT (2016) Novel efficient process for methanol synthesis by CO2 hydrogenation. Chem Eng J 284:260–269. doi:10.1016/j.cej.2015.08.101
Dong X, Li F, Zhao N, Xiao F, Wang J, Tan Y (2016) CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method. Appl Catal B Environ 191:8–17. doi:10.1016/j.apcatb.2016.03.014
Deerattrakul V, Dittanet P, Sawangphruk M, Kongkachuichay P (2016) CO2 hydrogenation to methanol using Cu-Zn catalyst supported on reduced graphene oxide nanosheets. J CO2 Util 16:104–113. doi:10.1016/j.jcou.2016.07.002
Witoon T, Kachaban N, Donphai W, Kidkhunthod P, Faungnawakij K, Chareonpanich M, Limtrakul J (2016) Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts. Energy Convers Manage 118:21–31. doi:10.1016/j.enconman.2016.03.075
Gaikwad R, Bansode A, Urakawa A (2016) High-pressure advantages in stoichiometric hydrogenation of carbon dioxide to methanol. J Catal 343:127–132. doi:10.1016/j.jcat.2016.02.005
Tisseraud C, Comminges C, Pronier S, Pouilloux Y, Le Valant A (2016) The Cu–ZnO synergy in methanol synthesis part 3: impact of the composition of a selective Cu@ZnOx core–shell catalyst on methanol rate explained by experimental studies and a concentric spheres model. J Catal 343:106–114. doi:10.1016/j.jcat.2015.12.005
Liang X-L, Dong X, Lin G-D, Zhang H-B (2009) Carbon nanotube-supported Pd–ZnO catalyst for hydrogenation of CO2 to methanol. Appl Catal B Environ 88(3–4):315–322. doi:10.1016/j.apcatb.2008.11.018
Kong H, Li H-Y, Lin G-D, Zhang H-B (2011) Pd-decorated CNT-promoted Pd-Ga2O3 catalyst for hydrogenation of CO2 to methanol. Catal Lett 141(6):886–894. doi:10.1007/s10562-011-0584-4
Liang X-L, Xie J-R, Liu Z-M (2015) A novel Pd-decorated carbon nanotubes-promoted Pd-ZnO catalyst for CO2 hydrogenation to methanol. Catal Lett 145(5):1138–1147. doi:10.1007/s10562-015-1505-8
Oyola-Rivera O, Baltanás MA, Cardona-MartÃnez N (2015) CO2 hydrogenation to methanol and dimethyl ether by Pd–Pd2Ga catalysts supported over Ga2O3 polymorphs. J CO2 Util 9:8–15. doi:10.1016/j.jcou.2014.11.003
Jiang X, Koizumi N, Guo X, Song C (2015) Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol. Appl Catal B Environ 170–171:173–185. doi:10.1016/j.apcatb.2015.01.010
Liao F, Wu X-P, Zheng J, Li M-J, Zeng Z, Hong X, Kroner A, Yuan Y, Gong X-Q, Tsang SCE (2016) Pd@Zn core–shell nanoparticles of controllable shell thickness for catalytic methanol production. Catal Sci Technol 6(21):7698–7702. doi:10.1039/c6cy01832g
DÃez-RamÃrez J, Valverde JL, Sánchez P, Dorado F (2015) CO2 hydrogenation to methanol at atmospheric pressure: influence of the preparation method of Pd/ZnO catalysts. Catal Lett 146(2):373–382. doi:10.1007/s10562-015-1627-z
Vesselli E, Schweicher J, Bundhoo A, Frennet A, Kruse N (2011) Catalytic CO2 hydrogenation on nickel: novel insight by chemical transient kinetics. J Phys Chem C 115(4):1255–1260. doi:10.1021/jp106551r
Sharafutdinov I, Elkjær CF, Pereira de Carvalho HW, Gardini D, Chiarello GL, Damsgaard CD, Wagner JB, Grunwaldt J-D, Dahl S, Chorkendorff I (2014) Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanol. J Catal 320:77–88. doi:10.1016/j.jcat.2014.09.025
Grabowski R, Słoczyński J, Śliwa M, Mucha D, Socha RP, Lachowska M, Skrzypek J (2011) Influence of polymorphic ZrO2 phases and the silver electronic state on the activity of Ag/ZrO2 catalysts in the hydrogenation of CO2 to methanol. ACS Catal 1(4):266–278. doi:10.1021/cs100033v
Pasupulety N, Driss H, Alhamed YA, Alzahrani AA, Daous MA, Petrov L (2015) Studies on Au/Cu–Zn–Al catalyst for methanol synthesis from CO2. Appl Catal A Gen 504:308–318. doi:10.1016/j.apcata.2015.01.036
Martin O, Martin AJ, Mondelli C, Mitchell S, Segawa TF, Hauert R, Drouilly C, Curulla-Ferre D, Perez-Ramirez J (2016) Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation. Angew Chem Int Ed 55(21):6261–6265. doi:10.1002/anie.201600943
Jia L, Gao J, Fang W, Li Q (2009) Carbon dioxide hydrogenation to methanol over the pre-reduced LaCr0.5Cu0.5O3 catalyst. Catal Commun 10(15):2000–2003. doi:10.1016/j.catcom.2009.07.017
Jia L, Gao J, Fang W, Li Q (2010) Influence of copper content on structural features and performance of pre-reduced LaMn1−xCuxO3 (0 ≤ x<1) catalysts for methanol synthesis from CO2/H2. J Rare Earth 28(5):747–751. doi:10.1016/s1002-0721(09)60193-9
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Wang, WH., Feng, X., Bao, M. (2018). Transformation of CO2 to Methanol Over Heterogeneous Catalysts. In: Transformation of Carbon Dioxide to Formic Acid and Methanol. SpringerBriefs in Molecular Science(). Springer, Singapore. https://doi.org/10.1007/978-981-10-3250-9_5
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