纳米CeO_2不同的制备方法对催化性能的影响
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摘要
采用快速氧化法、直接焙烧法、水热滴加法和水热倾倒法制备了纳米CeO_2催化剂,并用于催化甲醇与CO2合成碳酸二甲酯(DMC)。结果表明,水热滴加法制备的纳米CeO_2催化性能优于其他方法制备的催化剂。水热滴加法的最优条件为3 m L氨水和1.0 g CTAB,DMC产率最高可达0.772 0 mmol/mmolcat。此外,通过透射电镜(TEM)、X-射线衍射(XRD)、N2吸脱附、X-射线光电子能谱仪(XPS)和程序升温吸附(TPD)对所制备的催化剂进行表征。研究结果表明,纳米CeO_2上较高的Ce(Ⅳ)/Ce(Ⅲ)比值和适当的酸碱性位数量和强度对其催化性能有显著影响。
Nano-CeO_2 was prepared via fast oxidizing method,calcining method,hydrothermal dripping method and hydrothermal dumping method,and then was used as a catalyst for the synthesis of DMC from methanol and CO2. The catalytic results showed that nano-CeO_2 prepared by hydrothermal dripping method exhibited a superior catalytic performance. When the consumption of ammonia was 3 m L and that of CTAB was 1. 0 g,the DMC yield reached the highest( 0. 772 0 mmol / mmolcat). In addition,TEM,XRD,N2-absorption,XPS and TPD were used to characterize as-prepared catalysts,respectively. The results showed that the higher ratio of Ce( Ⅳ) / Ce( Ⅲ) as well as the appropriate concentration and the strength of acidic and basic sites on nano-CeO_2 had significant effects on the catalytic properties.
Nano-CeO_2 was prepared via fast oxidizing method,calcining method,hydrothermal dripping method and hydrothermal dumping method,and then was used as a catalyst for the synthesis of DMC from methanol and CO2. The catalytic results showed that nano-CeO_2 prepared by hydrothermal dripping method exhibited a superior catalytic performance. When the consumption of ammonia was 3 m L and that of CTAB was 1. 0 g,the DMC yield reached the highest( 0. 772 0 mmol / mmolcat). In addition,TEM,XRD,N2-absorption,XPS and TPD were used to characterize as-prepared catalysts,respectively. The results showed that the higher ratio of Ce( Ⅳ) / Ce( Ⅲ) as well as the appropriate concentration and the strength of acidic and basic sites on nano-CeO_2 had significant effects on the catalytic properties.
引文
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[2]KELLER N,REBMANN G,KELLER V.Catalysts,mechanisms and industrial processes for the dimethylcarbonate synthesis[J].J.Mol.Catal.A Chem.,2010,317(1):1-18.
[3]ONO Y.Dimethyl carbonate for environmentally benign reactions[J].Catal.Today,1997,35(2):15-25.
[4]PACHECO M A,MARSHALL C L.Review of dimethyl carbonate(DMC)manufacture and its characteristics as a fuel additive[J].Energ.Fuel.,1997,11(1):2-29.
[5]WANG Wei,WANG Sheng-ping,MA Xin-bin,et al.Recent advances in catalytic hydrogenation of carbon dioxide[J].Chem.Soc.Rev.,2011,40(7):3 703-3 727.
[6]DELLEDONNE D,RIVETTI F,ROMANO U.Developments in the production and application of dimethylcarbonate[J].Appl.Catal.A Gen.,2001,221(1):241-251.
[7]BOHM S,BUYSCH H J,KRIMM H.Process for the preparation of dimethyl carbonate:US,4 335 051[P].1982-06-15.
[8]KNIFTON J F.Process for cogeneration of ethylene glycol and dimethyl carbonate:US,5 214 182[P].1993-05-25.
[9]CURNUTT G L.Catalytic vapor phase process for producing dihydrocarbyl carbonates:US,5 004 827[P].1991-04-02.
[10]PENG Wei-cai,ZHAO Ning,XIAO Fu-kui,et al.Recent progress in phosgene-free methods for synthesis of dimethyl carbonate[J].Pure Appl.Chem.,2012,84(3):603-620.
[11]DELLEDONNE D,RIVETTI F,ROMANO U.Developments in the production and application of dimethylcarbonate[J].Appl.Catal.A Gen.,2001,221(1):241-251.
[12]RYU J Y.Process for making dialkyl carbonates:US,5 902 894[P].1999-05-11.
[13]KUMAR S,JAIN S L.Polyethylene glycol enfolded KBr assisted base catalyzed synthesis of dimethyl carbonate from methanol and carbon dioxide[J].Ind.Eng.Chem.Res.,2014,53(41):15 798-15 801.
[14]TOMISHIGE K,SAKAIHORI T,IKEDA Y,et al.A novel method of direct synthesis of dimethyl carbonate from methanol and carbon dioxide catalyzed by zirconia[J].Catal.Lett.,1999,58(4):225-229.
[15]XIE Shui-bo,BELL A T.An in situ Raman study of dimethyl carbonate synthesis from carbon dioxide and methanol over zirconia[J].Catal.Lett.,2000,70(3/4):137-143.
[16]ESCH F,FABRIS S,ZHOU Ling,et al.Electron localization determines defect formation on ceria substrates[J].Science,2005,309(5 735):752-755.
[17]ZHOU Ying-jie,XIAO Min,WANG Shuan-jin,et al.Effects of Mo promoters on the Cu-Fe bimetal catalysts for the DMC formation from CO2and methanol[J].Chin.Chem.Lett.,2013,24(4):307-310.
[18]ZHOU Ying-jie,WANG Shuan-jin,XIAO Min,et al.Novel Cu-Fe bimetal catalyst for the formation of dimethyl carbonate from carbon dioxide and methanol[J].RSC.Adv.,2012,2(17):6 831-6 837.
[19]ZHANG Zhi-fan,LIU Zhao-tie,LIU Zhong-wen,et al.DMC formation over Ce0.5Zr0.5O2prepared by complexdecomposition method[J].Catal.Lett.,2009,129(3/4):428-436.
[20]LEE H,PARK S,SONG I,et al.Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over Ga O/Ce Zr O catalysts:effect of acidity and basicity of the catalysts[J].Catal.Lett.,2011,141(4):531-537.
[21]FANG Tao,LIAO Chong-jing,DUAN Zhen-xiao,et al.Synthesis of dimethyl carbonate from carbon dioxide,propylene epoxide and methanol[J].Adv.Mater.Res.,2013,734/737:2 120-2 123.
[22]YOSHIDA Y,ARAI Y,KADO S,et al.Direct synthesis of organic carbonates from the reaction of CO2with methanol and ethanol over Ce O2catalysts[J].Catal.Today,2006,115(1/4):95-101.
[23]段慧娟,范杰,张娟,等.甲醇、CO2在活性炭为模板剂制备的Ce O2上合成碳酸二甲酯[J].化学试剂,2015,37(9):834-838.
[24]WANG Sheng-ping,ZHAO Li-fang,WANG Wei,et al.Morphology control of ceria nanocrystals for catalytic conversion of CO2with methanol[J].Nanoscale,2013,5(12):5 582-5 588.
[25]CAVINATO G,TONIOLO L.New aspects of the synthesis of dimethyl carbonate via carbonylation of methyl alcohol promoted by methoxycarbonyl complexes of palladium(Ⅱ)[J].J.Organomet.Chem.,1993,444(1/2):65-66.
[26]KING S T.Reaction mechanism of oxidative carbonylation of methanol to dimethyl carbonate in Cu-Y zeolite[J].J.Catal.,1996,161(2):530-538.
[27]WU Xiao-min,KANG Min,YIN Yan-long,et al.Synthesis of dimethyl carbonate by urea alcoholysis over Zn/Al bi-functional catalysts[J].Appl.Catal.A Gen.,2014,473:13-20.
[28]BHANAGA B M,FUJITA S I,IKUSHIMA Y,et al.Synthesis of dimethyl carbonate and glycols from carbon dioxide,epoxides,and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity[J].Appl.Catal.A Gen.,2001,219(1/2):259-266.
[29]WU Xiao-min,KANG Min,ZHAO Ning,et al.Dimethyl carbonate synthesis over Zn O-Ca O bi-functional catalysts[J].Catal.Commun.,2014,46(5):46-50.
[30]BHANAGA B M,FUJITA S,IKUSHIMA Y,et al.Synthesis of dimethyl carbonate and glycols from carbon dioxide,epoxides and methanol using heterogeneous Mg containing smectite catalysts:effect of reaction variables on activity and selectivity performance[J].Green Chem.,2003,5(1):71-75.