Effect of support calcination atmospheres on the activity of CuO/CeO2 catalysts for methanol steam reforming
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摘要: 采用沉淀法和浸渍法制备了具有氧空位的CeO2纳米材料和甲醇水蒸气重整制氢CuO/CeO2催化剂, 探索不同焙烧气氛对CeO2纳米材料结构、性质和甲醇水蒸气重整制氢性能的影响。采用SEM、XRD、BET、H2-TPR、N2O滴定和XPS等手段对催化剂进行了表征。结果表明, CuO/CeO2催化剂的催化活性与催化剂的Cu比表面积大小、Cu-Ce的相互作用强弱、表面缺陷和表面氧空位的多少有关。其中, 在氢气气氛下焙烧所得的CeO2负载CuO后的CuO/CeO2-H催化剂催化活性最佳。在反应温度为250℃, 水醇物质的量比为1.2时, 甲醇气体空速为800 h-1, 甲醇转化率达到了100%, 重整尾气中CO含量为0.87%。Abstract: In this paper, CeO2 nanomaterials with oxygen vacancies and CuO/CeO2 catalysts for hydrogen production from methanol steam reforming were prepared by precipitation and impregnation methods.The influence of different calcination atmosphere on the structure and properties of CeO2 nanomaterials and the hydrogen production performance of methanol steam reforming was investigated.SEM, XRD, BET, H2-TPR, N2O titration and XPS were adopted to characterize the catalyst materials.The results showed that the catalytic activity of CuO/CeO2 catalyst was closely related to the surface area of copper, the strength of Cu-Ce interaction, the number of surface defects and surface oxygen vacancies.When the reaction temperature was 250℃, the molar ratio of water to methanol was 1.2 and the gas hourly space velocity was 800 h-1, the methanol conversion was 100% and the CO concentration in the offgas was 0.87%.
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Key words:
- ceria /
- carbon monoxide /
- methanol steam reforming /
- hydrogen
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图 2 CeO2-X和CuO/CeO2-X催化剂的XRD谱图
a:CeO2-H; b:CeO2-N; c:CeO2-A;
d:CuO/CeO2-H; e:CuO/CeO2-N; f:CuO/CeO2-AFigure 2 XRD patterns of CeO2-X and CuO/CeO2-X
图 3 催化剂CuO/CeO2-X的H2-TPR谱图
a:CuO/CeO2-H; b:CuO/CeO2-N;c:CuO/CeO2-A
Figure 3 H2-TPR profiles of the CuO/CeO2-X catalysts
图 4 CuO/CeO2-X催化剂的Cu 2p XPS谱图(a)和Cu俄歇谱图(b)
a:CuO/CeO2-H; b:CuO/CeO2-N; c:CuO/CeO2-A
Figure 4 XPS spectra of Cu 2p binding energy region (a) and Auger spectra of Cu LMM (b) obtained from CuO/CeO2-X catalysts
图 5 CuO/CeO2催化剂Ce 3d的XPS谱图
a:CuO/CeO2-H; b:CuO/CeO2-N; c:CuO/CeO2-A
Figure 5 XPS spectra of Ce 3d binding energy region obtained from CuO/CeO2 catalysts
图 6 CuO/CeO2催化剂O 1s的XPS谱图
a:CuO/CeO2-H; b:CuO/CeO2-N; c:CuO/CeO2-A
Figure 6 XPS spectra of O 1s binding energy region obtained from CuO/CeO2 catalysts
图 7 反应温度对甲醇转化率的影响
(reaction conditions:W/M(molar ratio)=1.2,
GHSV=800 h-1, no carrier gas)Figure 7 Methanol conversion as a function of the reaction temperature
图 8 反应温度对产物中CO摩尔含量的影响
(reaction conditions:W/M(molar ratio)= 1.2,
GHSV = 800 h-1, no carrier gas)Figure 8 CO molar concentration in offgas as a function of the reaction temperature
表 1 催化剂的物化性质和产氢速率
Table 1 Physical characteristics of the prepared catalysts and hydrogen production rate in methanol steam reforming
Catalyst ABET/ (m2·g-1) Pore volume v/ (cm3·g-1) dCuOa/nm Cu dispersion/% Cu surface area A/ (m2·g-1) YH2b/ (μmol·kg-1 ·s-1) CeO2-H 54.8 0.25 - - - - CeO2-N 62.8 0.23 - - - - CeO2-A 37.4 0.10 - - - - CuO/CeO2-H 52.0 0.23 23.4 17.29 10.0 18008.9 CuO/CeO2-N 56.9 0.22 26.4 15.87 9.2 16897.3 CuO/CeO2-A 21.9 0.09 29.9 15.33 8.8 11322.3 a:the CuO average crystal size was calculated from CuO 2θ=38.7°; b:H2 production was calculated when temperature is 240 ℃, W/M(molar ratio)=1.2, GHSV=800 h-1 
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表 2 Cu LMM俄歇谱, Ce 3d XPS谱图以及表面Cu含量
Table 2 Results of Auger of Cu LMM, XPS of Ce 3d, and surface Cu content of the catalysts
Catalyst Cu+/%a Ce3+/%b Cu/(Cu+Ce) CuO/CeO2-H 54.7 22.08 0.23 CuO/CeO2-N 54.5 18.76 0.22 CuO/CeO2-A 43.9 18.50 0.19 a:the surface Cu+ content determined according to the Auger of Cu LMM result; b:the surface Ce3+ content determined according to the XPS of Ce 3d result
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[1] AGRELL J, BIRGERSSON H, BOUTONNET M, MELIAN-CABRERA I, NAVARRO R M, FIERRO J L G.Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2, and Al2O3[J].J Catal, 2003, 219(2):389-403. doi: 10.1016/S0021-9517(03)00221-5 [2] GU X K, LI W X.First-principles study on the origin of the different selectivities for methanol steam reforming on Cu(111) and Pd(111)[J].J Phys Chem C, 2010, 114(49):43-43. doi: 10.1021/jp107678d [3] TROVARELLI A.Catalytic properties of ceria and CeO-containing materials[J].Catal Rev, 1996, 38(4):439-520. doi: 10.1080/01614949608006464 [4] VALDES-SOLI T, MARBAN G, FUERTES A B.Nanosized catalysts for the production of hydrogen by methanol steam reforming[J].Catal Today, 2006, 116(3):354-360. doi: 10.1016/j.cattod.2006.05.063 [5] YANG S C, SU W N, LIN S D, RICK J, HWANG B J.Preparation of highly dispersed catalytic Cu from rod-like CuO-CeO2 mixed metal oxides:Suitable for applications in high performance methanol steam reforming[J].Catal Sci Technol, 2012, 2(4):807-812. doi: 10.1039/c2cy00330a [6] ZHOU J J, ZHANG Y, WU G S, MAO D S, LU G Z.Influence of the component interaction over Cu/ZrO2 catalysts induced with fractionated precipitation method on the catalytic performance for methanol steam reforming[J].RSC Adv, 2016, 6(36):30176-30183. doi: 10.1039/C5RA24163D [7] LAN H, ZHOU G L, LUO C J, YU Y R, XIE H M, ZHANG G Z.High efficiency CeCu composite oxide catalysts improved via preparation methods for propyl acetate catalytic combustion in air[J].Int J Chem React Eng, 2016, 14(3):757-768. https://www.deepdyve.com/lp/de-gruyter/high-efficiency-cecu-composite-oxide-catalysts-improved-via-QWhZ1ritOx [8] LI C C, LIN R J, LIN H P, LIN Y K, LIN Y G, CHANG C C, CHEN L C, CHEN K H.Catalytic performance of plate-type Cu/Fe nanocomposites on ZnO nanorods for oxidative steam reforming of methanol[J].Chem Commun, 2011, 47(5):1473-1475. doi: 10.1039/C0CC02918A [9] LANDI G, BARBATO P S, BENEDETTO A D, LISI L.Optimization of the preparation method of CuO/CeO2, structured catalytic monolith for CO preferential oxidation in H2-rich streams[J].Appl Catal B:Environ, 2016, 181(8):727-737. [10] LIU X, MEN Y, WANG J G, HE R, WANG Y Q.Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming[J].J Power Sources, 2017, 364:341-350. doi: 10.1016/j.jpowsour.2017.08.043 [11] JIRATOVA K, KOVANDA F, BALABANOVA J, KOLOUSEK D, KLEGOVA A, PACULTOVA K, OBALOVA L.Cobalt oxide catalysts supported on CeO2-TiO2, for ethanol oxidation and N2O decomposition[J].React Kinet Mech Catal, 2017, 121(1):121-139. doi: 10.1007/s11144-017-1142-x [12] ZAIBILSKIY M, DJINOVIC P, TCHERNYCHOVA E, TKACHENKO O P, KUSTOV L M, PINTAR A.Nanoshaped CuO/CeO2 materials:Effect of the exposed ceria surfaces on catalytic sctivity in N2O decomposition reaction[J].ACS Catal, 2015, 5(9):5357-5365. doi: 10.1021/acscatal.5b01044 [13] ZHOU X H, LI L, LI Z H, FAN L L, KANG W M, CHENG B W.The preparation of continuous CeO2/CuO/Al2O3, ultrafine fibers by electro-blowing spinning (EBS) and its photocatalytic activity[J].J Mater Sci:Mater Electron, 2017, 28(1):1-11. doi: 10.1007/s10854-016-5486-1 [14] SURESH R, POMMUSWAMY V, MARIAPPAN R.Effect of annealing temperature on the microstructural, optical and electrical properties of CeO2, nanoparticles by chemical precipitation method[J].Appl Surf Sci, 2013, 273:457-464. doi: 10.1016/j.apsusc.2013.02.062 [15] POLYCHRONOPOULOU K, ZEDAN A F, KATSIOTIS M S, BAKER M A, ALKHOORI A A, ALQARADAWI S Y, HINDER S J, ALHASSAN S.Rapid microwave assisted sol-gel synthesis of CeO2, and CexSm1-xO2, nanoparticle catalysts for CO oxidation[J].J Mol Catal A:Chem, 2017, 428:41-55. [16] MINAEI S, HAGHIGHI M, JODEIRI N, AJAMEIN H, ABDOLLAHIFAR M.Urea-nitrates combustion preparation of CeO2-promoted CuO/ZnO/Al2O3, nanocatalyst for fuel cell grade hydrogen production via methanol steam reforming[J].Adv Powder Technol, 2017, 28(3):842-853. doi: 10.1016/j.apt.2016.12.010 [17] 张磊, 雷俊腾, 田园, 胡鑫, 白金, 刘丹, 杨义, 潘立卫.前驱体和沉淀剂浓度对CuO/ZnO/CeO2-ZrO2甲醇水蒸气重整制氢催化剂性能的影响[J].燃料化学学报, 2015, 43(11):1366-1374. doi: 10.3969/j.issn.0253-2409.2015.11.012ZHANG Lei, LEI Jun-teng, TIAN Yuan, HU Xin, BAI Jin, LIU Dan, YANG Yi, PAN Li-wei.Effect of precursor and precipitant concentration on the performance of CuO/ZnO/CeO2-ZrO2 catalyst for methanol steam reforming[J].J Fuel Chem Technol, 2015, 43(11):1366-1374. doi: 10.3969/j.issn.0253-2409.2015.11.012 [18] RAO G R, SAHU H R, MISHRA B G.Surface and catalytic properties of Cu-Ce-O composite oxides prepared by combustion method[J].Colloids Surf A, 2003, 220(1):261-269. http://www.sciencedirect.com/science/article/pii/S0927775703000803 [19] 杨淑倩, 贺建平, 张娜, 隋晓伟, 张磊, 杨占旭.稀土掺杂改性Cu/Zn-Al水滑石衍生催化剂对甲醇水蒸气重整制氢性能的影响[J].燃料化学学报, 2018, 46(2):179-188. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract19166.shtmlYANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu.Rare-earth improvement of Cu/Zn-Al catalysts derived from hydrotalcite precursor for methanol steam reforming[J].J Fuel Chem Technol, 2018, 46(2):179-188. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract19166.shtml [20] SHANG H H, ZHANG X M, XU J, HAN Y F.Effects of preparation methods on the activity of CuO/CeO2 catalysts for CO oxidation[J].Fron Chem Sci Eng, 2017, 11(4):603-612. doi: 10.1007/s11705-017-1661-z [21] ZENG S H, LIU Y, WANG Y Q.CuO-CeO2/Al2O3/FeCrAl monolithic catalysts prepared by sol-pyrolysis method for preferential oxidation of carbon monoxide[J].Catal Lett, 2007, 117(3/4):119-125. [22] HE J P, YANG Z X, ZHANG L, LI Y, PAN L W.Cu supported on ZnAl-LDHs precursor prepared by in-situ synthesis method on γ-Al2O3, as catalytic material with high catalytic activity for methanol steam reforming[J].Int J Hydrogen Energy, 2017, 42(15):1-8. https://www.researchgate.net/profile/Karin_Foettinger [23] SHEN W W, MAO D S, LUO Z M, YU J.CO oxidation on mesoporous SBA-15 supported CuO-CeO2 catalyst prepared by a surfactant-assisted impregnation method[J].RSC Adv, 2017, 7(44):27689-27698. doi: 10.1039/C7RA02966G [24] AMADINE O, ESSAMLALI Y, FIHRI A, LARZAEK M, ZAHOUILY M.Effect of calcination temperature on the structure and catalytic performance of copper-ceria mixed oxide catalysts in phenol hydroxylation[J].RSC Adv, 2017, 7(21):12586-12597. doi: 10.1039/C7RA00734E [25] ZHANG L, PAN L W, NI C J, SUN T J, WANG S D, HU Y K, WANG A J, ZHAO S S.Effects of precipitation aging time on the performance of CuO/ZnO/CeO2-ZrO2, for methanol steam reforming[J].J Fuel Chem Technol, 2013, 41(7):883-888. doi: 10.1016/S1872-5813(13)60038-9 [26] DAS D, LLORCA J, DOMINGUEZ M, COLUSSI S, TROVARELLI A, GAYEN A.Methanol steam reforming behavior of copper impregnated over CeO2-ZrO2, derived from asurfactant assisted coprecipitation route[J].Int J Hydrogen Energy, 2015, 40(33):10463-10479. doi: 10.1016/j.ijhydene.2015.06.130 [27] LUO Z M, MAO D S, SHEN W W, ZHENG Y L, YU J.Preparation and characterization of mesostructured cellular foam silica supported Cu-Ce mixed oxide catalysts for CO oxidation[J].RSC Adv, 2017, 7(16):9732-9743. doi: 10.1039/C6RA25912J [28] BARABATO P S, COLUSSI S, BENEDETTO A D, LANDI G, LISI L, LLORCA J, TROVARELLI A.On the origin of high activity and selectivity of CuO/CeO2 catalysts prepared by solution combustion synthesis in CO-PROX reaction[J].J Phys Chen C, 2016, 120(24):13039-13048. doi: 10.1021/acs.jpcc.6b02433 [29] DOSA M, PIUMETTI M, BENSAID S, ANDANA T, NOVARA C, GIORGIS F, FINO D, RUSSO N.Novel Mn-Cu-Containing CeO2, nanopolyhedra for the oxidation of CO and diesel soot:Effect of dopants on the nanostructure and catalytic activity[J].Catal Lett, 2018, 148(1):298-311. doi: 10.1007/s10562-017-2226-y [30] ZENG S H, ZHANG W L, GUO S L, SU H Q.Inverse rod-like CeO2 supported on CuO prepared by hydrothermal method for preferential oxidation of carbon monoxide[J].Catal Commun, 2012, 23(21):62-66. http://www.sciencedirect.com/science/article/pii/S1566736712000854 [31] JI Y J, JIN Z Y, LI J, ZHANG Y, LIU H Z, SHI L S, ZHONG Z Y, SU F B.Rambutan-like hierarchically heterostructured CeO2-CuO hollow microspheres:Facile hydrothermal synthesis and applications[J].Nano Res, 2017, 10(2):381-396. doi: 10.1007/s12274-016-1298-0 [32] ZHANG L, PAN L, NI C, SUN T, ZHAO S, WANG S, WANG A, HU Y.CeO2-ZrO2-promoted CuO/ZnO catalyst for methanol steam reforming[J].Int J Hydrogen Energy, 2013, 38(11):4397-4406. doi: 10.1016/j.ijhydene.2013.01.053 [33] 张磊, 潘立卫, 倪长军, 孙天军, 赵生生, 王树东, 胡永康, 王安杰.沉淀温度对CuO/ZnO/CeO2/ZrO2甲醇水蒸气重整制氢催化剂性能的影响[J].催化学报, 2012, 33(12):1958-1964.ZHANG Lei, PAN Li-wei, NI Chang-jun, SUN Tian-jun, ZHAO Sheng-sheng, WANG Shu-dong, HU Yong-kang, WANG An-jie.Effect of precipitation temperature on the performance of CuO/ZnO/CeO2/ZrO2 catalyst for methanol steam reforming[J].Chin J Catal, 2012, 33(12):1958-1964. -
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