Regulation of metal-support interface of Ni/CeO2 catalyst and the performance of low temperature chemical looping dry reforming of methane
-
摘要: 本研究合成了四种CeO2形貌的Ni/CeO2催化剂(纳米棒、纳米立方体、纳米八面体和纳米多面体),并探讨了催化剂低温化学链甲烷干重整反应的结构依赖性。材料表征表明,Ni物种高度分散在CeO2载体表面,部分Ni离子进入CeO2晶格,从而引起氧空位的增加。化学链干重整性能测试结果表明,棒状结构Ni/CeO2催化剂表现出最高的还原性,具有最多氧空位和最高储氧能力。多面体状Ni/CeO2催化剂的结构为形状不规则的约10.3 nm的CeO2纳米单晶,具有较大的比表面积和较高的还原性,表现出低温甲烷反应活性,在550 ℃低温化学链甲烷干重整中显示最高的氧化还原活性和循环稳定性。本研究为设计高效的金属/CeO2催化剂提供了一种新策略,有望促进铈基催化剂在化学链技术中应用。Abstract: Interface regulation is an effective strategy to improve the interaction between carrier and active metal center, which can improve the catalytic activity and oxygen storage capacity of the catalysts. In this paper, Ni/CeO2 catalysts supported on CeO2 with different morphologies (nanorods, nanocubes, nanoctahedrons and nanopolyhedrons) were synthesized. The structure dependence of the catalysts for the low temperature chemical looping dry reforming of methane (CL-DRM) was investigated. The characterization results showed that Ni species were highly dispersed on the surface of CeO2 carrier, and some Ni ions entered the CeO2 lattice, resulting in the increase of oxygen vacancies. The Ni/ceria-rods catalyst had the highest reducibility, the most oxygen vacancies and the highest oxygen storage capacity. The irregular CeO2 nano single crystal of about 10.3 nm in the Ni/ceria-polyhedra led to high specific surface area and high reducibility which exhibited the highest redox activity and redox stability in low-temperature chemical looping dry reforming of methane at 550 ℃. This study provided a new strategy for the design of efficient metal/CeO2 catalysts, which was expected to promote the application of cerium-based catalysts in chemical looping technology.
-
Key words:
- chemical looping /
- CeO2 /
- carbon dioxide /
- methane /
- crystal facets
-
图 9 (a)在不同的Ni/CeO2氧化还原催化剂上,甲烷氧化步骤中CH4的转化率、CO的选择性和CO2的转化率;(b)甲烷氧化步骤中H2、CO和CO2的产率和CO2分裂步骤中CO的产率。
Figure 9 (a) CH4 conversion, CO selectivity and CO2 conversion in methane oxidation step over different Ni/CeO2 redox catalyst; (b)Yields of H2, CO and CO2 in methane oxidation step and CO yield in CO2 splitting step
图 10 用于CLDRM的Ni/CeO2氧化还原催化剂的氧化还原稳定性:(a)在550 ℃下,三种Ni/CeO2氧化还原催化剂在连续氧化还原循环中的CH4转化和CO2转化;(b) 在Ni/CeO2-P氧化还原催化剂上,甲烷氧化步骤中H2、CO和CO2的产率以及CO2分裂步骤中CO的产率
Figure 10 Redox stability of Ni/CeO2 redox catalysts for CL-DRM (a) CH4 conversion and CO2 conversion in successive redox cycles over three Ni/CeO2 catalyst at 550 ℃; (b) Yield of H2, CO and CO2 in methane oxidation step and CO yield in CO2 splitting step over Ni/CeO2-P catalyst at 550 ℃ for 50 redox cycles
表 1 CeO2纳米结构水热合成条件
Table 1 Hydrothermal synthesis conditions of CeO2 nanostructures
Support ${{C} }_{ {\rm{NaOH/Na_3PO_4} } }$
(mol·L−1)t/℃ t/h Structure Shape CeO2-R 6 100 24 cubic rods CeO2-C 7 180 24 cubic cubes CeO2-P 0.5 100 24 cubic particles CeO2-O 0.0003 170 10 cubic octahedra Note: Synthesized under [Ce3+] = 0.4 mol/L 表 2 Ni/CeO2样品中CeO2的晶格参数(a0)、结晶尺寸和微应变(ε)
Table 2 Lattice parameter (a0), crystalline size, and the microstrain (ε) of ceria in Ni/CeO2 samples
Sample d(111)-spacing/nm Lattice parameter/nm CeO2 crystalline size/nm ε/% (111) (220) (311) avg. Ni/CeO2-R 0.31122 0.541134 11.2 11.2 11.4 11.4 0.084 Ni/CeO2-C 0.31186 0.541058 > 100 > 100 > 100 319.7 0.020 Ni/CeO2-P 0.31207 0.540609 10.2 10.5 10.7 10.3 0.027 Ni/CeO2-O 0.31044 0.539575 60.1 53.9 51.3 55.1 0.058 表 3 煅烧后的Ni/CeO2催化剂的织构性能
Table 3 Textural properties and redox behaviors of calcined Ni/CeO2 catalysts
Sample SBET/(m2·g−1) Pore
volume/(cm3·g−1)Average pore
size/nmNi/CeO2-R 57.88 0.26 61.0 Ni/CeO2-C 7.93 0.02 19.2 Ni/CeO2-P 60.91 0.17 47.4 Ni/CeO2-O 12.01 0.03 24.5 -
[1] ARAMOUNI NA K, ZEAITER J, KWAPINSKI W, AHMAD, MN. Thermodynamic analysis of methane dry reforming: Effect of the catalyst particle size on carbon formation[J]. Energy Conv Manag,2017,150:614−622. doi: 10.1016/j.enconman.2017.08.056 [2] LARIONOV K B, GROMOV A A. Non-isothermal oxidation of coal with Ce(NO3)3 and Cu(NO3)2 additives[J]. Int J Coal Sci Technol,2019,6(1):37−50. doi: 10.1007/s40789-018-0229-y [3] CHEN S, ZAFFRAN J, YANG B. Dry reforming of methane over the cobalt catalyst: Theoretical insights into the reaction kinetics and mechanism for catalyst deactivation[J]. Appl Catal B: Environ,2020,270:9. [4] ZHANG X, ZHANG L, PENG H, YOU X, PENG C. Nickel nanoparticles embedded in mesopores of AlSBA-15 with a perfect peasecod-like structure: A catalyst with superior sintering resistance and hydrothermal stability for methane dry reforming[J]. Appl Catal B: Environ,2018,224:488−499. doi: 10.1016/j.apcatb.2017.11.001 [5] QING W, Lin C, CHENG W, XIAO X. Enhancing the activity of iron based oxygen carrier via surface controlled preparation for lignite chemical looping combustion[J]. Chem J Chin Univ,2015,36(1):116−123. [6] ZENG L, HUANG F, ZHU X, ZHENG M, LI K. Chemical looping of methane over CeO2-based and Co3O4-CeO2 oxygen carriers: Controlling of product selectivity[J]. Chem J Chin Univ,2017,38(1):11. [7] ZENG L, LI K, HUANG F, ZHU X, LI H. Effects of Co3Oz` nanocatalyst morphology on CO oxidation: Synthesis process map and catalytic activity[J]. Chin J Catal, 37(6): 908−922. [8] LOFBERG A, KANE T, GUERRERO-CABALLERO J, JALOWIECKI-DUHAME, L. Chemical looping dry reforming of methane: Toward shale-gas and biogas valorization[J]. Chem Eng Process,2017,122:523−529. doi: 10.1016/j.cep.2017.05.003 [9] ZHU X, GAO Y, WANG X, HARIBAL V, LIU J, NEAL L M. A tailored multi-functional catalyst for ultra-efficient styrene production under a cyclic redox scheme[J]. Nat Commun,2021,12(1):11−25. doi: 10.1038/s41467-020-20162-8 [10] ZHU X, IMTIAZ Q, DONAT F, MULLER CR, LI F. Chemical looping beyond combustion - a perspective[J]. Energy Environ Sci,2020,13(3):772−804. doi: 10.1039/C9EE03793D [11] NANDY A, LOHA C, GU S, SARKAR P, KARMAKAR MK, CHATTRJEE P K. Present status and overview of chemical looping combustion technology[J]. Renewable Sustainable Energy Rev,2016,59:597−619. doi: 10.1016/j.rser.2016.01.003 [12] ZHU M, SONG Y, CHEN S, LI M, ZHANG L, XIANG W. Chemical looping dry reforming of methane with hydrogen generation on Fe2O3/Al2O3 oxygen carrier[J]. Chem Eng J,2019,368:812−823. doi: 10.1016/j.cej.2019.02.197 [13] BUELENS L C, GALVITA V V, POELMAN H, DETAVERNIE C, MARIN GB. Super-dry reforming of methane intensifies CO2 utilization via Le Chatelier's principle[J]. Science,2016,354(6311):449−452. doi: 10.1126/science.aah7161 [14] AY H, UNER D. Dry reforming of methane over CeO2 supported Ni, Co and Ni-Co catalysts[J]. Appl Catal B: Environ,2015,179:128−138. doi: 10.1016/j.apcatb.2015.05.013 [15] YANG Z, LEI Z, GE B, XIONG X, JIN Y, JIAO K, CHEN F. Development of catalytic combustion and CO2 capture and conversion technology[J]. Int J Coal Sci Technol,2021,8(3):377−382. doi: 10.1007/s40789-021-00444-2 [16] CHEN L, BAO J, KONG L, COMBS M, NIKOLIC HS, FAN Z. The direct solid-solid reaction between coal char and iron-based oxygen carrier and its contribution to solid-fueled chemical looping combustion[J]. Appl Energy,2016,184:9−18. doi: 10.1016/j.apenergy.2016.09.085 [17] TANG M, XU L, FAN M. Progress in oxygen carrier development of methane-based chemical-looping reforming: A review[J]. Appl Energy,2015,151:143−156. doi: 10.1016/j.apenergy.2015.04.017 [18] ZHU X, ZHANG M, LI K, WEI Y, ZHENG Y, HU J, WANG H. Chemical-looping water splitting over ceria-modified iron oxide: Performance evolution and element migration during redox cycling[J]. Chem Eng Sci,2018,179:92−103. doi: 10.1016/j.ces.2018.01.015 [19] HAN Y, TIAN M, WANG C, KANG Y, KANG L, SU Y. Highly active and anticoke Ni/CeO2 with ultralow ni loading in chemical looping dry reforming via the strong metal-support interaction[J]. ACS Sustainable Chem Eng,2021,9(51):17276−17288. [20] ZHU X, WEI Y, WANG H. Ce-Fe oxygen carriers for chemical-looping steam methane reforming[J]. Int J Hydrog Energy,2013,38(11):4492−4501. doi: 10.1016/j.ijhydene.2013.01.115 [21] ZHU X, LI K, WEI Y, WANG H, SUN L. Chemical-looping steam methane reforming over a CeO2–Fe2O3 oxygen carrier: Evolution of its structure and reducibility[J]. Energy Fuels,2014,28(2):754−760. doi: 10.1021/ef402203a [22] DOU B, ZHANG H, SONG Y, ZHAO L, JIANG B, HE M, CHEN H. Hydrogen production from the thermochemical conversion of biomass: Issues and challenges[J]. Sustainable Energy Fuels,2019,3(2):314−342. doi: 10.1039/C8SE00535D [23] DE DIEGO L F, ORTIZ M, ADANEZ J. Synthesis gas generation by chemical-looping reforming in a batch fluidized bed reactor using Ni-based oxygen carriers[J]. Chem Eng J,2008,144(2):289−298. doi: 10.1016/j.cej.2008.06.004 [24] ZHU X, WANG H, WEI Y, LI K. Hydrogen and syngas production from two-step steam reforming of methane over CeO2-Fe2O3 oxygen carrier[J]. J Rare Earths,2010,28(6):907−913. doi: 10.1016/S1002-0721(09)60225-8 [25] DING W, ZHAO K, JIANG S, ZHAO Z, CAO Y, HE F. Alkali-metal enhanced LaMnO3 perovskite oxides for chemical looping oxidative dehydrogenation of ethane[J]. Appl Catal A: Gen,2021,609:8−19. [26] HUANG J, LIU W, HU W, METCALFE I, YANG Y, LIU B. Phase interactions in Ni-Cu-Al2O3 mixed oxide oxygen carriers for chemical looping applications[J]. Appl Energy,2019,236:635−647. doi: 10.1016/j.apenergy.2018.12.029 [27] MEJIA C, DEELEN T V, JONG K. Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity[J]. Nat Catal,2019,2(11):955−970. doi: 10.1038/s41929-019-0364-x [28] MAI H, SUN L, ZHANG Y, SI R, FENG W, ZHANG H, LIU H, YAN Ch. Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes[J]. J Phys Chem B,2005,109(51):24380−24385. doi: 10.1021/jp055584b [29] HE L, REN Y, FU Y, YUE B, TSANG S, HE H. Morphology-dependent catalytic activity of Ru/CeO2 in dry reforming of methane[J]. Molecules,2019,24(3):12−23. [30] YAN X, HU T, LIU P, LI S, ZHAO B, ZANG Q, JIAO W. Highly efficient and stable Ni/CeO2-SiO2 catalyst for dry reforming of methane: Effect of interfacial structure of Ni/CeO2 on SiO2[J]. Appl Catal B: Environ,2019,246:221−231. doi: 10.1016/j.apcatb.2019.01.070 [31] DATTA S, TORRENTE-MURCIANO L. Nanostructured faceted ceria as oxidation catalyst[J]. Curr Opin Chem Eng,2018,20:99−106. doi: 10.1016/j.coche.2018.03.009 [32] HUANG F, YE D, GUO X, ZHAN W, GUO Y, WANG L, WANG Y. Effect of ceria morphology on the performance of MnOx/CeO2 catalysts in catalytic combustion of N, N-dimethylformamide[J]. Catal Sci Technol,2020,10(8):2473−2483. doi: 10.1039/C9CY02384D [33] KIM H J, JANG M G, SHIN D, HAN J W. Design of ceria catalysts for low-temperature CO oxidation[J]. ChemCatChem,2020,12(1):11−26. [34] RODRIGUEZ J A, WANG X, LIU G, HANSONA J C, HRBEK J, PEDEN C H F, IGLESIAS-JUEZ A, FERNANDEZ-GARCIA M. Physical and chemical properties of Ce1−xZrxO2 nanoparticles and Ce1−xZrxO2(111) surfaces: synchrotron-based studies[J]. J Mol Catal A: Chem,2005,228(1/2):11−19. doi: 10.1016/j.molcata.2004.09.069 [35] FUKUHARA C, HAYAKAWA K, SUZUKI Y, KAWASAKI W, WATANABE R. A novel nickel-based structured catalyst for CO2 methanation: A honeycomb-type Ni/CeO2 catalyst to transform greenhouse gas into useful resources[J]. Appl Catal A: Gen,2017,532:12−18. doi: 10.1016/j.apcata.2016.11.036 [36] HUANG X, SUN H, WANG L, LIU Y, FAN K, CAO Y. Morphology effects of nanoscale ceria on the activity of Au/CeO2 catalysts for low-temperature CO oxidation[J]. Appl Catal B: Environ,2009,90(1/2):224−232. doi: 10.1016/j.apcatb.2009.03.015 [37] LI J, TA N, LI Y, SHEN W. Morphology effect of nano-scale CeO2 in heterogeneous catalytic reactions[J]. Chin J Catal,2008,29(9):823−830. [38] LIN Y, WU Z, WEN J, POEPPELMEIER K R, MARKS L D. Imaging the atomic surface structures of CeO2 nanoparticles[J]. Nano Lett,2014,14(1):191−196. doi: 10.1021/nl403713b [39] CABALLERO A, HOLGADO J P, GONZALEZ-DELACRUZ V M. In situ spectroscopic detection of SMSI effect in a Ni/CeO2 system: Hydrogen-induced burial and dig out of metallic nickel[J]. Chem Commun,2010,46(7):1097−1106. doi: 10.1039/B920803H [40] LAASSIRI S, ZEINALIPOUR-YAZDI C D, CATLOW C R A. The potential of manganese nitride based materials as nitrogen transfer reagents for nitrogen chemical looping[J]. Appl Catal B: Environ,2018,223:60−69. doi: 10.1016/j.apcatb.2017.04.073 [41] WEI Y, ZHANG Y, ZHANG P, XIONG J, MEI X, YU Q, ZHAO Z, LIU J. Boosting the removal of diesel soot particles by the optimal exposed crystal facet of CeO2 in Au/CeO2 catalysts[J]. Environ Sci Technol,2020,54(3):2002−2011. doi: 10.1021/acs.est.9b07013 [42] ZHANG X, YOU R, LI D, CAO T, HUANG W. Reaction sensitivity of ceria morphology effect on Ni/CeO2 catalysis in propane oxidation reactions[J]. ACS Appl Mater Interfaces,2017,9(41):35897−35907. doi: 10.1021/acsami.7b11536 [43] SHAPOVALOV V, METIU H. Catalysis by doped oxides: CO oxidation by AuxCe1−xO2[J]. J Catal,2007,245(1):205−214. doi: 10.1016/j.jcat.2006.10.009 [44] ABDULLAH B, GHANI N A A, VO D V N. Recent advances in dry reforming of methane over Ni-based catalysts[J]. J Clean Prod,2017,162:170−185. doi: 10.1016/j.jclepro.2017.05.176 [45] LONG Y, LI K, GU Z, ZHU X, WEI Y, LU C, LIN S, YANG K, CHENG X, TIAN D. Ce-Fe-Zr-O/MgO coated monolithic oxygen carriers for chemical looping reforming of methane to co-produce syngas and H2[J]. Chem Eng J,2020,388:13. [46] NAJERA M, SOLUNKE R, GARDNER T, VESER G. Carbon capture and utilization via chemical looping dry reforming[J]. Chem Eng Res Des,2011,89(9):1533−1543. doi: 10.1016/j.cherd.2010.12.017 [47] CHEIN R, HSU W. Thermodynamic analysis of syngas production via chemical looping dry reforming of methane[J]. Energy,2019,180:535−547. doi: 10.1016/j.energy.2019.05.083 [48] WANG Y, LIU H, XU B. Durable Ni/MgO catalysts for CO2 reforming of methane: Activity and metal-support interaction[J]. J Mol Catal A: Chem,2009,299(1/2):44−52. doi: 10.1016/j.molcata.2008.09.025 [49] WU Z, LI M, OVERBURY S H. On the structure dependence of CO oxidation over CeO2 nanocrystals with well-defined surface planes[J]. J Catal,2012,285(1):61−73. doi: 10.1016/j.jcat.2011.09.011 [50] LIU L, YAO Z, DENG Y, Gao F, LIU B, DONG L. Morphology and crystal-plane effects of nanoscale ceria on the activity of CuO/CeO2 for NO reduction by CO[J]. ChemCatChem,2011,3(6):978−989.