Abstract
In this study, Cu and Co doped Ni/Al2O3 nanocatalyst was synthesized via impregnation and sol–gel methods. The physiochemical properties of nanocatalyst were characterized by XRD, field emission scanning electron microscopy (FESEM), particle size distribution, BET, fourier transform infrared spectroscopy (FTIR), TG–DTA and energy dispersive X-ray (EDX) analysis. The samples were employed for CO2-reforming of methane in atmospheric pressure, temperature range from 550 to 850 °C, under various mixture of CH4/CO2 and different gas hourly space velocity. XRD patterns besides indicating the decline of the peaks intensity in sol–gel method, proved the potential of this procedure in diminishing the crystal size and preventing the NiAl2O4 spinel formation. Moreover, high surface area might derive of smaller particle size and uniform morphology of sol–gel prepared ones, confirmed by FESEM and BET analysis. TG–DTG analysis as well supported the higher surface area for sol–gel made ones, represented the proper calcination temperature (approximately 600 °C). Also, presence of the active phases and elemental composition of nanocatalysts determine via EDX analysis. Promoting the basicity and the adsorption rate of CO2, is attributed to the higher amount of OH groups for sol–gel prepared samples, proved by FTIR. Ni–Co/Al2O3 due to the synergetic effect of sol–gel method and cobalt addition depicted excellent characterization such as higher surface area, smaller particle size, supplying more stable support and enhanced morphology. Therefore, this nanocatalyst represented the best products yield (H2 = 98.21 and CO = 95.64), H2/CO close to unit (0.92–1.05) and stable conversion during 1,440 min stability test. So, Ni–Co/Al2O3 among all of the prepared nanocatalysts demonstrated the best catalytic performance and presented it as a highly efficient catalyst for dry reforming of methane. Despite of the stable yield of Ni–Cu/Al2O3, it depicted the lower catalytic activity and H2/CO ratio than the unprompted nanocatalysts.
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References
Ruckenstein E, Hu YH (1995) Carbon dioxide reforming of methane over nickel/alkaline earth metal oxide catalysts. Appl Catal A 133(1):149–161
Bradford MCJ, Vannice MA (1999) CO2 reforming of CH4. Catal Rev 41(1):1–42
Tomishige K, Chen Y-g, Fujimoto K (1999) Studies on carbon deposition in CO2 reforming of CH4 over nickel–magnesia solid solution catalysts. J Catal 181(1):91–103
Wei J-M, Xu B-Q, Li J-L, Cheng Z-X, Zhu Q-M (2000) Highly active and stable Ni/ZrO2 catalyst for syngas production by CO2 reforming of methane. Appl Catal A 196(2):L167–L172
San Jose-Alonso D, Illan-Gomez MJ, Roman-Martinez MC (2013) Low metal content Co and Ni alumina supported catalysts for the CO2 reforming of methane. Int J Hydrogen Energy 38(5):2230–2239
Ross JRH, van Keulen ANJ, Hegarty MES, Seshan K (1996) The catalytic conversion of natural gas to useful products. Catal Today 30(1–3):193–199
Xu L, Song H, Chou L (2011) Carbon dioxide reforming of methane over ordered mesoporous NiO–MgO–Al2O3 composite oxides. Appl Catal B 108–109:177–190
Roh H-S, Jun K-W, Baek S-C, Park S-E (2002) Carbon dioxide reforming of methane over Ni/θ-Al2O3 catalysts: effect of Ni content. Bull Korean Chem Soc 23:1166–1168
Zhang J, Wang H, Dalai AK (2008) Effects of metal content on activity and stability of Ni–Co bimetallic catalysts for CO2 reforming of CH4. Appl Catal A 339(2):121–129
Zhu J, Peng X, Yao L, Deng X, Dong H, Tong D, Hu C (2013) Synthesis gas production from CO2 reforming of methane over Ni–Ce/SiO2 catalyst: the effect of calcination ambience. Int J Hydrogen Energy 38(1):117–126
Li H, Wang J (2004) Study on CO2 reforming of methane to syngas over Al2O3–ZrO2 supported Ni catalysts prepared via a direct sol–gel process. Chem Eng Sci 59(22–23):4861–4867
Chen Y-g, Tomishige K, Yokoyama K, Fujimoto K (1997) Promoting effect of Pt, Pd and Rh noble metals to the Ni0.03Mg0.97O solid solution catalysts for the reforming of CH4 with CO2. Appl Catal A Gen 165(1–2):335–347
Kumar P, Sun Y, Idem RO (2008) Comparative study of Ni-based mixed oxide catalyst for carbon dioxide reforming of methane. Energy Fuels 22(6):3575–3582
Nagai M, Nakahira K, Ozawa Y, Namiki Y, Suzuki Y (2007) CO2 reforming of methane on Rh/Al2O3 catalyst. Chem Eng Sci 62(18–20):4998–5000
Nakagawa K, Anzai K, Matsui N, Ikenaga N, Suzuki T, Teng Y, Kobayashi T, Haruta M (1998) Effect of support on the conversion of methane to synthesis gas over supported iridium catalysts. Catal Lett 51(3–4):163–167
Juan-Juan J, Roman-Martinez MC, Illan-Gomez MJ (2004) Catalytic activity and characterization of Ni/Al2O3 and NiK/Al2O3 catalysts for CO2 methane reforming. Appl Catal A 264(2):169–174
Al-Fatesh ASA, Fakeeha AH, Abasaeed AE (2011) Effects of selected promoters on Ni/γ-Al2O3 catalyst performance in methane dry reforming. Chin J Catal 32(9–10):1604–1609
Rostrupnielsen JR, Hansen JHB (1993) CO2-reforming of methane over transition metals. J Catal 144(1):38–49
Cui Y, Zhang H, Xu H, Li W (2007) Kinetic study of the catalytic reforming of CH4 with CO2 to syngas over Ni/α-Al2O3 catalyst: the effect of temperature on the reforming mechanism. Appl Catal A 318:79–88
San-José-Alonso D, Juan-Juan J, Illán-Gómez MJ, Román-Martínez MC (2009) Ni, Co and bimetallic Ni–Co catalysts for the dry reforming of methane. Appl Catal A 371(1–2):54–59
Barroso-Quiroga MM, Castro-Luna AE (2010) Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane. Int J Hydrogen Energy 35(11):6052–6056
Fan M-S, Abdullah AZ, Bhatia S (2010) Utilization of greenhouse gases through carbon dioxide reforming of methane over Ni–Co/MgO–ZrO2: preparation, characterization and activity studies. Appl Catal B 100(1–2):365–377
Bouarab R, Akdim O, Auroux A, Cherifi O, Mirodatos C (2004) Effect of MgO additive on catalytic properties of Co/SiO2 in the dry reforming of methane. Appl Catal A 264(2):161–168
Shi C, Zhang P (2012) Effect of a second metal (Y, K, Ca, Mn or Cu) addition on the carbon dioxide reforming of methane over nanostructured palladium catalysts. Appl Catal B 115–116:190–200
Kim P, Kim Y, Kim H, Song IK, Yi J (2004) Synthesis and characterization of mesoporous alumina with nickel incorporated for use in the partial oxidation of methane into synthesis gas. Appl Catal A 272(1–2):157–166
Montoya JA, Romero-Pascual E, Gimon C, Del Angel P, Monzin A (2000) Methane reforming with CO2 over Ni/ZrO2–CeO2 catalysts prepared by sol–gel. Catal Today 63(1):71–85
Tang S, Ji L, Lin J, Zeng HC, Tan KL, Li K (2000) CO2 reforming of methane to synthesis gas over sol–gel-made Ni/γ-Al2O3 catalysts from organometallic precursors. J Catal 194(2):424–430
Zhang X, Lee CM, Mingos DM, Hayward D (2003) Carbon dioxide reforming of methane with Pt catalysts using microwave dielectric heating. Catal Lett 88(3–4):129–139
Wojcieszak R, Monteverdi S, Mercy M, Nowak I, Ziolek M, Bettahar MM (2004) Nickel containing MCM-41 and AlMCM-41 mesoporous molecular sieves: characteristics and activity in the hydrogenation of benzene. Appl Catal A 268(1–2):241–253
Savva PG, Goundani K, Vakros J, Bourikas K, Fountzoula C, Vattis D, Lycourghiotis A, Kordulis C (2008) Benzene hydrogenation over Ni/Al2O3 catalysts prepared by conventional and sol–gel techniques. Appl Catal B 79(3):199–207
Rahemi N, Haghighi M, Babaluo AA, Fallah Jafari M, Estifaee P (2013) CO2 reforming of CH4 over CeO2-doped Ni/Al2O3 nanocatalyst treated by non-thermal plasma. J Nanosci Nanotechnol 13(7):4896–4908
Goncalves G, Lenzi MK, Santos OAA, Jorge LMM (2006) Preparation and characterization of nickel based catalysts on silica, alumina and titania obtained by sol–gel method. J Non Cryst Solids 352(32–35):3697–3704
Gonzalez RD, Lopez T, Gomez R (1997) Sol–gel preparation of supported metal catalysts. Catal Today 35(3):293–317
Rogatis LD (2007) Design of nanostructured catalysts for H2 production and CO2 hydrogenation. University of Trieste, Trieste
Therdthianwong S, Therdthianwong A, Siangchin C, Yongprapat S (2008) Synthesis gas production from dry reforming of methane over Ni/Al2O3 stabilized by ZrO2. Int J Hydrogen Energy 33(3):991–999
Hao Z, Zhu Q, Jiang Z, Hou B, Li H (2009) Characterization of aerogel Ni/Al2O3 catalysts and investigation on their stability for CH4–CO2 reforming in a fluidized bed. Fuel Process Technol 90(1):113–121
Ji L, Tang S, Zeng HC, Lin J, Tan KL (2001) CO2 reforming of methane to synthesis gas over sol–gel-made Co/γ-Al2O3 catalysts from organometallic precursors. Appl Catal A 207(1–2):247–255
Li X, Ai J, Li W, Li D (2010) Ni–Co bimetallic catalyst for CH4 reforming with CO2. Front Chem Eng China 4(4):476–480
Takanabe K, Nagaoka K, Nariai K, Aika K-i (2005) Titania-supported cobalt and nickel bimetallic catalysts for carbon dioxide reforming of methane. J Catal 232(2):268–275
Zhang J, Wang H, Dalai AK (2007) Development of stable bimetallic catalysts for carbon dioxide reforming of methane. J Catal 249(2):300–310
Chen H-W, Wang C-Y, Yu C-H, Tseng L-T, Liao P-H (2004) Carbon dioxide reforming of methane reaction catalyzed by stable nickel copper catalysts. Catal Today 97(2–3):173–180
Halliche D, Bouarab R, Cherifi O, Bettahar MM (1996) Carbon dioxide reforming of methane on modified Ni/γ-Al2O3 catalysts. Catal Today 29(1–4):373–377
Lee J-H, Lee E-G, Joo O-S, Jung K-D (2004) Stabilization of Ni/Al2O3 catalyst by Cu addition for CO2 reforming of methane. Appl Catal A 269(1–2):1–6
Moradi GR, Khosravian F, Rahmanzadeh M (2012) Effects of partial substitution of Ni by Cu in LaNiO3 perovskite catalyst for dry methane reforming. Chin J Catal 33(4–6):797–801
Chen L, Zhu Q, Hao Z, Zhang T, Xie Z (2010) Development of a Co–Ni bimetallic aerogel catalyst for hydrogen production via methane oxidative CO2 reforming in a magnetic assisted fluidized bed. Int J Hydrogen Energy 35(16):8494–8502
Yue B, Wang X, Ai X, Yang J, Li L, Lu X, Ding W (2010) Catalytic reforming of model tar compounds from hot coke oven gas with low steam/carbon ratio over Ni/MgO–Al2O3 catalysts. Fuel Process Technol 91(9):1098–1104
Alberton AL, Souza MMVM, Schmal M (2007) Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts. Catal Today 123(1–4):257–264
Xu J, Zhou W, Li Z, Wang J, Ma J (2009) Biogas reforming for hydrogen production over nickel and cobalt bimetallic catalysts. Int J Hydrogen Energy 34(16):6646–6654
Regalbuto J (2007) Catalyst preparation: science and engineering. Taylor and Francis Group, LLC, Chicago
Bischoff BL, Anderson MA (1995) Peptization process in the sol–gel preparation of porous anatase (TiO2). Chem Mater 7(10):1772–1778
Hasin P (2007) Synthesis and characterization of NiAl2O4 spinel. Kasetsart University, Bangkok
Ding Y, Jin C, Meng Z (2000) The effects and mechanism of chemical additives on the pyrolysis evolution and microstructure of sol–gel derived Ba1−xSrxTiO3 thin films. Thin Solid Films 375(1–2):196–199
Cao C, Luo M, Zhu H (1999) PLZT films prepared by sol–gel process. J Non Cryst Solids 254(1–3):146–150
Yang W-D, Haile SM (2006) Influences of water content on synthesis of (Pb0.5Ba0.5)TiO3 materials using acetylacetone as chelating agent in a sol–gel process. J Eur Ceram Soc 26(15):3203–3210
Aronne A, Sannino F, Bonavolont SR, Fanelli E, Mingione A, Pernice P, Spaccini R, Pirozzi D (2012) Use of a new hybrid sol–gel zirconia matrix in the removal of the herbicide MCPA: a sorption/degradation process. Environ Sci Technol 46(3):1755–1763
van den Brom CR, Vogel N, Hauser CP, Goerres S, Wagner M, Landfester K, Weiss CK (2011) Interfacial activity of metal β-Diketonato complexes: in situ generation of amphiphiles by water coordination. Langmuir 27(13):8044–8053
Lemonnier S, Grandjean S, Robisson A-C, Jolivet J-P (2010) Synthesis of zirconia sol stabilized by trivalent cations (yttrium and neodymium or americium): a precursor for Am-bearing cubic stabilized zirconia. Dalton Trans 39(9):2254–2262
Kessler V, Spijksma G, Seisenbaeva G, Hykansson S, Blank DA, Bouwmeester HM (2006) New insight in the role of modifying ligands in the sol–gel processing of metal alkoxide precursors: a possibility to approach new classes of materials. J Sol Gel Sci Technol 40(2–3):163–179
Wang X, Pan X, Lin R, Kou S, Zou W, Ma J-X (2010) Steam reforming of dimethyl ether over Cu–Ni/γ-Al2O3 bi-functional catalyst prepared by deposition–precipitation method. Int J Hydrogen Energy 35(9):4060–4068
Kawabata T, Matsuoka H, Shishido T, Li D, Tian Y, Sano T, Takehira K (2006) Steam reforming of dimethyl ether over ZSM-5 coupled with Cu/ZnO/Al2O3 catalyst prepared by homogeneous precipitation. Appl Catal A 308:82–90
Ryczkowski J (2001) IR spectroscopy in catalysis. Catal Today 68(4):263–381
Debasis D, Panchanan P (2004) Particle size and comparison of soft-chemically prepared nickel and copper aluminate spinels. Paper presented at the international symposium of research students on materials science and engineering, Chennai, India
Djelloul A, Aida MS, Bougdira J (2010) Photoluminescence, FTIR and X-ray diffraction studies on undoped and Al-doped ZnO thin films grown on polycrystalline alumina substrates by ultrasonic spray pyrolysis. J Lumin 130(11):2113–2117
Seo JG, Youn MH, Jung JC, Cho KM, Park S, Song IK (2008) Preparation of Ni/Al2O3–ZrO2 catalysts and their application to hydrogen production by steam reforming of LNG: effect of ZrO2 content grafted on Al2O3. Catal Today 138(3–4):130–134
Abbasi Z, Haghighi M, Fatehifar E, Saedy S (2011) Synthesis and physicochemical characterizations of nanostructured Pt/Al2O3–CeO2 catalysts for total oxidation of VOCs. J Hazard Mater 186(2–3):1445–1454
Wang S, Gu F, Li C, Cao H (2007) Shape-controlled synthesis of CeOHCO3 and CeO2 microstructures. J Cryst Growth 307(2):386–394
Goula MA, Lemonidou AA, Efstathiou AM (1996) Characterization of carbonaceous species formed during reforming of CH4 with CO2 over Ni/CaO–Al2O3 catalysts studied by various transient techniques. J Catal 161(2):626–640
Brockner W, Ehrhardt C, Gjikaj M (2007) Thermal decomposition of nickel nitrate hexahydrate, Ni(NO3)2·6H2O, in comparison to Co(NO3)2·6H2O and Ca(NO3)2·4H2O. Thermochim Acta 456(1):64–68
Ehrhardt C, Gjikaj M, Brockner W (2005) Thermal decomposition of cobalt nitrato compounds: preparation of anhydrous cobalt (II) nitrate and its characterization by Infrared and Raman spectra. Thermochim Acta 432(1):36–40
Morozov IV, Znamenkov KO, Korenev YM, Shlyakhtin OA (2003) Thermal decomposition of Cu(NO3)2·3H2O at reduced pressures. Thermochim Acta 403(2):173–179
Sarkar D, Adak S, Mitra NK (2007) Preparation and characterization of an Al2O3–ZrO2 nanocomposite, Part I: powder synthesis and transformation behavior during fracture. Compos A Appl Sci Manuf 38(1):124–131
Haghighi M, Sun Z-q, Wu J-h, Bromly J, Wee HL, Ng E, Wang Y, Zhang D-k (2007) On the reaction mechanism of CO2 reforming of methane over a bed of coal char. Proc Combust Inst 31(2):1983–1990
Nikoo MK, Amin NAS (2011) Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation. Fuel Process Technol 92(3):678–691
Zanganeh R, Rezaei M, Zamaniyan A (2013) Dry reforming of methane to synthesis gas on NiO–MgO nanocrystalline solid solution catalysts. Int J Hydrogen Energy 38(7):3012–3018
Coq B, Tichit D, Ribet S (2000) Co/Ni/Mg/Al layered double hydroxides as precursors of catalysts for the hydrogenation of nitriles: hydrogenation of acetonitrile. J Catal 189(1):117–128
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The authors gratefully acknowledge Sahand University of Technology for the financial support of the research and Iran Nanotechnology Initiative Council for complementary financial supports.
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Sajjadi, S.M., Haghighi, M., Eslami, A.A. et al. Hydrogen production via CO2-reforming of methane over Cu and Co doped Ni/Al2O3 nanocatalyst: impregnation versus sol–gel method and effect of process conditions and promoter. J Sol-Gel Sci Technol 67, 601–617 (2013). https://doi.org/10.1007/s10971-013-3120-8
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DOI: https://doi.org/10.1007/s10971-013-3120-8