Multiwall carbon nanotube-supported molybdenum catalysts for ammonia decomposition reaction under microwave effect

In this study, microwave-assisted ammonia decomposition reaction was investigated over molybdenum incorporated catalysts. Due to the selective, volumetric, and noncontact heating properties of the microwave system, higher conversion values could be achieved at relatively lower reaction temperatures, which is important for on-site COx-free hydrogen production. Multiwall carbon nanotube-supported molybdenum catalysts were prepared following the impregnation procedure with different metal loading 3.5%-12.5% wt% , and inductively coupled plasma, nitrogen physisorption, X-ray diffraction, and transmission electron microscopic techniques were employed to characterize the fresh and used samples. Reaction experiments were performed under the flow of pure ammonia with a gas hourly space velocity of 36,000 mL/gcat.h for both the microwave and conventionally heated reaction systems. It was found that ammonia conversion was obtained even at 400 °C, reaching 40%, and total conversion was observed even at 450 °C, while the activities of these catalysts were negligible at a reaction temperature lower than 550 °C, in the conventional heatedsystem, whichincludedanelectricallyheatedfurnace. Crystalsof α-Mo2CaswellasMoO2 wereobservedinthe structures of the synthesized catalysts and the formation of nitride species was more easily observable under microwave heating, possibly due to the nitridation of molybdenum carbide species during the reaction.

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  • 1. Choudhary TV, Sivadinarayana C, Goodman DW. Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications. Catalysis Letters 2001; 72: 197-201.
  • 2. Schu¨th F, Palkovits R, Schlo¨gl R, Su DS. Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition. Energy and Environmental Science 2012; 5: 6278-6289.
  • 3. Ma Y, Guan G, Hao X, Cao J, Abudula A. Molybdenum carbide as alternative catalyst for hydrogen productionA review. Renewable and Sustainable Energy Reviews 2017; 75: 1101-1129.
  • 4. Li XK, Ji WJ, Zhao J, Wang SJ, Au CT. Ammonia decomposition over Ru and Ni catalysts supported on fumed SiO2 , MCM-41, and SBA-15. Journal of Catalysis 2005; 236: 181-189.
  • 5. Li L, Zhu ZH, Yan ZF, Lu GQ, Rintoul L. Catalytic ammonia decomposition over Ru/carbon catalysts: the importance of the structure of carbon support. Applied Catalysis A: General 2007; 320: 166-172.
  • 6. Varisli D, Elverisli EE. Synthesizing hydrogen from ammonia over Ru incorporated SiO2 type nanocomposite catalysts. International Journal of Hydrogen Energy 2014; 39: 10399-10408.
  • 7. Zhang J, Comotti M, Schu¨th F, Schlo¨gl R, Su DS. Commercial Fe- of Co-containing carbon nanotubes as catalysts for NH3 decomposition. Chemical Communications 2007; 1916-1918.
  • 8. Lorenzut B, Montini T, Bevilacqua M, Fornasiero P. FeMo-based catalysts for H2 production by NH3 decomposition. Applied Catalysis B: Environmental 2012; 125: 409-417.
  • 9. Duan X, Ji J, Qian G, Zhou X, Chen D. Recent advances in synthesis of reshaped Fe and Ni particles at the tips of carbon nanofibers and their catalytic applications. Catalysis Today 2015; 249-251.
  • 10. Varisli D, Kaykac NG. COx free hydrogen production over cobalt incorporated silicate structured mesoporous catalysts. Applied Catalysis B: Environmental 2012; 127: 389-398.
  • 11. Varisli D, Kaykac NG. Hydrogen from ammonia over cobalt incorporate silicate structured catalyts prepared using different cobalt salts. International Journal of Hydrogen Energy 2016; 41: 5955-5968.
  • 12. Bell TE, Torrente-Murciano L. H2 Production via Ammonia Decomposition Using Non-Noble Metal Catalysts: A Review. Topic in Catalysis 2016; 59: 1438-1457.
  • 13. Domiìnguez A, Fidalgo B, Fernaìndez Y, Pis JJ, Meneìndez JA. Microwave-assisted catalytic decomposition of methane over activated carbon for CO2 -free hydrogen production. International Journal of Hydrogen Energy 2007; 32: 4792-4799.
  • 14. Bermuìdez JM, Beneroso D, Rey-Raap N, Arenillas A, Meneìndez JA. Energy consumption estimation in the scaling-up of microwave heating processes. Chemical Engineering and Processing 2015; 95: 1-8.
  • 15. Meneìndez JA, Arenillas A, Fidalgo B, Fernaìndez Y, Zubizarreta L et al. Microwave heating processes involving carbon materials. Fuel Processing Technology 2010; 91: 1-8.
  • 16. Bonnet C, Estel L, Ledoux A, Mazari B, Louis A. Study of the thermal repartition in a microwave reactor: application to the nitrobenzene hydrogenation. Chemical Engineering and Processing 2004; 43: 1435-1440.
  • 17. Fidalgo B, Fernandez Y, Zubizarreta L, Arenillas A, Domınguez A et al. Growth of nanofilaments on carbon-based materials from microwave-assisted decomposition of CH4 . Applied Surface Science 2008; 254: 3553-3557.
  • 18. Gunduz S, Dogu T. Hydrogen by steam reforming of ethanol over Co–Mg incorporated novel mesoporous alumina catalysts in tubular and microwave reactors. Applied Catalysis B: Environmental 2015; 168-169: 497-508.
  • 19. Chen WH, Lin BJ. 2010. Effect of microwave double absorption on hydrogen generation from methanol steam reforming. International Journal of Hydrogen Energy 2010; 35: 1987-1997.
  • 20. Fidalgo B, Dominguez A, Pis JJ, Menendez JA. Microwave-assisted dry reforming of methane. International Journal of Hydrogen Energy 2008; 33: 4337-4344.
  • 21. Zhaohui Z, Hanbo Z, Weiming L. Effect of rare earth and other cationic promoters on properties of CoMoNx/CNTs catalysts for ammonia decomposition. Journal of Rare Earths 2013; 31:247-250.
  • 22. Duan X, Qian G, Zhou X, Sui Z, Chen D et al. Tuning the size and shape of Fe nanoparticles on carbon nanofibers for catalytic ammonia decomposition. Applied Catalysis B: Environmental 2011; 101: 189-196.
  • 23. Lu AH, Nitz JJ, Comotti M, Weidenthaler C, Schlichte K et al. Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition. Journal of the American Chemical Society 2010; 132: 14152-14162.
  • 24. Li L, Chu W, Ding C, Xi X, Jiang R et al. Embedded MoN@C nanocomposites as an advanced catalyst for ammonia decomposition to COx-free hydrogen. International Journal of Hydrogen Energy 2017; 42: 30630-30638.
  • 25. Varisli D, Korkusuz C, Dogu T. Microwave-assisted ammonia decomposition reaction over iron incorporated mesoporous carbon catalysts. Applied Catalysis B: Environmental 2017; 201: 370-380.
  • 26. Guler M, Dogu T, Varisli D. 2017. Hydrogen Production over molybdenum loaded mesoporous carbon catalysts in MWRS. Applied Catalysis B: Environmental 2017; 219: 173-182.
  • 27. Torrente-Murciano L, Hill AK, Bell TE. Ammonia decomposition over cobalt/carbon catalyst-effect of carbon support and electronic donating promoter on activity. Catalysis Today 2017; 286: 131-140.
  • 28. Liao SY, Ko AN. Potassium-promoted Mo/MWCNTs catalysts for effective partial oxidation of 1-dodecanol to 1-dodecanal. Applied Catalysis A: General 2015; 496: 79-85.
  • 29. Li L, Zhu ZH, Yan ZF, Lu GQ, Rintoul L. Catalytic ammonia decomposition over Ru/carbon catalysts: The importance of the structure of carbon support. Applied Catalysis A: General 2007; 320: 166-172.
  • 30. Lee JS, Oyama ST, Boudart M. Molybdenum carbide catalysts: I. Synthesis of unsupported powders. Journal of Catalysis 1987; 106: 125-133.
  • 31. Yang Z, Cai P, Shi L, Gu Y, Chen L et al. A facile preparation of nanocrystalline Mo 2 C from graphite or carbon nanotubes. Journal of Solid State Chemistry 2006; 179: 29-32.
  • 32. Zhu Q, Chen Q, Yang X, Ke D. A new method for the synthesis of molybdenum carbide. Materials Letters 2007; 61: 5173-5174.
  • 33. Mai EF, Machado MA, Davies TE, Lopez-Sanchez JA, Teixeira da Silva V. Molybdenum carbide nanoparticles within carbon nanotubes as superior catalysts for γ -valerolactone production via levulinic acid hydrogenation. Green Chemistry 2014; 16: 4092-4097.
  • 34. Vitale G, Guzman H, Frauwallner ML, Scott CE, Pereira-Almao P. Synthesis of nanocrystalline molybdenum carbide materials and their characterization. Catalysis Today 2015; 250: 123-133.
  • 35. Theerthagiri J, Senthil RA, Buraidah MH, Madhavan J, Arof AK. Synthesis of α-Mo 2 C by carburization of α– MoO3 Nanowires and its electrocatalytic activity towards tri-iodide reduction for dye-sensitized solar cells. Journal of Material Science and Technology 2016; 32: 1339-1344.
  • 36. Xia K, Guo J, Xuan C, Huang T, Deng Z et al. Ultrafine molybdenum carbide nanoparticles supported on nitrogen doped carbon nanosheets for hydrogen evolution reaction. Chinese Chemical Letters 2019; 30: 192-196.
  • 37. Bokhonov B, Borisova Y, Korchagin M. Formation of encapsulated molybdenum carbide particles by annealing mechanically activated mixtures of amorphous carbon with molybdenum. Carbon 2004; 42: 2067-2071.
  • 38. Durka T, Stefanidis GD, Gerven TV, Stankiewicz AI. Microwave-activated methanol steam reforming for hydrogen production. International Journal of Hydrogen Energy 2011; 36: 12843-12852.
  • 39. Krech T, Krippendorf R, Jäger B, Präger M, Scholz P et al. Microwave radiation as a tool for process intensification in exhaust gas treatment. Chemical Engineering and Processing 2013; 71: 31-36.
  • 40. Fidalgo B, Fernandez Y, Domınguez A, Pis JJ, Menendez JA. Microwave-assisted pyrolysis of CH4 /N2 mixtures over activated carbon. Journal of Analytical and Applied Pyrolysis 2008; 82: 158-162.
  • 41. Hunt J, Ferrari A, Lita A, Crosswhite M, Ashley B et al. Microwave-specific enhancement of the carbon-carbon dioxide (Boudouard) reaction. Journal of Physical Chemistry C 2013; 117: 26871-26880.
  • 42. A. Ferrari, J. Hunt, A. Lita, B. Ashley, A.E. Stiegman, Microwave-specific effectson the equilibrium constants an thermodynamic of the steam-carbon and related reactions, J. Phys. Chem. C 118 (2014) 9346-9356.
  • 43. Vallance SR, Kingman S, Gregory DH. Ultra-rapid processing of refractory carbides; 20s synthesis of molybdenum carbide. Chemical Communications 2012; 742-744.
  • 44. Yacob AR, Mustajab MKAA, Suhaimi NH. The effect of carbon on molybdenum in the preparation of microwave induced molybdenum carbide. International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering. 2012; 6: 1036-1039.
  • 45. Liang C, Li W, Wei Z, Xin Q, Li C. Catalytic decomposition of ammonia over nitrided MoNx/-Al 2 O3 and NiMoNy/-Al 2 O3 catalysts. Industrial & Engineering Chemistry Research 2000; 39: 3694-3697.
  • 46. Tagliazucca V, Schlichte K, Schuth F, Weidenthaler C. Molybdenum-based catalysts for the decomposition of ammonia: in situ X-ray diffraction studies, microstructure, and catalytic properties. Journal of Catalysis 2013; 305: 277-289.
  • 47. Jauberteau I, Bessaudou A, Mayet R, Cornette J, Jauberteau JL et al. Molybdenum nitride films: crystal structures, synthesis, mechanical, electrical and some other properties .Coatings 2015; 5: 656-687.
  • 48. Maoujoud M, Jardinier-Offergeld M, Bouillon F. Synthesis and characterization of thin-film molybdenum nitrides. Applied Surface Science 1993; 64: 81-89.
  • 49. Zheng W, Cotter TP, Kaghazchi P, Jacob T, Frank B et al. Experimental and theoretical investigation of molybdenum carbide and nitride as catalysts for ammonia decomposition. Journal of American Chemical Society 2013; 135: 3458-3464.
  • 50. Podila S, Zaman SF, Driss H, Alhamed YA, Al-Zahrani AA et al. Hydrogen production by ammonia decomposition using high surface area Mo 2 N and Co 3 Mo 3 N catalysts. Catalysis Science & Technology 2016; 6: 1496-1506.
  • 51. Ji J, Duan X, Qian G, Zhou X, Tong G et al. Towards an efficient CoMo/Al 2 O3 catalyst using metal amine metallate as an active phase precursor: enhanced hydrogen production by ammonia decomposition. International Journal of Hydrogen Energy 2014; 39: 12490-12498.
  • 52. Zhang H, Alhamed YA, Chu W, Ye Z, Alzahrani A et al. Controlling Co-support interaction in Co/MWCNTs catalysts and catalytic performance for hydrogen production via NH3 decomposition. Applied Catalysis A: General 2013; 464-465: 156-164.
  • 53. Huang C, Yu Y, Yang J, Yan Y, Wang D et al. Ru/La 2 O3 catalyst for ammonia decomposition to hydrogen. Applied Surface Science 2019; 476: 928-936.
  • 54. Wang L, Chen J, Ge L, Zhu Z, Rudolph V. Hallosite-nanotube-supported Ru nanoparticles for ammonia catalytic decomposition to produce COx-free hydrogen. Energy Fuel 2011; 25:3408-3416.
  • 55. Varisli D, Elverisli EE. Synthesizing hydrogen from ammonia over Ru incorporated SiO2 type nanocomposite catalysts. International Journal of Hydrogen Energy 2014; 39: 10399-10408.
  • 56. Guler M, Korkusuz C, Varisli D. Catalytic decomposition of ammonia for hydrogen production over carbon nanofiber supported Fe and Mo catalysts in a microwave heated reactor. International Journal of Chemical Reactor Engineering 2019; 17 (6). doi: 10.1515/ijcre-2018-0162