Mechanism of Low Pressure Plasma-Assisted CO2 Hydrogenation Over Ni-USY by Microsecond Time-resolved FTIR Spectroscopy

Zeolite H-USY doped with nickel (14% wt.) was used as a catalyst in the plasma-assisted CO2 hydrogenation under partial vacuum. CO was found to be the main product of the reaction and it is generated by plasma-assisted CO2 dissociation in the gas phase. The CO2 molecules vibrationally excited by plasma are also adsorbed on metallic nickel as formates which are further transformed into linear carbonyls. These species are then hydrogenated to form methane. Since the catalyst presents a low basic behavior, methane is produced from hydrogenation of linear carbonyls on nickel surface rather than from carbonates species. A detailed mechanism for this reaction assisted by plasma (glow discharge) is proposed using Operando time-resolved FTIR spectroscopic data.

[1]  L. Magistri,et al.  A study of the methanation of carbon dioxide on Ni/Al2O3 catalysts at atmospheric pressure , 2014 .

[2]  Xin Wang,et al.  Catalysis mechanisms of CO2 and CO methanation , 2016 .

[3]  A. Bogaerts,et al.  Influence of the Material Dielectric Constant on Plasma Generation inside Catalyst Pores , 2016 .

[4]  Masato R. Nakamura,et al.  Mechanisms of methanation of carbon dioxide and carbon monoxide over nickel/alumina catalysts , 1993 .

[5]  Hong Lei,et al.  Hydrogenation of CO2 to CH3OH over Cu/ZnO catalysts with different ZnO morphology , 2015 .

[6]  R. Hayes,et al.  Surface intermediates in the nickel catalysed methanation of carbon monoxide as revealed by computer enhanced multiple reflectance infrared spectroscopy , 1983 .

[7]  M. Götz,et al.  Review on methanation – From fundamentals to current projects , 2016 .

[8]  R. Snyders,et al.  Plasma assisted catalytic decomposition of CO2 , 2016 .

[9]  A. Bogaerts,et al.  Can plasma be formed in catalyst pores? A modeling investigation , 2016 .

[10]  V. Valtchev,et al.  Ultra-fast framework stabilization of Ge-rich zeolites by low-temperature plasma treatment , 2014 .

[11]  Chang-jun Liu,et al.  Improved activity of Ni/MgAl2O4 for CO2 methanation by the plasma decomposition , 2015 .

[12]  Yanqiang Huang,et al.  CO2 methanation over TiO2-Al2O3 binary oxides supported Ru catalysts , 2016 .

[13]  D. King,et al.  Adsorption and decomposition of formic acid on Ni{110} , 1995 .

[14]  G. Hutchings,et al.  Pd/ZnO catalysts for direct CO2 hydrogenation to methanol , 2016 .

[15]  T. Nozaki,et al.  Pulsed dry methane reforming in plasma-enhanced catalytic reaction , 2015 .

[16]  A. Fridman.  Plasma Chemistry: Frontmatter , 2008 .

[17]  R. Behm,et al.  Methanol formation by CO2 hydrogenation on Au/ZnO catalysts – Effect of total pressure and influence of CO on the reaction characteristics , 2016 .

[18]  K. Ostrikov,et al.  Plasma Catalysis: Synergistic Effects at the Nanoscale. , 2015, Chemical reviews.

[19]  Jumras Limtrakul,et al.  Theoretical study of modes of adsorption of water dimer on H-ZSM-5 and H-Faujasite zeolites. , 2005, The journal of physical chemistry. B.

[20]  Hyuck-Mo Lee,et al.  Bifunctional Mechanism of CO2 Methanation on Pd-MgO/SiO2 Catalyst: Independent Roles of MgO and Pd on CO2 Methanation , 2010 .

[21]  B. Davis,et al.  Fischer-Tropsch synthesis over iron-based catalysts in a slurry reactor. Reaction rates, selectivities and implications for improving hydrocarbon productivity , 1997 .

[22]  C. Henriques,et al.  Insight into CO2 methanation mechanism over NiUSY zeolites: An operando IR study , 2015 .

[23]  F. Thibault-Starzyk,et al.  Microsecond time-resolved Fourier transform infrared analytics in a low pressure glow discharge reactor. , 2010, The Review of scientific instruments.

[24]  T. Nozaki,et al.  Non-thermal plasma catalysis of methane: Principles, energy efficiency, and applications , 2013 .

[25]  Chengfa Jiang,et al.  Mesoporous nickel catalyst supported on multi-walled carbon nanotubes for carbon dioxide methanation ☆ , 2016 .

[26]  Xiang Wang,et al.  Kinetic modeling and transient DRIFTS–MS studies of CO 2 methanation over Ru/Al 2 O 3 catalysts , 2016 .

[27]  C. Berrueco,et al.  High-loaded nickel–alumina catalyst for direct CO2 hydrogenation into synthetic natural gas (SNG) , 2013 .

[28]  Anne-Cécile Roger,et al.  Catalytic CO2 valorization into CH4 on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy , 2013 .

[29]  P. Christopher,et al.  Mechanism of CO2 reduction by H2 on Ru(0 0 0 1) and general selectivity descriptors for late-transition metal catalysts , 2016 .

[30]  Annemie Bogaerts,et al.  Understanding plasma catalysis through modelling and simulation—a review , 2014 .

[31]  Robert J. Farrauto,et al.  Kinetics of CO2 methanation over Ru/γ-Al2O3 and implications for renewable energy storage applications , 2015 .

[32]  Antoine Beuls,et al.  Methanation of CO2: Further insight into the mechanism over Rh/gamma-Al2O3 catalyst , 2012 .

[33]  Zhong Li,et al.  Insights into the mechanisms of CO2 methanation on Ni(111) surfaces by density functional theory , 2015 .

[34]  L. Pierella,et al.  Synthesis and characterization of MEL and FAU zeolites doped with transition metals for their application to the fine chemistry under microwave irradiation , 2013 .

[35]  Shudong Wang,et al.  Insight into the reaction route of CO2 methanation: Promotion effect of medium basic sites , 2014 .

[36]  M. Dry,et al.  Fischer–Tropsch reactions and the environment , 1999 .

[37]  Chunfei Wu,et al.  Plasma-photocatalytic conversion of CO2 at low temperatures: Understanding the synergistic effect of plasma-catalysis , 2016 .

[38]  G. Weatherbee.  Hydrogenation of CO2 on group VIII metals: II. Kinetics and mechanism of CO2 hydrogenation on nickel , 1982 .

[39]  Ping Liu,et al.  CO2 hydrogenation on Pt, Pt/SiO2 and Pt/TiO2: Importance of synergy between Pt and oxide support , 2016 .

[40]  Wei Chu,et al.  Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. , 2007, Chemical reviews.

[41]  J. Whitehead,et al.  Plasma–catalysis: the known knowns, the known unknowns and the unknown unknowns , 2016 .

[42]  R. Kikuchi,et al.  Mechanistic study and catalyst development for selective carbon monoxide methanation , 2015 .

[43]  M. Dry,et al.  The Fischer–Tropsch process: 1950–2000 , 2002 .

[44]  S. Pratsinis,et al.  Effect of Ba and K addition and controlled spatial deposition of Rh in Rh/Al2O3 catalysts for CO2 hydrogenation , 2014 .

[45]  L. Thompson,et al.  Low temperature CO2 hydrogenation to alcohols and hydrocarbons over Mo2C supported metal catalysts , 2016 .

[46]  E. Neyts.  Plasma-Surface Interactions in Plasma Catalysis , 2015, Plasma Chemistry and Plasma Processing.