B, N‐co‐doped graphene‐supported Ir and Pt clusters for methane activation and C─C coupling: A density functional theory study

Methane conversion by using transition metal catalysts plays in an important role in various usages of the industrial process. The mechanism of methane conversion on B, N‐co‐doped graphene supported Ir and Pt clusters, BNG‐Ir4 and BNG‐Pt4, have been investigated using density functional theory calculations. Methane was found to adsorb on BNG‐Ir4 and BNG‐Pt4 clusters via strong agostic interactions. The first step of methane dehydrogenation on BNG‐Ir4 has a lower energy barrier, indicating a facile methane dissociation on BNG‐Ir4. In addition, it shows that hydrogen molecule can form on the BNG‐Ir4 and hydrogen can desorb from the surface. Besides, the C‐C coupling reaction of CH3 to form ethane is a more thermodynamically favorable process than CH3 dehydrogenation on BNG‐Ir4. Further, ethane is easier to desorb from the surface due to its low desorption energy. Therefore, the BNG‐Ir4 cluster is a potential catalyst for activating methane to form ethane and to produce hydrogen. © 2019 Wiley Periodicals, Inc.

[1]  T. Pham,et al.  Effect of External Electric Field on Methane Conversion on IrO2(110) Surface: A Density Functional Theory Study , 2019, ACS Catalysis.

[2]  Riguang Zhang,et al.  The dehydrogenation of CH4 on Rh(1 1 1), Rh(1 1 0) and Rh(1 0 0) surfaces: A density functional theory study , 2012 .

[3]  Hongjun Fan,et al.  Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen , 2014, Science.

[4]  Jennifer D. Schuttlefield,et al.  Renewable energy based catalytic CH4 conversion to fuels , 2014 .

[5]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[6]  Jing Zhao,et al.  Oxidative coupling of methane in solid oxide fuel cell tubular membrane reactor with high ethylene yield , 2017 .

[7]  M. Janik,et al.  Correlation of Methane Activation and Oxide Catalyst Reducibility and Its Implications for Oxidative Coupling , 2016 .

[8]  Baitao Li,et al.  Methane dissociation on Pt(1 1 1), Ir(1 1 1) and PtIr(1 1 1) surface: A density functional theory study , 2013 .

[9]  Riguang Zhang,et al.  The adsorption and dissociation of methane on cobalt surfaces: thermochemistry and reaction barriers , 2014 .

[10]  S. Kamarudin,et al.  Direct conversion technologies of methane to methanol: An overview , 2016 .

[11]  C. Lo,et al.  Platinum Nanoclusters Exhibit Enhanced Catalytic Activity for Methane Dehydrogenation , 2012, Topics in Catalysis.

[12]  R. Lobo,et al.  Catalytic conversion of methane to methanol on Cu-SSZ-13 using N2O as oxidant. , 2016, Chemical communications.

[13]  Riguang Zhang,et al.  Insight into the adsorption and dissociation of CH4 on Pt(h k l) surfaces: A theoretical study , 2012 .

[14]  T. Pham,et al.  Ethylene formation by methane dehydrogenation and C–C coupling reaction on a stoichiometric IrO2 (110) surface – a density functional theory investigation , 2015 .

[15]  Mayank Gupta,et al.  Heterogeneous Catalytic Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based Catalysts , 2011 .

[16]  Ali Taheri Najafabadi,et al.  Hydrogen production through partial oxidation of methane in a new reactor configuration , 2013 .

[17]  J. Limtrakul,et al.  Modification of the catalytic properties of the Au4 nanocluster for the conversion of methane-to-methanol: synergistic effects of metallic adatoms and a defective graphene support. , 2015, Physical chemistry chemical physics : PCCP.

[18]  E. Kondratenko,et al.  Methane conversion into different hydrocarbons or oxygenates: current status and future perspectives in catalyst development and reactor operation , 2017 .

[19]  Minkyu Kim,et al.  Low-temperature activation of methane on the IrO2(110) surface , 2017, Science.

[20]  Chia-Ching Wang,et al.  C–H Bond Activation of Methane via σ–d Interaction on the IrO2(110) Surface: Density Functional Theory Study , 2012 .

[21]  D. Dixon,et al.  Low-lying electronic states of Ir(n) clusters with n = 2-8 predicted at the DFT, CASSCF, and CCSD(T) levels. , 2013, The journal of physical chemistry. A.

[22]  Yuriy Román‐Leshkov,et al.  Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature , 2016, ACS central science.

[23]  S. Linic,et al.  A Viewpoint on Direct Methane Conversion to Ethane and Ethylene Using Oxidative Coupling on Solid Catalysts , 2016 .

[24]  E. Iglesia,et al.  Structural and mechanistic requirements for methane activation and chemical conversion on supported iridium clusters. , 2004, Angewandte Chemie.

[25]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[26]  J. V. van Bokhoven,et al.  Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond. , 2017, Accounts of chemical research.

[27]  M. Scheffler,et al.  A Critical Assessment of Li/MgO-Based Catalysts for the Oxidative Coupling of Methane , 2011 .

[28]  K. Qiao,et al.  A review of the direct oxidation of methane to methanol , 2016 .

[29]  Joong-Kee Lee,et al.  Conversion of natural gas to hydrogen and carbon black by plasma and application of plasma carbon black , 2004 .

[30]  Lichang Wang,et al.  Methane activation on Pt and Pt4: a density functional theory study. , 2007, The journal of physical chemistry. B.

[31]  E. Steen,et al.  Further Investigation into the Formation of Alcohol during Fischer Tropsch Synthesis on Fe-based Catalysts , 2012 .

[32]  Lijuan Song,et al.  The properties of Irn (n = 2-10) clusters and their nucleation on γ-Al₂O₃ and MgO surfaces: from ab initio studies. , 2015, Physical chemistry chemical physics : PCCP.

[33]  Surendra Kumar,et al.  Hydrogen production by partial oxidation of methane: Modeling and simulation , 2009 .

[34]  I. Hermans,et al.  Oxidative methane upgrading. , 2012, ChemSusChem.

[35]  J. Nørskov,et al.  Monocopper Active Site for Partial Methane Oxidation in Cu-Exchanged 8MR Zeolites , 2016 .

[36]  L. Ricardez‐Sandoval,et al.  Methane dissociation on Ni (1 0 0), Ni (1 1 1), and Ni (5 5 3): A comparative density functional theory study , 2012 .

[37]  Jinlan Wang,et al.  Greatly Improved Methane Dehydrogenation via Ni Adsorbed Cu(100) Surface , 2013 .

[38]  Zhe Lu,et al.  The effect of potassium on steam-methane reforming on the Ni4/Al2O3 surface: a DFT study , 2017 .

[39]  S. Järås,et al.  Catalytic partial oxidation of methane over nickel and ruthenium based catalysts under low O2/CH4 ratios and with addition of steam , 2015 .

[40]  Mohammad Taghi Hamed Mosavian,et al.  A comparative theoretical study of methane adsorption on the nitrogen, boron and lithium doped graphene sheets including density functional dispersion correction , 2016 .

[41]  Z. Zuo,et al.  A density functional theory study of CH4 dehydrogenation on Co(1 1 1) , 2010 .

[42]  E. Wolf.  Methane to Light Hydrocarbons via Oxidative Methane Coupling: Lessons from the Past to Search for a Selective Heterogeneous Catalyst. , 2014, The journal of physical chemistry letters.

[43]  M. Ferreira,et al.  Sublattice asymmetry of impurity doping in graphene: A review , 2014, Beilstein journal of nanotechnology.

[44]  P. Srivastava,et al.  Electronic and transport properties of boron and nitrogen doped graphene nanoribbons: an ab initio approach , 2014, Applied Nanoscience.

[45]  Remo Guidieri.  Res , 1995, RES: Anthropology and Aesthetics.

[46]  Wesley S. Farrell,et al.  Catalytic Production of Isothiocyanates via a Mo(II)/Mo(IV) Cycle for the “Soft” Sulfur Oxidation of Isonitriles , 2016 .

[47]  L. Ricardez‐Sandoval,et al.  Effect of Metal–Support Interface During CH4 and H2 Dissociation on Ni/γ-Al2O3: A Density Functional Theory Study , 2013 .

[48]  T. P. Kaloni,et al.  Electronic properties of boron- and nitrogen-doped graphene: a first principles study , 2012, Journal of Nanoparticle Research.

[49]  Ponien Lai,et al.  A First Principles study on Boron-doped Graphene decorated by Ni-Ti-Mg atoms for Enhanced Hydrogen Storage Performance , 2015, Scientific Reports.

[50]  Weixin Huang,et al.  Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy , 2013, Scientific Reports.

[51]  Xiyuan Sun,et al.  A theoretical study on small iridium clusters: structural evolution, electronic and magnetic properties, and reactivity predictors. , 2010, The journal of physical chemistry. A.

[52]  M. J. Silva.  Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM) , 2016 .

[53]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[54]  J. Lunsford,et al.  Oxidative dimerization of methane over a lithium-promoted magnesium oxide catalyst , 1985 .

[55]  Minhua Zhang,et al.  DFT research of methane preliminary dissociation on aluminum catalyst , 2013 .

[56]  M. Pumera,et al.  Chemical nature of boron and nitrogen dopant atoms in graphene strongly influences its electronic properties. , 2014, Physical chemistry chemical physics : PCCP.

[57]  K. Yoshizawa,et al.  Adsorption and Activation of Methane on the (110) Surface of Rutile-type Metal Dioxides , 2018, The Journal of Physical Chemistry C.

[58]  R. A. Santen,et al.  Methane Dissociation on High and Low Indices Rh Surfaces , 2011 .

[59]  S. Baykara,et al.  Hydrogen production by partial oxidation of methane over Co based, Ni and Ru monolithic catalysts , 2015 .

[60]  Chien-Hao Lin,et al.  Density-functional calculations of the conversion of methane to methanol on platinum-decorated sheets of graphene oxide. , 2015, Physical chemistry chemical physics : PCCP.

[61]  Wei Zhou,et al.  High-capacity methane storage in metal-organic frameworks M2(dhtp): the important role of open metal sites. , 2009, Journal of the American Chemical Society.

[62]  Yasuhiro Hirata,et al.  Studies of iridium nanoparticles using density functional theory calculations. , 2005, The journal of physical chemistry. B.

[63]  H. Chacham,et al.  Band Gaps of BN-Doped Graphene: Fluctuations, Trends, and Bounds , 2015 .

[64]  K. Jun,et al.  Partial oxidation of methane over nickel catalysts supported on various aluminas , 2002 .

[65]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[66]  Graham J. Hutchings,et al.  Oxidative coupling of methane using oxide catalysts , 1989 .

[67]  Ponien Lai,et al.  Efficient hydrogen storage in boron doped graphene decorated by transition metals – A first-principles study , 2014 .

[68]  Ding Ma,et al.  Methane activation: the past and future , 2014 .

[69]  G. Henkelman,et al.  A climbing image nudged elastic band method for finding saddle points and minimum energy paths , 2000 .

[70]  Jack H. Lunsford.  The Catalytic Oxidative Coupling of Methane , 1995 .