Mechanisms of Hydrogen-Assisted CO2 Reduction on Nickel.

Mechanistic details of catalytic reactions are critical to the development of improved catalysts. Here, we perform high quality Born-Oppenheimer molecular dynamics simulations of the reaction mechanisms associated with hydrogen-assisted CO2 reduction on Ni(110). The simulation results show direct theoretical evidence for both associative and redox mechanisms in the reaction of atomic hydrogen with CO2. Because H2 is dissociatively chemisorbed on Ni(110) with nearly unit probability, the mechanisms we find are also relevant to the reverse water-gas shift reaction (H2 with adsorbed CO2). Furthermore, we provide the first real-time demonstration of both Eley-Rideal (ER) and hot atom (HA) mechanisms when H impinges on adsorbed CO2, and we show that both occur even for low kinetic energies. The trade-off between ER or HA mechanisms is found to be strongly dependent on CO2 coverage. The results are compared with recent gas/surface measurements.

[1]  Hua Guo,et al.  Ab Initio Molecular Dynamics Study of Dissociative Chemisorption and Scattering of CO2 on Ni(100): Reactivity, Energy Transfer, Steering Dynamics, and Lattice Effects , 2017 .

[2]  G. Schatz,et al.  Reducing CO2 to CO and H2O on Ni(110): The Influence of Subsurface Hydrogen , 2016 .

[3]  M. Salmeron,et al.  Recycling of CO2: Probing the Chemical State of the Ni(111) Surface during the Methanation Reaction with Ambient-Pressure X-Ray Photoelectron Spectroscopy. , 2016, Journal of the American Chemical Society.

[4]  Christopher W. Jones,et al.  Direct Capture of CO2 from Ambient Air. , 2016, Chemical reviews.

[5]  Adam H Mepham,et al.  Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration , 2016, Nature.

[6]  R. Schlögl,et al.  Reverse Water-Gas Shift or Sabatier Methanation on Ni(110)? Stable Surface Species at Near-Ambient Pressure. , 2016, Journal of the American Chemical Society.

[7]  Maor F. Baruch,et al.  Light-Driven Heterogeneous Reduction of Carbon Dioxide: Photocatalysts and Photoelectrodes. , 2015, Chemical reviews.

[8]  R. Schlögl,et al.  Reactivity of Carbon Dioxide on Nickel: Role of CO in the Competing Interplay between Oxygen and Graphene. , 2014, The journal of physical chemistry letters.

[9]  Ib Chorkendorff,et al.  Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol. , 2014, Nature chemistry.

[10]  Anker Degn Jensen,et al.  CO hydrogenation to methanol on Cu–Ni catalysts: Theory and experiment , 2012 .

[11]  S. Sibener,et al.  CO2 hydrogenation to formic acid on Ni(110) , 2012 .

[12]  S. Sibener,et al.  CO2 Hydrogenation to Formic Acid on Ni(111) , 2012 .

[13]  N. Kruse,et al.  Catalytic CO2 Hydrogenation on Nickel: Novel Insight by Chemical Transient Kinetics† , 2011 .

[14]  A. Baldereschi,et al.  Imaging and characterization of activated CO2 species on Ni(110) , 2010 .

[15]  A. Baldereschi,et al.  Hydrogen-Assisted Transformation of CO2 on Nickel: The Role of Formate and Carbon Monoxide , 2010 .

[16]  M. Mavrikakis,et al.  Structure sensitivity of methanol electrooxidation on transition metals. , 2009, Journal of the American Chemical Society.

[17]  A. Baldereschi,et al.  Carbon dioxide hydrogenation on Ni(110). , 2008, Journal of the American Chemical Society.

[18]  B. Jackson,et al.  Quasiclassical study of Eley-Rideal and hot atom reactions of H atoms with Cl adsorbed on a Au(111) surface. , 2005, The Journal of chemical physics.

[19]  J. Nørskov,et al.  DFT Study of Formaldehyde and Methanol Synthesis from CO and H2 on Ni(111) , 2004 .

[20]  M. Persson,et al.  ELEY-RIDEAL AND HOT-ATOM REACTIONS OF H(D) ATOMS WITH D(H)-COVERED CU(111)SURFACES; QUASICLASSICAL STUDIES , 1999 .

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

[22]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[23]  C. Rettner,et al.  Distinguishing the Direct and Indirect Products of a Gas-Surface Reaction , 1994, Science.

[24]  G. Ertl,et al.  Dynamics of interaction of H2 and D2 with Ni(110) and Ni(110) surfaces , 1985 .

[25]  M. W. Roberts,et al.  Surface chemistry of carbon dioxide , 1996 .