Towards more accurate prediction of activation energies for polyalcohol dehydrogenation on transition metal catalysts in water

To sustain the development of novel metal-supported catalysts for transformation of polyalcohol molecules in silico, the development of efficient and accurate linear relationships to predict activation energies represents a major milestone. We establish here Bronsted–Evans–Polanyi relationships for CH and OH cleavages in monoalcohol molecules H-bonded with a chemisorbed water molecule over a series of transition metal surfaces. Then, we demonstrate that these relations can be used to predict glycerol and 1,2-propanediol dehydrogenation over Rh with remarkable accuracy and almost no systematic deviation. Lastly, we discuss the conditions to use these relations safely for screening dense catalytic reaction networks on different metallic surfaces.

[1]  A. Bell,et al.  Efficient methods for finding transition states in chemical reactions: comparison of improved dimer method and partitioned rational function optimization method. , 2005, The Journal of chemical physics.

[2]  A. Alavi,et al.  Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces. , 2003, Journal of the American Chemical Society.

[3]  Jonathan E. Sutton,et al.  Brønsted–Evans–Polanyi and Transition State Scaling Relations of Furan Derivatives on Pd(111) and Their Relation to Those of Small Molecules , 2014 .

[4]  G. Henkelman,et al.  Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points , 2000 .

[5]  J. Nørskov,et al.  Universal transition state scaling relations for (de)hydrogenation over transition metals. , 2011, Physical chemistry chemical physics : PCCP.

[6]  Sebastian Kozuch,et al.  The rate-determining step is dead. Long live the rate-determining state! , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[7]  Jonathan E. Sutton,et al.  A Theoretical and Computational Analysis of Linear Free Energy Relations for the Estimation of Activation Energies , 2012 .

[8]  R. Palkovits,et al.  Hydrogenolysis goes bio: from carbohydrates and sugar alcohols to platform chemicals. , 2012, Angewandte Chemie.

[9]  Zhipan Liu,et al.  General trends in the barriers of catalytic reactions on transition metal surfaces , 2001 .

[10]  M. Stamatakis,et al.  A review of multiscale modeling of metal-catalyzed reactions: Mechanism development for complexity and emergent behavior , 2011 .

[11]  J. Nørskov,et al.  Effect of Boron Modifications of Palladium Catalysts for the Production of Hydrogen from Formic Acid , 2015 .

[12]  Philippe Sautet,et al.  Trade-Off between Accuracy and Universality in Linear Energy Relations for Alcohol Dehydrogenation on Transition Metals , 2015 .

[13]  J. Nørskov,et al.  Modeling ethanol decomposition on transition metals: a combined application of scaling and Brønsted-Evans-Polanyi relations. , 2009, Journal of the American Chemical Society.

[14]  J. Brønsted.  Acid and Basic Catalysis. , 1928 .

[15]  P. Daoutidis,et al.  Automated identification of energetically feasible mechanisms of complex reaction networks in heterogeneous catalysis: application to glycerol conversion on transition metals , 2014 .

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

[17]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[18]  J. Greeley,et al.  A density functional theory analysis of trends in glycerol decomposition on close-packed transition metal surfaces. , 2013, Physical chemistry chemical physics : PCCP.

[19]  J. Nørskov,et al.  Towards the computational design of solid catalysts. , 2009, Nature chemistry.

[20]  Catherine Pinel,et al.  Conversion of biomass into chemicals over metal catalysts. , 2014, Chemical reviews.

[21]  D. Vlachos,et al.  An Efficient Reaction Pathway Search Method Applied to the Decomposition of Glycerol on Platinum , 2011 .

[22]  Joseph J. Bozell,et al.  Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited , 2010 .

[23]  B. Liu,et al.  Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study , 2011 .

[24]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

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

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

[27]  Thomas Bligaard,et al.  Density functional theory in surface chemistry and catalysis , 2011, Proceedings of the National Academy of Sciences.

[28]  Matthew Neurock,et al.  Reactivity theory of transition-metal surfaces: a Brønsted-Evans-Polanyi linear activation energy-free-energy analysis. , 2010, Chemical reviews.

[29]  M. Polanyi,et al.  On the introduction of thermodynamic variables into reaction kinetics , 1937 .

[30]  Catherine Pinel,et al.  Unravelling the mechanism of glycerol hydrogenolysis over rhodium catalyst through combined experimental-theoretical investigations. , 2011, Chemistry.

[31]  M. G. Evans,et al.  Inertia and driving force of chemical reactions , 1938 .

[32]  James A. Dumesic,et al.  Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass , 2013 .

[33]  Philippe Sautet,et al.  C–H versus O–H Bond Dissociation for Alcohols on a Rh(111) Surface: A Strong Assistance from Hydrogen Bonded Neighbors , 2011 .

[34]  P. Sautet,et al.  Linear Energy Relations As Predictive Tools for Polyalcohol Catalytic Reactivity , 2014 .

[35]  P. Sautet,et al.  Fast prediction of selectivity in heterogeneous catalysis from extended Brønsted-Evans-Polanyi relations: a theoretical insight. , 2009, Angewandte Chemie.

[36]  P. Gallezot,et al.  Conversion of biomass to selected chemical products. , 2012, Chemical Society reviews.

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

[38]  R. Bell,et al.  The Theory of Reactions Involving Proton Transfers , 1936 .

[39]  P. Sautet,et al.  Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone. , 2014, Chemical communications.

[40]  C. Pinel,et al.  Catalytic transformation of glycerol on several metal systems supported on ZnO , 2012 .