Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study.

Hydration reactions on a carbonate-terminated cubic ZrO2(110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H2O molecules (Zr-OH2) and monodentate hydroxyl groups (Zr-OH-). Similar to a carbonate-free hydrated surface, Zr-OH2, Zr-OH-, and polydentate hydroxyl groups ([double bond splayed left]OH+) were observed, while the ratio of acidic Zr-OH2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr-OH2 is not affected. As a result, protons released from [double bond splayed left]OH+ react with Zr-OH- to form Zr-OH2, leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

[1]  Y. Tateyama,et al.  Catalytic Proton Dynamics at the Water/Solid Interface of Ceria-Supported Pt Clusters. , 2016, Journal of the American Chemical Society.

[2]  Y. Shibuta,et al.  Proton Migration on Hydrated Surface of Cubic ZrO2: Ab initio Molecular Dynamics Simulation , 2015 .

[3]  R. Rousseau,et al.  Structure, dynamics and stability of water/scCO2/mineral interfaces from ab initio molecular dynamics simulations , 2015, Scientific Reports.

[4]  L. Halonen,et al.  First and second deprotonation of H₂SO₄ on wet hydroxylated (0001) α-quartz. , 2014, Physical chemistry chemical physics : PCCP.

[5]  N. Kuwata,et al.  Low-Temperature Protonic Conduction Based on Surface Protonics: An Example of Nanostructured Yttria-Doped Zirconia , 2014 .

[6]  A. Michaelides,et al.  Solvent-Induced Proton Hopping at a Water–Oxide Interface , 2014, The journal of physical chemistry letters.

[7]  Jun Cheng,et al.  Understanding surface acidity of gibbsite with first principles molecular dynamics simulations , 2013 .

[8]  L. Halonen,et al.  Dissociation of HCl into Ions on Wet Hydroxylated (0001) α-Quartz , 2013 .

[9]  M. Kogler,et al.  In Situ FT-IR Spectroscopic Study of CO2 and CO Adsorption on Y2O3, ZrO2, and Yttria-Stabilized ZrO2 , 2013, The journal of physical chemistry. C, Nanomaterials and interfaces.

[10]  Tiffany R Walsh,et al.  First-principles molecular dynamics simulations of NH4(+) and CH3COO(-) adsorption at the aqueous quartz interface. , 2012, The Journal of chemical physics.

[11]  D. Costa,et al.  Ab Initio Molecular Dynamics Study of the AlOOH Boehmite/Water Interface: Role of Steps in Interfacial Grotthus Proton Transfers , 2012 .

[12]  Michiel Sprik,et al.  The Silica-Water Interface: How the Silanols Determine the Surface Acidity and Modulate the Water Properties. , 2012, Journal of chemical theory and computation.

[13]  H. Takamura,et al.  Electrical conductivity of dense nanocrystalline ceria under humidified atmosphere , 2010 .

[14]  Michiel Sprik,et al.  Acidity of the Aqueous Rutile TiO2(110) Surface from Density Functional Theory Based Molecular Dynamics. , 2010, Journal of chemical theory and computation.

[15]  A. Krause,et al.  Structure and Stability of Formates and Carbonates on Monoclinic Zirconia: A Combined Study by Density Functional Theory and Infrared Spectroscopy , 2008 .

[16]  Priya Vashishta,et al.  Electronic processes in fast thermite chemical reactions: a first-principles molecular dynamics study. , 2008, Physical review. E, Statistical, nonlinear, and soft matter physics.

[17]  Manfred Martin,et al.  Unprecedented Room‐Temperature Electrical Power Generation Using Nanoscale Fluorite‐Structured Oxide Electrolytes , 2008 .

[18]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[19]  W. Langel,et al.  Simulation of the interface between titanium oxide and amino acids in solution by first principles MD , 2003 .

[20]  Rajiv K. Kalia,et al.  Linear-scaling density-functional-theory calculations of electronic structure based on real-space grids: design, analysis, and scalability test of parallel algorithms , 2001 .

[21]  A. Bell,et al.  Investigation of CO and CO2 Adsorption on Tetragonal and Monoclinic Zirconia , 2001 .

[22]  K. Sasaki,et al.  Characterization of adsorbed water layers on Y2O3-doped ZrO2 , 2001 .

[23]  M. Odelius.  Mixed Molecular and Dissociative Water Adsorption on MgO[100] , 1999 .

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

[25]  C. Su,et al.  In Situ Infrared Speciation of Adsorbed Carbonate on Aluminum and Iron Oxides , 1997 .

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

[27]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[28]  Tsutomu Yamaguchi.  Application of ZrO2 as a catalyst and a catalyst support , 1994 .

[29]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[30]  Mark E. Tuckerman,et al.  Reversible multiple time scale molecular dynamics , 1992 .

[31]  Hoover,et al.  Canonical dynamics: Equilibrium phase-space distributions. , 1985, Physical review. A, General physics.

[32]  Werner Weppner,et al.  Vehicle Mechanism, A New Model for the Interpretation of the Conductivity of Fast Proton Conductors , 1982 .

[33]  J. André,et al.  Thermodynamic Properties of Adsorbed Water Molecules and Electrical Conduction in Montmorillonites and Silicas , 1965 .

[34]  R. S. Mulliken.  Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I , 1955 .

[35]  K. Arata,et al.  Synthesis of solid superacid of tungsten oxide supported on zirconia and its catalytic action for reactions of butane and pentane , 1988 .

[36]  G. A. Parks,et al.  Electrical conductivity of silica gel in the presence of adsorbed water , 1968 .