First Principles Computations of Interfacial Phenomena for Environment-Friendly Catalysis
EMSL Project ID
35193
Abstract
A fundamental knowledge of the chemical and physical properties at gas-solid or liquid-solid interfaces is essential for the design and discovery of breakthrough materials for cleaner and more efficient catalysts. Computational strategies using high performance computing provide the opportunity to design surfaces and interfaces with desired functionalities. This requires both an understanding of the processes that are occurring at the interfaces as well as relating catalytic properties to key calculated parameters such as adsorption energies, which can be used in screening many potential candidates. This proposal is focused on both the understanding of structure-function relationships as well as use of this insight to help design new materials for processes involving heterogeneous catalysis, electrocatalysis, and photocatalysis. The computational studies will be based on state-of-the-art electronic structure methods including density functional theory, a powerful tool for understanding and design of new catalysts. The proposed computational studies involve collaboration with world-class experimentalists at the Pacific Northwest National Laboratory and Argonne National Laboratory. New catalysts are needed for making and breaking specific bonds for energy efficient and environmentally friendly catalysts. Recent studies have shown that supported subnanometer clusters exhibit novel catalytic properties for breaking C-H bonds. We will carry out systematic studies to explore the unusual catalytic properties of these clusters and to determine how they might be tailored to make and break specific bonds. These computations will play a key role in the design and discovery of environmentally friendly catalysts for industrial processes. Another interesting area of heterogeneous catalysis is synthesis of nanocarbons, which have many potential applications.
Electrocatalysis provides a low-temperature, energy efficient alternative to heterogeneous catalysis that has potential uses for chemical transformations as well as the development of alternative energy sources. We will investigate carbon dioxide electroreduction, wherein CO2 is electrochemically reduced to CO and hydrogenated products in acidic solution. This reaction has the potential to both produce useful chemicals from an essentially limitless feedstock and reduce atmospheric greenhouse gas loadings. Among the most exciting possibilities presented by this reaction is the electrochemical production of methanol. We will also investigate oxygen reduction catalysis, which is important for energy conversion by fuel cells.
A third focus of the proposed work is photocatalysis. Efficient utilization of solar energy through photocatalysis would be a significant step towards easing current energy demands. TiO2 is a prototypical photocatalyst used for organic pollutant degradation and also for water splitting (H₂O → H₂ + ½O₂), H2 being an important fuel source. Despite the importance of TiO2, there are many fundamental issues that are not well understood, such as how photoexcited holes and electrons interact with surface adsorbates and lead to their catalytic decomposition. Molecular modeling methods provide an excellent way to study surface reactions and provide insights into the intermediates and reaction pathways. We will study the reactivity of organic molecules over TiO2, better characterize the nature of electrons/holes and their transport properties, and model the interactions of holes/electrons at the surface in the presence of adsorbate molecules.
Project Details
Project type
Capability Research
Start Date
2009-10-01
End Date
2012-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Assary RS, AC Atesin, Z Li, LA Curtiss, and TJ Marks. 2013. "Reaction Pathways and Energetics of Etheric C?O Bond Cleavage Catalyzed by Lanthanide Triflates." ACS Catalysis 3(9):1908–1914. doi:10.1021/cs400483q
Assary RS, and LA Curtiss. 2012. "Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose." ChemCatChem 4(2):200-205. doi:10.1002/cctc.201100280
Assary RS, PC Redfern, JP Greeley, and LA Curtiss. 2011. "Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods." Journal of Physical Chemistry B 115(15):4341-4349. doi:10.1021/jp1104278
Assary RS, PC Redfern, JR Hammond, JP Greeley, and LA Curtiss. 2010. "Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid." Journal of Physical Chemistry B 114(27):9002-9009. doi:10.1021/jp101418f.
Assary RS, T Kim, J Low, JP Greeley, and LA Curtiss. 2012. "Glucose and Fructose to Platform Chemicals: Understanding the Thermodynamic Landscapes of Acid-Catalysed Reactions Using High-Level ab Initio Methods ." Physical Chemistry Chemical Physics. PCCP 14:16603-16611. doi:10.1039/C2CP41842H
Cheng L, LA Curtiss, RS Assary, JP Greeley, T Kerber, and J Sauer. 2011. "Adsorption and Diffusion of Fructose in Zeolite HZSM-5: Selection of Models and Methods for Computational Studies." Journal of Physical Chemistry C 115(44):21785-21790. doi:10.1021/jp2062018
Deskins NA, Rousseau R, Dupuis M. 2010. "Defining the Role of Excess Electrons in the Surface Chemistry of TiO2." The Journal of Physical Chemistry C 2010, 114, 5891-5897.
Deskins NA, Rousseau R, Dupuis M. 2010. “Localized Electronic States from Surface Hydroxyls and Polarons in TiO2(110)." Journal of Physical Chemistry C, 113(33):14583-14586, 2010.
Dimitrijevic N, BK Vijayan, OG Poluektov, T Rajh, KA Gray, H He, and P Zapol. 2011. "Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania." Journal of the American Chemical Society 133(11):3964-3971. doi:10.1021/ja108791u
D. Strmcnik, K. Kodama, D. van der Vliet, J. Greeley, V.R. Stamenkovic, N.M. Markovic. 2010. “The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum.” Nature Chemistry 1(6):466-472 (2009). doi:10.1038/nchem.330
Du P, J Lu, KC Lau, X Luo, J Bareno, X Zhang, Y Ren, Z Zhang, LA Curtiss, YK Sun, and K Amine. 2013. "Compatibility of Lithium Salts with Solvent of the Non-Aqueous Electrolyte in Li–O2 Batteries." Physical Chemistry Chemical Physics. PCCP (15):5572-5581. doi:10.1039/c3cp50500f
Du Y, Deskins NA, Zhang Z, Dohnalek Z, Dupuis M, Lyubinetsky I. "Formation of O adatom pairs and charge transfer upon O(2) dissociation on reduced TiO(2)(110)." Physical Chemistry Chemical Physics:PCCP 2010, 12, 6337-44.
Du Y, NA Deskins, Z Zhang, Z Dohnalek, M Dupuis, and I Lyubinetsky. 2010. "Water Interactions with Terminal Hydroxyls on TiO2 (110)." Journal of Physical Chemistry C 114(40):17080-17084. doi:10.1021/jp1036876
Du Y, NG Petrik, NA Deskins, Z Wang, MA Henderson, GA Kimmel, and I Lyubinetsky. 2012. "Hydrogen Reactivity on Highly-hydroxylated TiO2(110) Surfaces Prepared via Carboxylic Acid Adsorption and Photolysis." Physical Chemistry Chemical Physics. PCCP 14(9):3066-3074. doi:10.1039/C1CP22515D
F. Mehmood, J. Greeley, L. A. Curtiss. 2010. “Density Functional Studies of Methanol Decomposition on Subnanometer Pd Clusters.” Journal of Physical Chemistry B, 113(52):21789-21796. DOI:10.1021/jp907772c
Gonzalez Maldonado GM, RS Assary, JA Dumesic, and LA Curtiss. 2012. "Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution." Energy & Environmental Science 5:6981-6989. doi:10.1039/c2ee03465d
Greeley JP. 2010. "Structural Effects on Trends in the Deposition and Dissolution of Metal-Supported Metal Adstructures." Electrochimica Acta 55(20):5545-5550. doi:10.1016/j.electacta.2010.04.055
He H, P Zapol, and LA Curtiss. 2010. "A Theoretical Study of CO2 Anions on Anatase (101) Surface." Journal of Physical Chemistry C 114(49):21474–21481. doi:10.1021/jp106579b
He H, P Zapol, and LA Curtiss. 2012. "Computational Screening of Dopants for Photocatalytic Two-Electron Reduction of CO2 on Anatase (101) Surfaces." Energy & Environmental Science 5(3):6196-6205. doi:10.1039/C2EE02665A
Henderson MA, NA Deskins, RT Zehr, and M Dupuis. 2011. "Generation of Organic Radicals During Photocatalytic Reactions on TiO2." Journal of Catalysis 279(1):205-212.
Iddir H, and LA Curtiss. 2010. "Li Ion Diffusion Mechanisms in Bulk Monoclinic Li2CO3 Crystals from Density Functional Studies." Journal of Physical Chemistry C 114(48):20903-20906. doi:10.1021/jp1086569
Jaber-Ansari L, H Iddir, LA Curtiss, and MC Hersam. 2014. "Influence of Electronic Type Purity on the Lithiation of Single-Walled Carbon Nanotubes." ACS Nano 8(3):2399-2409. doi:10.1021/nn405921t
Kandoi S, JP Greeley, DA Simonetti, J Shabaker, JA Dumesic, and M Mavrikakis. 2010. "Reaction Kinetics of Ethylene Glycol Reforming over Platinum in the Vapor versus Aqueous Phases." Journal of Physical Chemistry C 115(4):961–971. doi:10.1021/jp104136s
Kim T, RS Assary, CL Marshall, DJ Gosztola, LA Curtiss, and PC Stair. 2012. "Studies of the Raman Spectra of Cyclic and Acyclic Molecule." Chemical Physics Letters 531:210-215. doi:10.1016/j.cplett.2012.02.002
Lau KC, LA Curtiss, and JP Greeley. 2011. "Density Functional Investigation of the Thermodynamic Stability of Lithium Oxide Bulk Crystalline Structures as a Function of Oxygen Pressure." Journal of Physical Chemistry C 115(47):23625–23633. doi:10.1021/jp206796h
Lei C, C Yin, F Mehmood, B Liu, JP Greeley, S Lee, B Lee, S Seifert, RE Winans, D Teschner, R Schlogl, S Vajda, and LA Curtiss. 2013. "Reaction Mechanism for Direct Propylene Epoxidation by Alumina-Supported Silver Aggregates: The Role of the Particle / Support Interface." ACS Catalysis 4(1):32-39. doi:10.1021/cs4009368
Lei Y, B Liu, RJ Lobo-Lapidus, T Wu, H Feng, X Xia, AU Mane, JA Libera, JP Greeley, JT Miller, and JW Elam. 2012. "Synthesis of Pt?Pd Core?Shell Nanostructures by Atomic Layer Deposition: Application in Propane Oxidative Dehydrogenation to Propylene." Chemistry of Materials 24:3525?3533. doi:10.1021/cm300080w
Liu B, and JP Greeley. 2011. "Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study." Journal of Physical Chemistry C 115(40):19702–19709. doi:10.1021/jp202923w
Liu B, and JP Greeley. 2012. "Density Functional Theory Study of Selectivity Considerations for C–C Versus C–O Bond Scission in Glycerol Decomposition on Pt(111)." Topics in Catalysis 55(5-6):280-289. doi:10.1007/s11244-012-9806-2
Liu B, and JP Greeley. 2013. "A Density Functional Theory Analysis of Trends in Glycerol Decomposition on Close-Packed Transition Metal Surfaces ." Physical Chemistry Chemical Physics. PCCP 15:6475-6485. doi:10.1039/C3CP44088E
Lu J, HJ Jung, KC Lau, Z Zhang, JA Schlueter, P Du, RS Assary, JP Greeley, GA Ferguson, HH Wang, J Hassoun, H Iddir, J Zhou, L Zuin, Y Hu, YK Sun, B Scrosati, LA Curtiss, and K Amine. 2013. "Magnetism in Lithium–Oxygen Discharge Product." ChemSusChem 6(7):1196-1202. doi:10.1002/cssc.201300223
Lyubinetsky I, Deskins NA, Du Y, Vestergaard EK, Kim DJ, Dupuis M. "Adsorption states and mobility of trimethylacetic acid molecules on reduced TiO(2)(110) surface." Physical Chemistry Chemical Physics: PCCP 2010, 12.
Mehmood F, JP Greeley, P Zapol, and LA Curtiss. 2010. "Comparative Density Functional Study of Methanol Decomposition on Cu4 and Co4 Clusters." Journal of Physical Chemistry B 114(45):14458-14466. doi:10.1021/jp101594z
Mehmood F, RB Rankin, and LA Curtiss. 2012. "Trends in Methanol Decomposition on Transition Metal Alloy Clusters from Scaling and Brønsted–Evans–Polanyi Relationships." Physical Chemistry Chemical Physics. PCCP 14:8644–8652. doi:10.1039/c2cp00052k
P. Strasser, S. Koh, T. Anniyev, J. Greeley, K. More, C. Yu, Z. Liu, Zengcai, S. Kaya, D. Nordlund, H. Ogasawara, M. Toney, A. Nilsson. 2010. “Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts.” Nature Chemistry 2(6):454-460. doi:10.1038/nchem.623
Rajeev S. Assary, Paul C. Redfern, Jeff R. Hammond, Jeffrey Greeley, and Larry A. Curtiss. 2010. "Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid." J. Phys. Chem. B 2010, 114(27):9002–9009. doi: 10.1021/jp101418f
Rankin RB, and JP Greeley. 2012. "Trends in Selective Hydrogen Peroxide Production on Transition Metal Surfaces from First Principles." ACS Catalysis 2:2664?2672. doi:10.1021/cs3003337
S. Lee, B. Lee, F. Mehmood, S. Seifert, J.. Libera, J. W. Elam, J. Greeley, P. Zapol, L. A. Curtiss, Michael J. Pellin, P. C. Stair, R. E. Winans, and S. Vajda. 2010. "Oxidative Decomposition of Methanol on Subnanometer Palladium Clusters: The Effect of Catalyst Size and Support Composition." Journal of Physical Chemistry B 114(23):10342-10348. DOI: 10.1021/jp912220w
The Distribution of Ti3+ Surface Sites in Reduced TiO2
Wang Z, NA Deskins, and I Lyubinetsky. 2012. "Direct Imaging of Site-Specific Photocatalytic Reactions of O2 on TiO2(110)." The Journal of Physical Chemistry Letters 3(1):102-106. doi:10.1021/jz2014055
Yildirim H, JP Greeley, and S Sankaranarayanan. 2011. "Effect of Concentration on the Energetics and Dynamics of Li Ion Transport in Anatase and Amorphous TiO2." Journal of Physical Chemistry C 115(31):15661–15673. doi:10.1021/jp202514j
Y. Lei, F. Mehmood, S. Lee, J. Greeley, B. Lee, S. Seifert, R. E. Winans, J. W. Elam, R. J. Meyer, P. C. Redfern, D. Teschner, R. Schlögl, M. J. Pellin, L. A. Curtiss and S. Vajda. 2010. "Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects.” Science, 328, 224 (2010).
Zehr RT, NA Deskins, and MA Henderson. 2010. "Photochemistry of 1,1,1-Trifluoroacetone on Rutile TiO2(110)." Journal of Physical Chemistry C 114(40):16900-16908.
Zhang Z, J Lu, RS Assary, P Du, HH Wang, YK Sun, Y Qin, KC Lau, JP Greeley, PC Redfern, H Iddir, LA Curtiss, and K Amine. 2011. "Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes." Journal of Physical Chemistry C 115(51):25535–25542. doi:10.1021/jp2087412