Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Rajeev Surendran Assary Project Name: Cat_Biomass Division: MSD Project title: Computational Studies of Biomass Catalysis Associated funding: BES Other Systems: CNM Argonne, Blue Gene/P Argonne Science: This work will be done as part of the new Energy Frontier Research center at Argonne and will be done in close collaboration with the experimental part of the Center involving researchers from Argonne, Northwestern University, Purdue University, and the University of Wisconsin. Efficient chemical transformation of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level chemical conversion of naturally abundant sugar molecules to alternative fuel precursor chemicals (hydroxyl-methyl-furfural, γ-valero-lactone, levulinic acid) require accurate molecular level understanding of reaction energetics and kinetics. High-level quantum chemical methods can provide accurate energetics for important chemical transformations of sugar molecules and assist experimental efforts for efficient production of alternative fuels and fuel precursors. Kinetics and thermodynamics of complex sugar decomposition pattern is another area of huge importance that requires fundamental understanding to limit undesired reactions. Due to development of fast computers and reliable, accurate computational methods now allows us to compute the energetics of many important reactions in the Biomass conversion. Micro-kinetic modeling of various reactio ns based from accurate ab-initio calculations is another useful area and need a great deal of computational studies. Industrial level chemical transformation of biomass to useful chemicals requires sustainable, efficient and economical catalysts and this require design of multifunctional catalysts. Mineral or Lewis acid catalyzed reaction is envisioned for the conversion of glucose to hydroxy-methyl-furfural, levulinic acid, γ-valero-lactone and this require detailed understanding of possible reactions of sugar molecules with a variety of acid sites and elucidation of reaction mechanisms Computational modeling of catalyst design, binding modes of sugar molecules and reaction sequences are essential to compliment experimental efforts towards an industrial level biomass conversion Project description: Biomass has the potential to become a sustainable precursor to industrial chemicals and transportation fuels, hence reducing the dependency of fossil fuels and petroleum derivatives. Acid catalyzed dehydration is widely used method to produce platform chemicals such as furfural (FF), predominantly from C5 sugars, hydroxy-methyl-furfural (HMF), from C6 sugars, and levulinic acid/ethyl levulinate (LA/EL), from C5 or C6 sugars. The hydrogen content in these platform chemicals are relatively smaller than their parent sugar molecules due to the removal of water molecules, and the dehydration reactions results in the formation of chemically stable keto (-C=O) compounds (for example, removal of three water molecules from fructose and xylose gives HMF and FF, respectively). An essential transformation of these compounds to alternate fuels and desired industrial chemicals require hydrogen, interestingly biomass is a potential source. The key reactions involve the process of the converting the biomass to useful chemicals are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Investigating these important reactions and modeling efficient catalysts for industrial use, by using computational chemistry methods is the aim of this project. Acid-Base hydrolysis and pyrolysis techniques are currently practiced as the ways to convert biomass to useful platform chemicals. These decomposition reactions are typically complex; include structural rearrangements, dehydration, oxidation and reduction. In order to assess the accurate kinetic and thermodynamic feasibilities of possible reactions, computational modeling is alternative approach to experiments. Application of methods such as G4/G4MP2, a CCSD(T) based energy evaluation method has been employed in the recent past to gain accurate understanding of energetics along with the help of density functional methods to investigate structures. Due to the complex chemical pathways of reactions in the biomass conversion, micro-kinetic models would be more appropriate and needed to assist the experimental interpretations or predict the outcome of such chemical transformations. This would require a significant amount of computational resources. Development of possible micro-k inetic models for following reactions would enhance the fundamental understanding of biomass catalysis: (1) Acid hydrolysis and Pyrolysis of Cellobiose/triose (2) Understanding the oligomerization processes during hydrolysis and pyrolysis Chemical transformation that cleave C-O bonds to form enols and hydrogenation of this enol to alcohol is one of the clean way to reduce the cross links in the complex furan derivatives obtained from the feed stokes. Recently, Atesin et al has reported a selective etheric C-O bond hydrogenolysis catalyzed by Ln(Otf)3/Pd-nanoparticle in ionic liquid. The etheric C-O bond cleavage to an enol is an endothermic process (ΔH= ~14 kcal/mol) and the hydrogenation of enol is very exothermic (ΔH= ~- 25 kcal/mol). Therefore the success of the overall conversion of ether to an alcohol depends on the effective coupling of C-O bond scission and the hydrogenation of alkenols. Due to the endothermicity of the ring opening process, the kinetics and the thermodynamics that controls the catalytic ether ring opening process is a key feature that requires a molecular level understanding for designing more efficient catalyst. In order to gain a deeper understanding of the catalysis a molecular le vel understanding of the following are essential: (1) Liquid phase catalytic hydrogenation energetics and reaction mechanism (2) Application of Lanthanide(Ln=La,Yb,Y, Eu, Al, Ti,Ta) -based catalysts in Ionic liquid These studies would lead to building of a thermochemical database and can be used as future reference tool for the thermodynamics/kinetics for biomass transformations. Additionally our computations would identify catalytic materials with high efficiency and this information would be valuable to our experimental collaborators. And computational modeling of these reactions would also enable us to understand the mechanistic details at the atomistic level. Project URL: http://www.anl.gov/catalysis-science/ Current FY Hours Used: undetermined amount New FY Requested allocation: 1600000 Q1: 400000 Q2: 400000 Q3: 400000 Q4: 400000 Justification: During the past three years we have gained significant progresses to understand the thermodynamic feasibilities of important reactions involve in the transformation of biomass to platform chemicals. Significant progresses were made for the molecular level understanding of conversion reaction for fructose to hydroxy-methyl-furfural, furfuryl alcohol to levulinic acid, polymerization of furfuryl alcohol, pyrolysis of glucose. These studies have provided an improved insight to the experimentalists in the IACT at Argonne and scientists working in the area of biomass to bioenergy area. We gratefully acknowledged the grants for the computer time during the past two years. We have acknowledged LCRC for the computational resources in the following publications during the past three years: 1. Thermochemistry and reaction barriers for the formation of Levoglucosenone from Cellobiose, Rajeev S. Assary†, Larry A. Curtiss, 2012, ChemCatChem, 4,200-205 (cover story) 2. Comparison of Sugar molecule decomposition through Glucose and Fructose: A High level quantum mechanical study, Rajeev S. Assary†, Larry A. Curtiss, Energy & Fuels, 2012, 26, 1344-1352 3. Theoretical studies for the formation of γ-valero-lactone from levulinic acid and formic acid by homogeneous catalysis, Rajeev S. Assary†, Larry A. Curtiss, Chemical Physics Letters, 2012 , 541, 21-26 4. Brønsted-Evans-Polanyi relationships for C-C bond formation and cleavage in Thiamine-catalyzed enzyme catalysis for 2-keto acids, Rajeev S. Assary†, Linda J. Broadbelt, Larry A. Curtiss, Journal of Molecular Modeling, 2012, 18, 144-150 5. Glucose to Platform Chemicals (hydroxy-methyl-furfural, furfuryl alcohol, levulinic acid): Understanding the Thermodynamic landscapes of Acid-catalyzed reactions using High-level Ab initio Methods, Rajeev S. Assary†, Taejin Kim, John Low, Jeff Greeley, Larry A. Curtiss, Physical Chemistry Chemical Physics, 2012, advance article (10.1039/C2CP41842H ) 6. Experimental and Theoretical Studies of the Acid-catalyzed conversion of Furfuryl alcohol to Levulinic acid in Aqueous solution, Gretchen Gonzales Maldonaldo, Rajeev S. Assary, James A. Dumesic, Larry A. Curtiss, Energy & Environmental Science, 2012, 5, 6981-6989 7. Metalloenzyme-like Catalyzed Isomerizations of Sugars by Lewis Acid Zeolites, Ricardo Bermejo-Deval, Rajeev S. Assary, Eranda Nikolla, Manuel Moliner, Yuriy Roman-Leshkov, Son-Jong Hwang, Arna Palsdottir, Dorothy Silverman, Raul Lobo, Larry A. Curtiss, Mark E. Davis, Proceedings of National Academy of Science ,2012, 109, 9727-9732 8. Acid-Catalyzed Conversion of Furfuryl Alcohol to Ethyl Levulinate in Liquid Ethanol, Gretchen Gonzalez Maldonaldo, Rajeev S. Assary, James A. Dumesic, Larry A. Curtiss, 2012, Energy & Environmental Science, advance article, (10.1039/C2EE22486K) 9. Investigation of the Raman Spectra of Organic Chemicals: Combination and Prediction Spectrum Methods, Taijen Kim, Rajeev S. Assary, Larry A. Curtiss, Christopher Marshal, Peter Stair, Chemical Physics Letters, 2012, 212,210-215. 10. Mechanistic insights into the decomposition of fructose to hydroxy-methyl-furfural in neutral and acid environments using high-level quantum chemical methods, Rajeev S. Assary†, Paul C. Redfern, Jeff Greeley, Larry A. Curtiss, Journal of Physical Chemistry B, 2011, 115, 4341-49. 11. Theoretical study of 1,2-hydride shift associated with the Isomerization of Glyceraldehyde to Dihydroxy acetone by Lewis acid active site models, Rajeev S. Assary†, Larry A. Curtiss, Journal of Physical Chemistry A, 2011, 115, 8754-60. 12. Acid-catalyzed Furfuryl Alcohol Polymerization : Characterizations of Molecular Structures and Thermodynamic Properties, Taijen Kim, Rajeev S. Assary, Larry A. Curtiss, Christopher Marshal, Peter Stair, ChemCatChem, 2011, 3, 1451-58, (Cover story). 13. Vibrational Properties of Levulinic acid and furan derivatives: Raman spectroscopy and theoretical calculations, Taijen Kim, Rajeev S. Assary, Larry A. Curtiss, Christopher Marshal, Peter Stair, Journal of Raman Spectroscopy, 2011,42,2069-76 14. Quantum chemical studies of Fructose catalytic conversion by Solid acid: Adsorption, Protonation and Mass transfer of fructose by HZSM-5, Lei Cheng, Larry A. Curtiss, Rajeev S. Assary, Jeff Greeley, Joachim Sauer, Torsten Kerber, Journal of Physical Chemistry C, 2011,115, 21785-21790 15. Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid, Rajeev S. Assary, Paul C. Redfern, Jeff Hammond, Jeff Greeley, Larry A. Curtiss, Journal of Physical Chemistry B, 2010, 114, 9002-9009. 16. Predicted Thermochemistry for Chemical Conversion of 5-hydroxymethylfurfural, Rajeev S. Assary†, Paul C. Redfern, Jeff Hammond, Jeff Greeley, Larry A. Curtiss, Chemical Physics Letters, 2010 497, 123-128. Software We indent to use Gaussian 09 and NWChem for quantum-mechanical calculations. In Gaussian 09, the DFT calculations scales well up to 64 processors, however the high-level ab initio methods scale only up to 16 processors. Therefore these calculations do require a longer execution time. We have made use of excellent use of the computational allocation and our computations resulted in high-impact publications and we intend to contnue our studies and the support from LCRC is greatly appreciated. Thank You, The LCRC Accounts System