Advancing Heterogeneous Catalysis of Routes for the Conversion of Complex Biogenic Feedstocks in Aqueous and Apolar Solvents
EMSL Project ID
48810
Abstract
This proposal aims to provide molecular insight into elementary reaction steps and their kinetics in condensed phases at an atomic and molecular level, which rivals the currently possible insight into catalysis at the gas-solid interface. Fundamental conversion steps of bio-derived molecules and polymers to hydrocarbons in aqueous and apolar phases are used as examples. Insight is tested via synthesis of new catalysts and exploration of new catalytic routes to convert lignin components. Three reactions are critical: depolymerization of ligneous biomass, hydrogenation/hydrodeoxygenation of the intermediates, and adjusting the product molecular weight by acid-base catalyzed C–C coupling. Substituted phenols, furans, and light alcohols are initial model reactants. We use physicochemical methods to characterize the state of the catalyst, spectroscopy to characterize interactions of reacting molecules, and detailed kinetic investigations that will yield quantitative kinetic parameters as monitored by in situ MAS NMR. Theory will complement the understanding of spectroscopic and kinetic phenomena and will guide synthesis of new catalysts. We will order active sites synthetically at a nanoscopic level and arrange the sites at a mesoscopic level to enable catalysis along selected pathways. We will focus on the impact of a sterically and chemically tailored reaction space around the active centers (Brønsted acid centers, hydronium ions and metal particles) to enhance the desired reaction rates. While tailoring the space around the acid centers is used to increase rates of acid-catalyzed reactions, reactions involving hydrogen will be increased by providing hydronium ions close to active metal centers, decoupling H availability and H addition rates.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2015-10-01
End Date
2017-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Abreu Resende K., C.E. Hori, F. Bellot Noronha, H. Shi, O.Y. Gutierrez-Tinoco, D.M. Camaioni, and J.A. Lercher. 2017. "Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO2." Applied Catalysis. A, General 548. PNNL-SA-125711. doi:10.1016/j.apcata.2017.08.005
Cai Q, J Wang, Y Wang, and D Mei. 2016. "First-principles Thermodynamics Study of the Spinel MgAl2O4 Surface Stability." Journal of Physical Chemistry C 120(34):19087-19096. doi:10. 1021/acs. jpcc. 6b02998
Chase Z, S Kasakov, H Shi, A Vjunov, JL Fulton, DM Camaioni, M Balasubramanian, C Zhao, Y Wang, and JA Lercher. 2015. "State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media." Chemistry - A European Journal 21(46):16541-16546. doi:10.1002/chem.201502723
Denk C., S.D. Foraita, L. Kovarik, K.A. Stoerzinger, Y. Liu, E. Barath, and J.A. Lercher. 2019. "Rate enhancement by Cu in NixCu1-x/ZrO2 bimetallic catalysts for hydrodeoxygenation of stearic acid." Catalysis Science & Technology 9, no. 10:2620-2629. PNNL-SA-140851. doi:10.1039/c9cy00181f
Hu J.Z., C. Wan, A. Vjunov, M. Wang, Z. Zhao, M.Y. Hu, and D.M. Camaioni, et al. 2017. "27Al MAS NMR Studies of HBEA Zeolite at Low to High Magnetic Fields." Journal of Physical Chemistry C 121, no. 23:12849-12854. PNNL-SA-125685. doi:10.1021/acs.jpcc.7b03517
Liang X, N Liu, H Qiu, C Zhang, D Mei, and B Chen. 2017. "Hydrogen Assisted Synthesis of Branched Nickel Nanostructures: A Combined Theoretical and Experimental Study." Physical Chemistry Chemical Physics. PCCP 19(39):26718-26727. doi:10.1039/C7CP04673A
Liang X, Z Ren, X Zhu, Q Zhang, D Mei, and B Chen. 2017. "Competitive Adsorption-Assisted Formation of One-Dimensional Cobalt Nanochains with High CO Hydrogenation Activity." Journal of Physical Chemistry C 121(44):24588-24593. doi:10.1021/acs.jpcc.7b07460
Mei D. 2018. "Monitoring the methanol conversion process in H-ZSM-5 using synchrotron X-ray powder diffraction-mass spectrometry." Journal of Catalysis 365. PNNL-SA-123879. doi:10.1016/j.jcat.2018.06.027
Platero-Prats AE, A League, SV Bernales Candia, J Ye, LC Gallington, A Vjunov, N Schweitzer, Z Li, J Zheng, BL Mehdi, AJ Stevens, A Dohnalkova, M Balasubramanian, O Farha, J Hupp, ND Browning, JL Fulton, DM Camaioni, JA Lercher, DG Truhlar, L Gagliardi, C Cramer, and KW Chapman. 2017. "Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-hydroxo Clusters to Form Hetero-Bimetallic Nanowires." Journal of the American Chemical Society 139(30):10410-10418. doi:10.1021/jacs.7b04997
Prodinger S, MA Derewinski, A Vjunov, SD Burton, I Arslan, and JA Lercher. 2016. "Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects." Journal of the American Chemical Society 138(13):4408–4415. doi:10.1021/jacs.5b12785
Prodinger S, VRS Vemuri, T Varga, BP McGrail, RK Motkuri, and MA Derewinski. 2016. "Impact of chabazite SSZ-13 textural properties and chemical composition on CO2 adsorption applications." New Journal of Chemistry 40(5):4375-4385. doi: 10.1039/C5NJ03205A
Sun J, Q Cai, Y Wan, S Wan, L Wang, J Lin, D Mei, and Y Wang. 2016. "The promotional effects of cesium promoter on higher alcohol synthesis from syngas over cesium-promoted Cu/ZnO/Al2O3 catalysts." ACS Catalysis 6(9):5771-5785. doi:10. 1021/acscatal. 6b00935
Vjunov A, M Wang, N Govind, T Huthwelker, H Shi, D Mei, JL Fulton, and JA Lercher. 2017. "Tracking the chemical transformations at the Brønsted acid site upon water-induced deprotonation in a zeolite pore." Chemistry of Materials 29(21):9030-9042. doi:10.1021/acs.chemmater.7b02133
Wang M, OY Gutierrez-Tinoco, DM Camaioni, and JA Lercher. 2018. "Palladium?Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds." Angewandte Chemie International Edition 130(14):3809-3813. doi:10.1002/ange.201709445
Zhao Z, H Shi, C Wan, MY Hu, Y Liu, D Mei, DM Camaioni, JZ Hu, and JA Lercher. 2017. "“On the Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy”." Journal of the American Chemical Society 139(27):9178-9185. doi:10.1021/jacs.7b02153
Zhi Y, H Shi, L Mu, Y Liu, D Mei, DM Camaioni, and JA Lercher. 2015. "Dehydration pathways of 1-propanol on HZSM-5 in the presence and absence of water." Journal of the American Chemical Society 137(50):15781-15794. doi:10.1021/jacs.5b09107