Understanding structure-function relationships for developing catalysts for energy storage and production reactions.
EMSL Project ID
47453
Abstract
The DOE Basic Energy Sciences Energy Frontier Research Center entitled “Center for Molecular Electrocatalysis” (Bullock), the DOE Basic Energy Sciences “Modular Energy-Based Approach to Molecular Catalyst Design” (Appel), and the DOE Basic Energy Sciences Early Career Research Program “Catalyst Biomimics: A novel approach to catalyst design” (Shaw) are three research program focusing on the development of electrocatalysts for energy storage, energy production, or carbon fixation reactions in order to develop efficient and practical alternative energy sources. The different research programs use catalysts with different active site metals and structural types ranging from small molecules to large multi-peptide systems, but they all focus on developing an in depth understanding of how the structure of the catalysts influences the turnover observed. Specifically, the goal of the proposed research is to use the EMSL facilities, high Field NMR, EPR, CD, mass spectroscopies and computational studies, to characterize ligand structural dynamics, protons movement, substrate binding and catalysts’ lifetimes. High field NMR, EPR, CD, and mass spectroscopies will provide the opportunity to determine catalyst structure as well as structural information about catalytic intermediates and decomposition products formed under different catalytic conditions. High field NMR as well as computational studies will be used to investigate dynamic processes and the mechanisms by which these processes occur, such as proton shuttling to and from external sources. These studies are necessary to guide the design of future, more efficient catalysts.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2012-10-01
End Date
2014-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Bays JT, N Priyadarshani, MS Jeletic, EB Hulley, AM Appel, JC Linehan, and WJ Shaw. 2014. "The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)2 CO2 Hydrogenation Catalysts." PNNL-SA-103717, Pacific Northwest National Laboratory, Richland, WA. [Unpublished]
Bhattacharya P., D.E. Prokopchuk, and M.T. Mock. 2017. "Exploring the Role of Pendant Amines in Transition Metal Complexes for the Reduction of N2 to Hydrazine and Ammonia." Coordination Chemistry Reviews 334. PNNL-SA-117030. doi:10.1016/j.ccr.2016.07.005
Chen S, MH Ho, RM Bullock, DL DuBois, M Dupuis, RJ Rousseau, and S Raugei. 2014. "Computing Free Energy Landscapes: Application to Ni-based Electrocatalysts with Pendant Amines for H2 Production and Oxidation." ACS Catalysis 4(1):229-242. doi:10.1021/cs401104w
Das AK, MH Engelhard, F Liu, RM Bullock, and JA Roberts. 2013. "The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface." Inorganic Chemistry 52(23):13674-13684. doi:10.1021/ic402247n
Das AK, MH Engelhard, SJ Lense, JA Roberts, and RM Bullock. 2015. "Covalent Attachment of Diphosphine Ligands to Glassy Carbon Electrodes via Cu-Catalyzed Alkyne-Azide Cycloaddition. Metallation with Ni(II)." PNNL-SA-107506, Pacific Northwest National Laboratory, Richland, WA. [Unpublished]
Elnaas A.R., D. Grice, J. Han, Y. Feng, A. Di Capau, T. Mak, and J.A. Laureanti, et al. 2020. "Discovery of a Natural Product that Binds to the Mycobacterium tuberculosis Protein Rv1466 by Native Mass Spectrometry." Molecules 25, no. 10:2384. PNNL-SA-152797. doi:10.3390/molecules25102384
Fang M, MH Engelhard, Z Zhu, ML Helm, and JA Roberts. 2014. "Electrodeposition From Acidic Solutions of Nickel Bis(benzenedithiolate) Produces a Hydrogen-Evolving Ni-S Film on Glassy Carbon." ACS Catalysis 4(1):90-98. doi:10.1021/cs400675u
Franz JA, MJ O'Hagan, MH Ho, TL Liu, ML Helm, S Lense, DL DuBois, WJ Shaw, AM Appel, S Raugei, and RM Bullock. 2013. "Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation." Organometallics 32(23):7034-7042. doi:10.1021/om400695w
Heiden ZM, S Chen, LAN Labios, RM Bullock, ED Walter, EL Tyson, and MT Mock. 2014. "Proton and Electron Additions to Iron (II) Dinitrogen Complexes Containing Pendant Amines." Organometallics 33(6):1333-1336. doi:10.1021/om401089d
Helm ML, PP Das, RM Stolley, and EF Van Der Eide. 2014. "A Ni(II) Bis(diphosphine) Hydride Complex Containing Proton Relays: Structural Characterization and Electrocatalytic Studies." European Journal of Inorganic Chemistry [epub ahead of print]:, doi:10.1002/ejic.201402250
Ho, M.-H.; Raugei, S.; Rousseau, R.; Dupuis, M.; Bullock. R. M. "Evaluation of the Role of Water in the H2 Bond Formation by Ni(II)-Based Electrocatalysts." J. Chem. Theory Comput. 2013, 9, 3505-3514. DOI: 10.1021/ct400396s.
Laureanti J.A., G.W. Buchko, S. Katipamula, Q. Su, J.C. Linehan, O. Zadvornyy, and J.W. Peters, et al. 2018. "Protein Scaffold Activates Catalytic CO2 Hydrogenation by a Rhodium Bis(diphosphine) Complex." ACS Catalysis 9, no. 1:620-625. PNNL-SA-135805. doi:10.1021/acscatal.8b02615
Liu TL, Y Shao, G Li, M Gu, JZ Hu, S Xu, Z Nie, X Chen, CM Wang, and J Liu. 2014. "A Facile Approach Using MgCl2 to Formulate High Performance Mg2+ Electrolytes for Rechargeable Mg Batteries." Journal of Materials Chemistry A 2(10):3430 - 3438. doi:10.1039/c3ta14825d
Nasybulin EN, W Xu, MH Engelhard, Z Nie, SD Burton, L Cosimbescu, ME Gross, and J Zhang. 2013. "Effects of electrolyte salts on the performance of Li-O2 batteries." Journal of Physical Chemistry C 117(6):2635-2645. doi:10.1021/jp311114u
Reback ML, B Ginovska-Pangovska, GW Buchko, A Dutta, N Priyadarshani, BL Kier, ML Helm, S Raugei, and WJ Shaw. 2016. "Investigating the role of chain and linker length on the catalytic activity of an H2 production catalyst containing a b-hairpin peptide." Journal of Coordination Chemistry. [In Press]
Stewart MP, II, MH Ho, S Wiese, ML Lindstrom, CE Thogerson, S Raugei, RM Bullock, and ML Helm. 2013. "High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Diphosphine Ligands Containing One Pendent Amine." Journal of the American Chemical Society 135(16):6033-6046. doi:10.1021/ja400181a
van der Eide EF, ML Helm, ED Walter, and RM Bullock. 2013. "Structural and Spectroscopic Characterization of 17- and 18-Electron Piano-Stool Complexes of Chromium. Thermochemical Analyses of Weak Cr-H Bonds." Inorganic Chemistry 52(3):1591-1603. doi:10.1021/ic302460y
Wongnate T, D Sliwa, B Ginovska-Pangovska, DMA Smith, MW Wolf, N Lehnert, and S Raugei. 2016. "The Radical Mechanism of Biological Methane Synthesis by Methyl-Coenzyme M Reductase." Science 352(6288):953-958. doi:10. 1126/science. aaf0616