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
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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
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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
The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface
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
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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
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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
Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation
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
High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine
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
Structural and Spectroscopic Characterization of 17- and 18-Electron Piano-Stool Complexes of Chromium. Thermochemical Analyses of Weak Cr–H Bonds
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
Effects of Electrolyte Salts on the Performance of Li–O2 Batteries
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