Bioinspired Electrocatalysts for Energy Storage and Production Reactions.
EMSL Project ID
44681
Abstract
Electrocatalysts can convert electrical energy into chemical bonds in fuels, such as H2. In the reverse reaction, electrocatalysts can use the fuel to generate electrical energy on demand. This General EMSL research proposal is in support of three DOE Basic Energy Sciences research programs that focus on developing electrocatalysts for energy storage and production reactions using a wide variety of small molecule substrates. Reactions of interest include the production and oxidation of hydrogen, reduction of oxygen and nitrogen, alcohol oxidation and CO2 reduction. These reactions require the movement of multiple protons and electrons during catalysis. The catalyst designs have incorporated pendent amines as proton relays to facilitate proton movement during catalysis. The EMSL resources of High Field NMR and EPR, CD, mass spectroscopies and computational studies will provide unique insight into the structures, dynamics and mechanisms involved in the proton shuttling of these systems, which are crucial studies to guide the design of more efficient catalysts. The three research programs are the DOE Basic Energy Sciences Energy Frontier Research Center entitled "Center for Molecular Electrocatalysis" created in 2009 (Bullock), the DOE Basic Energy Sciences "Modular Energy-Based Approach to Molecular Catalyst Design" (DuBois), and the DOE Basic Energy Sciences Early Career Research Program "Catalyst Biomimics: A novel approach to catalyst design" (Shaw).
Project Details
Project type
Exploratory Research
Start Date
2011-10-14
End Date
2012-10-14
Status
Closed
Released Data Link
Team
Principal Investigator
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 [Unpublished]
Buchko GW, A Jain, ML Reback, and WJ Shaw. 2013. "Structural characterization of the model amphipathic peptide Ac-LKKLLKLLKKLLKL-NH2 in aqueous solution and with 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoroisopropanol." Canadian Journal of Chemistry 91(6):406-413. doi:10.1139/cjc-2012-0429
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
Chen S, RJ Rousseau, S Raugei, M Dupuis, DL DuBois, and RM Bullock. 2011. "Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations." Organometallics 30(22):6108-6118. doi:10.1021/om200645x
Dutta A, S Lense, J Hou, MH Engelhard, JA Roberts, and WJ Shaw. 2013. "Minimal Proton Channels Enable H2 Oxidation and Production with a Water Soluble Nickel-Based Catalyst ." Journal of the American Chemical Society 135(49):18490-18496. doi:10.1021/ja407826d
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
Ho MH, S Raugei, RJ Rousseau, M Dupuis, and RM Bullock. 2013. "Evaluation of the Role of Water in the H2 Bond Formation by Ni(II)-based Electrocatalysts ." Journal of Chemical Theory and Computation 9(8):3505-3514. doi:10.1021/ct400396s
Jain A, GW Buchko, ML Reback, MJ O'Hagan, B Ginovska-Pangovska, JC Linehan, and WJ Shaw. 2012. "Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere." ACS Catalysis 2(10):2114-2118. doi:10.1021/cs3004177
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
O'Hagan MJ, MH Ho, JY Yang, AM Appel, M Rakowski DuBois, S Raugei, WJ Shaw, DL DuBois, and RM Bullock. 2012. "Proton Delivery and Removal in [Ni(PR2NR?2)2]2+ Hydrogen Production and Oxidation Catalysts." Journal of the American Chemical Society 134(47):19409-19424. doi:10.1021/ja307413x
Priyadarshani N, A Dutta, B Ginovska-Pangovska, GW Buchko, MJ O'Hagan, S Raugei, and WJ Shaw. 2016. "Achieving Reversible H2/H+ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study." ACS Catalysis 6(9):6037-6049. doi:10. 1021/acscatal. 6b01433
Raugei S, S Chen, MH Ho, B Ginovska-Pangovska, RJ Rousseau, M Dupuis, DL DuBois, and RM Bullock. 2012. "The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes." Chemistry - A European Journal 18(21):6493-6506. doi:10.1002/chem.201103346
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]
Reback ML, B Ginovska-Pangovska, MH Ho, A Jain, TC Squier, S Raugei, JA Roberts, and WJ Shaw. 2013. "The Role of a Dipeptide Outer-Coordination Sphere on H2 -Production Catalysts: Influence on Catalytic Rates and Electron Transfer." Chemistry - A European Journal 19(6):1928-1941. doi:10.1002/chem.201202849
Reback ML, GW Buchko, BL Kier, B Ginovska-Pangovska, Y Xiong, S Lense, J Hou, JA Roberts, CM Sorensen, S Raugei, TC Squier, and WJ Shaw. 2014. "Electron Design From the Bottom Up: An Active Nickel Electrocatalyst with a Peptide Outer Coordination Sphere." Chemistry - A European Journal 20(6):1510-1514. doi:10.1002/chem.201303976
Reback ML, GW Buchko, BL Kier, B Ginovska-Pangovska, Y Xiong, S Lense, J Hou, JA Roberts, CM Sorensen, S Raugei, TC Squier, and WJ Shaw. 2014. "Electron design from the bottom up: an active nickel electrocatalyst with a peptide outer coordination sphere." Chemistry - A European Journal. doi:10.1002/chem.201303976
Shaw WJ, B Ginovska-Pangovska, A Dutta, ML Reback, and JC Linehan. 2014. "Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation." Accounts of Chemical Research [epub ahead of print]:, doi:10.1021/ar5001742
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, P Yang, ED Walter, TL Liu, and RM Bullock. 2012. "Dinuclear Metalloradicals Featuring Unsupported Metal-Metal Bonds." Angewandte Chemie International Edition 51(33):8361-8364. doi:10.1002/anie.201203531
van der Eide EF, TL Liu, DM Camaioni, ED Walter, and RM Bullock. 2012. "Facile Thermal W-W Bond Homolysis in the N-Heterocyclic Carbene-Containing Tungsten Dimer [CpW(CO)2(IMe)]2." Organometallics 31(5):1775-1789. doi:10.1021/om201162g