Shiyu Zhang obtained B.S. in Chemistry and Biology from Jilin University, China (2010) and Ph.D. in Chemistry from Georgetown University (2015). As a graduate student, he worked in the group of Prof. Timothy Warren where he was awarded the ACS DIC Young Investigator Award in recognition of his work in the bioinorganic chemistry of nitric oxide. From 2015 to 2017, Shiyu conducted postdoctoral research under the joint supervision of Prof. Christopher Cummins at MIT and Prof. Daniel Nocera at Harvard, where he had the opportunity to develop novel electrolytes for electrochemical energy storage systems, such as Li-ion, Li-Air and redox flow batteries.
Cooperative Reactivity of Bimetallic Complexes
Metalloenzymes play a crucial role in multi-electron transfer reactions that are fundamental to all domains of life. These challenging cellular reactions, such as hydrocarbon oxidation and CO2 reduction, are driven by the cooperative reactivity of bimetallic protein sites composed of Earth-abundant transition metals. The Zhang group aims to synthetically model biological centers with high reactivities that have yet to be replicated by synthetic systems. We aim to (1) understand the fundamental bioinorganic chemistry underlying the bimetallic synergy, (2) mimic the enzymatic reactivities with synthetic bimetallic catalysts, and (3) develop new reactions that are beyond the scope of what biology accomplishes itself.
High Power Radical Battery
Conversion and storage of renewable energy to electrical power are key challenges across the world for realizing net zero carbon emission. On a smaller scale, further breakthroughs of secondary batteries are required to fulfill the future desires for electric vehicles. With the driving range of commercial EV now approaches 300 miles, the slow charging rate of the current lithium-ion battery technology has become one of the most pressing issues that the electric vehicle industry faces today. The Zhang lab seeks to develop a general approach to prepare high rate organic radical battery. Our goal is to synthesize redox-active molecules with multiple reversible redox couples and systematically optimize their performance in batteries.
Metal-free Energy Conversion
In nature, enzymes exploit organic functional groups to construct well-defined reaction microenvironments that recognize substrates, activate substrates and minimize undesirable side reactions by protecting the reactive intermediates in inert confinement, thereby allowing incompatible reactions to proceed in parallel. We are interested in designing all organic catalysts that capture small molecules, particularly those that carry a positive or negative charge. These studies will lead to new all organic molecular catalysts for multielectron transformations, such as proton reduction, carbon dioxide reduction, and oxygen evolution.
Stauber J. M., Zhang, S., Jiang, Y., Avena, L., Stevenson, K. G., Cummins, C. C., “Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization and Electrochemical Evaluation for Non-Aqueous Redox-Flow Battery Applications,” J. Am. Chem. Soc., 2018, 140, 538-541.
Zhang, S.†; Nava, M. J.†; Chow, G. K.; Britt, R. D.; Nocera, D. G.*; Cummins, C. C.*, “On the Incompatibility of Metal-Air Battery Technology with CO2.” Chem. Sci., 2017, 8, 6117 – 6122. † equal contribution.
Morasch, R.; Kwabi, D. G.; Tulodziecki, M.; Risch, M.; Zhang, S.; Shao-Horn, Y. “Insights into Electrochemical Oxidation of NaO2 in Na-O2 Batteries via Rotating Ring Disk and Spectroscopic Measurements” ACS Appl. Mater. Interfaces, 2017, 9, 4374-4381.
Zhang, S.; Fallah, H.; Gardner, E. J.; Kundu, S.; Bertke, J. A.; Cundari, T. R.; Warren, T. H. “A Dinitrogen Dicopper(I) Complex via a Mixed-Valence Dicopper Hydride.” Angew. Chem., Int. Ed. 2016, 55, 9927 –9931.
Zhang, S.; Melzer, M. M.; Sen, S. N.; Çelebi-Ölcü̧m, N.; Warren, T. H. “A Motif for Reversible Nitric Oxide Interactions in Metalloenzymes.” Nat. Chem. 2016, 8, 663-669.
Zhang, S.; Çelebi-Ölcü̧m, N.; Melzer, M. M.; Houk, K. N.; Warren, T. H. “Copper(I) Nitrosyls from Reaction of Copper(II) Thiolates with S‑Nitrosothiols: Mechanism of NO Release from RSNOs at Cu.” J. Am. Chem. Soc., 2013, 135, 16746-16749.
Zhang, S.; Warren, T.H. “Three Coordinate Model for CuA Electron-Transfer Site.” Chem. Sci., 2013, 4, 1786-1792.
Melzer, M. M.; Mossin, S.; Cardenas, A. J. P.; Williams, K. D.; Zhang, S.; Meyer, K.; Warren, T. H. “A Copper(II) Thiolate from Reductive Cleavage of an S-Nitrosothiol.” Inorg. Chem., 2012, 51, 8658-8660.
The Zhang group is looking for graduate and undergraduate students who are interested in synthetic chemistry, bioinorganic chemistry, energy conversion, or energy storage. Contact Shiyu for more information.