Miller, Alexander J. M. - The University of North Carolina at Chapel Hill

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Miller, Alexander J. M. Professor 收藏完善纠错
The University of North Carolina at Chapel Hill Department of Chemistry
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个人简介

Education 2011 Ph.D. in Chemistry California Institute of Technology, Pasadena, CA Advisors: John E. Bercaw and Jay A. Labinger 2005 B.S. in Chemistry University of Chicago, Chicago, IL Advisor: Gregory L. Hillhouse Professional Experience 7/2022–present Professor, Department of Chemistry University of North Carolina at Chapel Hill, Chapel Hill, NC 1/2023-present Director, Solar Energy Research Center University of North Carolina at Chapel Hill, Chapel Hill, NC 7/2021-present Director of Graduate Studies, Department of Chemistry University of North Carolina at Chapel Hill, Chapel Hill, NC 7/2018−6/2022 Associate Professor, Department of Chemistry University of North Carolina at Chapel Hill, Chapel Hill, NC 8/2018−7/2021 Deputy Director, Department of Energy AMPED Energy Frontier Research Center University of North Carolina at Chapel Hill, Chapel Hill, NC 7/2012−6/2018 Assistant Professor, Department of Chemistry University of North Carolina at Chapel Hill, Chapel Hill, NC 1/2011−6/2012 Dreyfus Environmental Chemistry Postdoctoral Fellow Advisors: Karen I. Goldberg and James M. Mayer University of Washington, Seattle, WA Honors 2021 Distinguished Speaker of the Year award, NC Section of the American Chemical Society 2019 J. Carlyle Sitterson Award for Teaching First-Year Students, UNC 2018 Chemical Communications Emerging Investigator Lectureship 2017 Organometallics Distinguished Author Award 2016 Sloan Research Fellowship 2016 National Science Foundation CAREER Award 2016 Early Excellence Profile in Journal of Physical Organic Chemistry 2014 University Research Council James Moeser Award for Distinguished Research, UNC 2013 Junior Faculty Development Award, UNC 2013 Named to Forbes “30 Under 30: Energy” list 2011 Camille and Henry Dreyfus Environmental Chemistry Postdoctoral Fellow 2011 Herbert Newby McCoy Award for Outstanding Graduate Research, Caltech

研究领域

The Miller group takes a mechanism-guided approach to the discovery of new catalysts for the sustainable synthesis of chemicals and fuels. Our approach starts with the design and synthesis of transition metal catalysts, then shifts to examining catalyst performance with a focus on understanding reaction mechanism in order to inform catalyst improvements. Externally Controlled Catalysis: Switchable and Tunable Reactivity Chemists are constantly seeking new ways to control catalytic activity, selectivity, and longevity. The traditional (and still highly successful) approach to catalyst discovery involves tuning metal and ligand properties until a desired reaction outcome is obtained. An alternative and complementary approach involves preparing a single catalyst that can respond to external additives (also called stimuli or cofactors) to adopt multiple different structures, each with unique reactivity. This “controlled catalysis” approach could streamline catalyst discovery and enable new reactivity traits, such as temporally controlled generation of different products with a single catalyst system or preparation of advanced copolymer morphologies. To explore these applications, organometallic chemists need an improved fundamental understanding of how to design and employ controlled catalysts. We have developed a new family of pincer ligands that utilize an aza-crown ether as one of the donor arms to promote cation-controllable reactivity based on cation-macrocycle interactions occurring near the active site of a transition metal catalyst. The Miller lab is exploring small molecule activation chemistry that takes advantage of the unique pincer-crown ether ligand motif. Metal Hydride Photochemistry and Thermochemistry Hydride transfer is a critical step in many reactions, including energy-storing reactions to produce chemical fuels, such as hydrogen evolution and CO2 reduction. What if the hydride transfer step could be controlled using visible light? The ability to trigger a hydride transfer at will, or generate a more reactive species using visible light, could lead to dramatically improved catalysts. We are working to realize this goal by understanding the thermodynamic and kinetic factors associated with excited state hydride transfer to a range of substrates. Dinitrogen Reduction The catalytic synthesis of ammonia via the Haber-Bosch process stands as one of the most transformative chemistry discoveries in history. Because this process relies on fossil-fuel-derived hydrogen gas, however, current ammonia synthesis methods have dire environmental consequences. We envision an alternative ammonia synthesis based on electrocatalytic reduction of N2 to ammonia. Our research in this area is focuses on a pathways in which reductive N2 binding and formation of an end-on bridging N2 complex is followed by splitting into a pair of metal nitrides, followed by proton-coupled electron transfer (PCET) to release ammonia. Carbon Dioxide Reduction The reduction of carbon dioxide to fuels represents a promising approach to sustainable energy conversion. Molecular electrocatalysts hold promise in this area due to their high selectivity and tunability. We have focused on catalysts that pair one “redox-active” ligand with another strong-trans-effect ligand. By minimizing electronic coupling between the site that accepts electrons and the site that controls the rates of key chemical steps, activity and overpotential can be tuned independently. Although the trans effect is a foundational principle of organometallic chemistry, it had not been systematically studied in the context of CO2 electroreduction.

近期论文

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Acosta-Calle, S.; Huebsch, E.Z.; Kolmar, S.S.; Whited, M.T.; Chen, C.-H.; Miller, A.J.M. “Regulating Access to Active Sites via Hydrogen Bonding and Cation-Dipole Interactions: A Dual Cofactor Approach to Switchable Catalysis” Cloward, I.N.; Liu, T.; Rose, J.; Bonn, A.G.; Jurado, T.; Chambers, M.B.; Pitman, C.L.; ter Horst, M.A.; Miller, A.J.M. “Catalyst Self-Assembly Accelerates Bimetallic Light-Driven Electrocatalytic H2 Evolution in Water.” Yoo, C.; Bhattacharya, S.; See, X.Y.; Cunningham, D.W.; Acosta-Calle, S.; Perri, S.T.; West, N.M.; Mason, D.C.; Meade, C.D.; Osborne, C.W.; Turner, P.W.; Kilgore, R.W.; King, J.; Cowden, J.H.; Grajeda, J.; Miller, A.J.M. “Nickel-catalyzed ester carbonylation promoted by imidazole-derived carbenes and salts.” Science 2023, 382, 815-820. McMillion, N.D.; Bruch, Q.J.; Chen, C.-H.; Hasanayn, F.; Miller, A.J.M. “Synthesis and Bonding Analysis of Pentagonal Bipyramidal Rhenium Carboxamide Oxo Complexes” Dalton Trans. 2023, 52, 15115-15123. Elsby, M.R.; Espinosa, M.R.; Ertem, M.Z.; Deziel, A.P.; Hazari, N.; Miller, A.J.M.; Paulus, A.H.; Pecoraro, M.V. “Carbon Dioxide Insertion Reactions into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships Between Thermodynamic and Kinetic Hydricity” Organometallics 2023, 42, 3005-3012. McMillion, N.D.; Smith, A.M.; Miller, A.J.M. “Responsibility as a Foundation of Safety Culture.” ACS Chem. Health Saf. 2023, 30, 3, 105-107 Acosta-Calle, S.; Miller, A.J.M. “Tunable and Switchable Catalysis Enabled by Cation-Controlled Gating with Crown Ether Ligands.” Acc. Chem. Res. 2023, 56, 971–981. Dodge, H.M.; Natinsky, B.S.; Jolly, B.J.; Zhang, H.; Mu, Y.; Chapp, S.M.; Tran, T.V.; Diaconescu, P.L.; Do, L.H.; Wang, D.; Liu, C.; Miller, A.J.M. “Polyketones from Carbon Dioxide and Ethylene by Integrating Electrochemical and Organometallic Catalysis.” ACS Catal. 2023, 13, 4053–4059. Deng, S.; Jolly, B.; Wilkes, J.; Mu, Y.; Byers, J.; Do, L.; Miller, A.J.M.; Wang, D.; Liu, C.; Diaconescu, P.L. “Spatiotemporal control for integrated catalysis“ Nature Review Methods Primers 2023, 3, 28. Hasanayn, F.; Holland, P.L.; Goldman, A.S.; Miller, A.J.M. “Lewis Structures and the Bonding Classification of End-on Bridging Dinitrogen Transition Metal Complexes.” J. Am. Chem. Soc. 2023, 145, 4326–4342.. Bruch, Q.J.; McMillion, N.D.; Chen, C.-H.; Miller, A.J.M. “Oxidative Addition of a Phosphinite P–O Bond at Nickel.” Inorg. Chem. 2023, 62, 2389–2393. Hegg, A.S.; Mercado, B.Q.; Miller, A.J.M.; Holland, P.S. “Catalytic Reduction of Dinitrogen to Ammonia using Porphyrin-Molybdenum Catalysts.” Faraday Discussions, 2023, 243, 429-449 Farquhar, A.; Gardner, K.; Acosta-Calle, S.; Camp, A.; Chen, C.; Miller, A.J.M. “Cation-Controlled Olefin Isomerization Catalysis with Palladium Pincer Complexes.” Organometallics 2022, 41, 3366-3372. Assaf, E.A.; Gonell, S.; Chen, C.; Miller, A.J.M. “Accessing and Photo-Accelerating Low-Overpotential Pathways for CO2 Reduction: A Bis-Carbene Ruthenium Terpyridine Catalyst.” ACS Catal. 2022, 12, 12596-12606. Espinosa, M.R.; Ertem, M.Z.; Barakat, M.; Bruch, Q.J.; Deziel, A.P.; Elsby, M.R.; Hasanayn, F.; Hazari, N.; Miller, A.J.M.; Pecoraro, M.V.; Smith, A.M.; Smith, N.E. ” Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides.” J. Am. Chem. Soc. 2022, 144, 17939–17954. Bruch, Q.J.; Malakar, S.; Goldman, A.S.; Miller, A.J.M. “Mechanisms of Electrochemical N2 Splitting by a Molybdenum Pincer Complex.” Inorg. Chem. 2022, 61, 2307-2318. Gonell, S.; Assaf, E.A.; Lloret-Fillol, J.; Miller, A.J.M. “An Iron Bis(carbene) Catalyst for Low Overpotential CO2 Electroreduction to CO: Mechanistic Insights from Kinetic Zone Diagrams, Spectroscopy, and Theory.” ACS Catal. 2021, 11, 15212–15222. Stratakes, B.M.; Wells, K.A.; Kurtz, D.A.; Castellano, F.N.; Miller, A.J.M. “Photochemical H2 Evolution from Bis(diphosphine) Nickel Hydrides Enables Low-Overpotential Electrocatalysis.” J. Am. Chem. Soc. 2021, 143, 21388–21401. Stratakes, B. M.; Dempsey, J. L.; Miller, A.J.M. “Determining the Overpotential of Electrochemical Fuel Synthesis Mediated by Molecular Catalysts: Recommended Practices, Standard Reduction Potentials, and Challenges.” ChemElectroChem 2021, 8, 1–21. Yoo, C.; Miller, A.J.M. “Stepwise Iodide-Free Methanol Carbonylation via Methyl Acetate Activation by Pincer Iridium Complexes.” J. Am. Chem. Soc. 2021, 143, 12633–12643. Yamout, L. S.; Ataya, M.; Hasanayn, F.; Holland, P.; Miller, A.J.M.; Goldman, A. “Understanding Terminal versus End-on N2 Coordination in Transition Metal Complexes.” J. Am. Chem. Soc. 2021,143, 9744–9757. Kaphan, D.; Brereton, K.; Klet, R.; Witzke, R.; Miller, A.J.M.; Mulfort, K.; Delferro, M.; Tiede, D. “Photocatalytic Transfer Hydrogenation in Water: Insight into Mechanism and Catalyst Speciation.” Organometallics. 2021, 40, 1482–1491. Shada, A.D.R.; Miller, A.J.M.; Emge, T.J.; Goldman, A.S. “Catalytic Dehydrogenation of Alkanes by PCP–Pincer Iridium Complexes Using Proton and Electron Acceptors.” ACS Catal. 2021, 11, 3009–3016. Camp, A.; Kita, M.; Blackburn, P. T.; Dodge, H.; Chen, C.H.; Miller, A.J.M. “Selecting Double Bond Positions with a Single Cation-Responsive Iridium Olefin Isomerization Catalyst.” J. Am. Chem. Soc. 2021, 143, 2792-2800. Hu, J.; Bruch, Q.J.; Miller, A.J.M. “Temperature and Solvent Effects on H2 Splitting and Hydricity: Ramifications on CO2 Hydrogenation by a Rhenium Pincer Catalyst.” J. Am. Chem. Soc. 2021, 143, 945-954. Gonell, S.; Lloret-Fillol, J.; Miller, A.J.M. “An Iron Pyridyl-Carbene Electrocatalyst for Low Overpotential CO2 Reduction to CO.” ACS Catal. 2021, 11, 615-626. Dodge, H. M.; Kita, M. R.; Chen, C.; Miller, A.J.M. “Identifying and Evading Olefin Isomerization Deactivation Pathways Resulting from Ion-Tunable Hemilability.” ACS Catal. 2020, 10, 13019-13030. Yoo, C.; Dodge, H. M.; Farquhar, A. H.; Gardner, K. E.; Miller, A.J.M. “Decarbonylative ether dissection by iridium pincer complexes.” Chem. Sci. 2020, 11, 12130-12138. Bruch, Q.J.; Connor, G.P.; McMillion, N.D.; Goldman, A.S.; Hasanayn, F.; Holland, P.; Miller, A.J.M. “Considering Electrocatalytic Ammonia Synthesis via Bimetallic Dinitrogen Cleavage.” ACS Catal. 2020, 10, 10826-10846. Brereton, K.R.; Smith, N.E.; Hazari, N.; Miller, A.J.M. “Thermodynamic and kinetic hydricity of transition metal hydrides” Chem. Soc. Rev. 2020, 49, 7929-7948. Stratakes, B.M.; Miller, A.J.M. “H2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst” ACS Catal. 2020, 10, 9006-9018. Hochman, G.; Goldman, A.; Felder, F. A.; Mayer, J.; Miller, A. J. M.; Holland, P. L.; Goldman, L.; Manocha, P.; Song, Z.; Aleti, S. “The Potential Economic Feasibility of Direct Electrochemical Nitrogen Reduction as a Route to Ammonia.” ACS Sustainable Chem. Eng. 2020, 8, 8938-8948. Gonell, S.; Assaf, E. A.; Duffee, K.; Schauer, C.K.; Miller, A. J. M. “Kinetics of the Trans Effect in Ruthenium Complexes Provide Insight into the Factors that Control Activity and Stability in CO2 Electroreduction.” J. Am. Chem. Soc. 2020, 142, 8980-8999. Farquhar, A. H.; Brookhart, M.; Miller, A. J. M. “Oligomerization and Polymerization of 5-ethylidene-2-norbornene by Cationic Palladium and Nickel Catalysts.” Polym. Chem. 2020, 11, 2576-2584. Barrett, S. M.; Stratakes, B. M.; Chambers, M.; Kurtz, D. A.; Pitman, C. L.; Dempsey, J. L.; Miller, A. J. M. “Mechanistic Basis for Tuning Iridium Hydride Photochemistry from H2 Evolution to Hydride Transfer Hydrodechlorination.” Chem. Sci. 2020, 11, 6442-6449. Bruch, Q. J.; Miller, A. J. M. “A Bis(arylphosphinito)amide Pincer Ligand that Binds Nickel Forming Six-Membered Metallacycles.” Polyhedron, 2020, 179, 114380. van Alten, R. S.; Wätjen, F.; Demeshko, S.; Miller, A. J. M.; Würtele, C.; Siewert, I.; Schneider, S. “(Electro-)chemical Splitting of Dinitrogen with a Rhenium Pincer Complex.” Eur. J. Inorg. Chem. 2020, 15, 1402-1410.

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