Research Inorganic

Inorganic Research

Inorganic chemistry is a discipline that spans areas ranging from materials chemistry to organic synthesis and on to broad problems in energy. The Inorganic Division at the University of North Carolina ranks among the top ten nationally and has been a major strength of the Chemistry Department for decades.

Graduate students in the Inorganic Division are exposed to an exciting research environment, cutting-edge characterization and catalysis facilities, an exciting educational curriculum, and a collegial mentoring environment, all of which together provide an excellent foundation for future careers in industry and academia.

The Inorganic Division is deeply involved in several overarching departmental themes. Catalysis is a particularly prominent research area at UNC, with ongoing activities involving the synthesis of complexes for a broad range of homogeneous catalysis applications – energy, biomass remediation, small molecule synthesis, site-selective activation, asymmetric catalysis, and polymerization – and the exploitation of transition metal complexes in photocatalytic water splitting and carbon dioxide reduction and for applications in biotechnology.

Functional materials chemistry is another strength at UNC, with highly visible research activities in solar fuels, nanoparticles/quantum dots, and photovoltaics.

Recent Research Results

Identifying and Evading Olefin Isomerization Catalyst Deactivation Pathways Resulting from Ion-Tunable Hemilability

Hemilabile ligands are found in many leading organometallic catalysts, but it can be challenging to tune the degree of hemilability in a particular catalyst. This work explores the impact of cation-tunable hemilability on the speciation of iridium(III) pincer-crown ether catalysts during high-activity olefin isomerization.

Tunneling and Thermally Activated Electron Transfer in Dye-Sensitized SnO2 vertical bar TiO2 Core vertical bar Shell Nanostructures

A model is proposed wherein ET in annealed SnO2|TiO2 is rate-limited by electron transport in the shell, while ET in unannealed SnO2|TiO2 is rate-limited by electron escape from the core. The model is consistent with a comparative study of ZrO2|TiO2 materials for which insulating ZrO2 cores are energetically inaccessible to electrons. These mechanistic insights provide guidance on how to manipulate core|shell nanostructures for applications in solar water splitting.

Considering Electrocatalytic Ammonia Synthesis via Bimetallic Dinitrogen Cleavage

Despite advances in the development of molecular catalysts capable of reducing dinitrogen to ammonia using proton donors and chemical reductants, few molecular electrocatalysts have been discovered. This Perspective considers the prospects of electrocatalyst development based on a mechanism featuring the cleavage of N-2 into metal nitride complexes.

Representative Publications

ACS Catalysis.
Identifying and Evading Olefin Isomerization Catalyst Deactivation Pathways Resulting from Ion-Tunable Hemilability Henry M. Dodge, Matthew R. Kita, Chun-Hsing Chen, and Alexander J. M. Miller ACS Catalysis 2020 10 (21), 13019-13030 DOI: 10.1021/acscatal.0c03784

The Journal of Physical Chemistry.
Tunneling and Thermally Activated Electron Transfer in Dye-Sensitized SnO2|TiO2 Core|Shell Nanostructures Rachel E. Bangle, Michael J. Mortelliti, Ludovic Troian-Gautier, Jillian L. Dempsey, and Gerald J. Meyer The Journal of Physical Chemistry C 2020 124 (45), 25148-25159 DOI: 10.1021/acs.jpcc.0c08200

Proton-Coupled Electron Transfer Kinetics for the Photoinduced Generation of a Cobalt(III)-Hydride Complex.
Kurtz, Daniel A., Dempsey, Jillian L..
Inorg. Chem. 2019, 58, 24, 16510-16517

Delayed Photoacidity Produced through the Triplet–Triplet Annihilation of a Neutral Pyranine Derivative.
J. Christian Lennox, Evgeny O. Danilov, Jillian L. Dempsey.
Phys. Chem. Chem. Phys., 2019, 21, 16353-16358

On Decomposition, Degradation, and Voltammetric Deviation: the Electrochemist's Field Guide to Identifying Precatalyst Transformation.
Lee, Katherine, McCarthy, Brian, Dempsey, Jillian.
Chemical Society Review, Volume: 48, Issue: 11, Pages: 2927-2945

Electron-Promoted X-Type Ligand Displacement at CdSe Quantum Dot Surfaces.
Electron-Promoted X-Type Ligand Displacement at CdSe Quantum Dot Surfaces.
Nano Lett., 2019, 19 (2), pp 1151–1157

Stable Molecular Surface Modification of Nanostructured, Mesoporous Metal Oxide Photoanodes by Silane and Click Chemistry.
Wu, Lei, Eberhart, Michael, Shan, Bing, Nayak, Animesh, Brennaman, M. Kyle), Miller, Alexander J. M., Shao, Jing, Meyer, Thomas J..
ACS Appl. Mater. Interfaces 2019, 11, 4, 4560-4567

Charge Transfer from Upconverting Nanocrystals to Semiconducting Electrodes: Optimizing Thermodynamic Outputs by Electronic Energy Transfer.
Bing Shan, Ting-Ting Li, M. Kyle Brennaman, Animesh Nayak, Lei Wu, and Thomas J. Meyer.
J. Am. Chem. Soc., 2019, 141 (1), pp 463–471

Switching between Stepwise and Concerted Proton-Coupled Electron Transfer Pathways in Tungsten Hydride Activation.
Tao Huang, Eric S. Rountree, Andrew P. Traywick, Magd Bayoumi, and Jillian L. Dempsey.
J. Am. Chem. Soc., 2018, 140 (44), pp 14655–14669