Sensitivity-enhanced solid-state NMR spectroscopy of materials

Our research is centered on the development of solid-state nuclear magnetic resonance (NMR) spectroscopy to enable the structure determination of catalysts and energy materials. Solid-state NMR spectroscopy has a low detection sensitivity which makes it challenging to elucidate the atomic-level structure of dilute species, surfaces, interfaces or defects, which are frequently the sites of interest in novel materials. Our group will develop powerful sensitivity enhancement approaches to accelerate solid-state NMR spectroscopy of materials.

Methodological advances will focus on the development of high field dynamic nuclear polarization (DNP), fast magic angle spinning (MAS) and indirect detection techniques to enable multinuclear, multidimensional solid-state NMR spectroscopy. We will apply these advanced solid-state NMR techniques to characterize catalytic and energy-relevant materials such as organometallic compounds, heterogeneous catalysts, nanomaterials, and porous solids such as zeolites and metal organic frameworks. While our lab will primarily focus on experimental work, our scientific approach will be supported by theory and computations to investigate chemical structure. The comprehensive understanding provided by NMR in combination with other techniques will ultimately guide the rational design of efficient catalysts and materials to tackle global challenges such as climate change, rising energy demands and waste accumulation.

Research in our lab will be focused in three areas:

1. Design of dynamic nuclear polarization polarizing agents, methods and sample preparation techniques.
2. Development of indirect detection solid-state NMR strategies and pulse sequences.
3. Structure characterization of materials using solid-state NMR spectroscopy and other techniques.

Our lab will house state-of-the-art 400 MHz MAS DNP and 600 MHz Bruker solid-state NMR spectrometers. In addition, our group will have access to an 800 MHz solid-state NMR spectrometer at UVA Chemistry. Researchers in our group will gain expertise in the development and application of solid-state NMR spectroscopy of materials, and have opportunities to utilize liquid-state NMR, electron paramagnetic resonance (EPR) spectroscopy, density functional theory (DFT) and other characterization techniques.

Representative publications:

A. Venkatesh, G. Casano, R. Wei, Y. Rao, H. Lingua, H. Karoui, M. Yulikov, O. Ouari, L. Emsley. Rational Design of Dinitroxide Polarizing Agents for Dynamic Nuclear Polarization to Enhance Overall Sensitivity. Angew. Chem. Int. Ed. 2024, 63, e202317337. DOI: 10.1002/anie.202317337

A. Venkatesh, G. Casano, Y. Rao, F. De Biasi, F. A. Perras, D. J. Kubicki, D. Siri, S. Abel, H. Karoui, M. Yulikov, O. Ouari, L. Emsley. Deuterated TEKPol Biradicals and the Spin-Diffusion Barrier in MAS DNP. Angew. Chem. Int. Ed. 2023, 62, e202304844. DOI: 10.1002/anie.202304844

A. Venkatesh, D. Gioffrè, B. Atterberry, L. Rochlitz, S. Carnahan, Z. Wang, G. Menzildjian, A. Lesage, C. Coperét, A. Rossini. The Molecular and Electronic Structure of Isolated Platinum Sites Enabled by Expedient Measurement of ¹⁹⁵Pt Chemical Shift Anisotropy. J. Am. Chem. Soc. 2022, 144, 13511-13525. DOI: 10.1021/jacs.2c02300

A. Venkatesh, A. Lund, L. Rochlitz, R. Jabbour, C. P. Gordon, G. Menzildjian, J. Viger-Gravel, P. Berruyer, D. Gajan, C. Copéret, A. Lesage, A. J. Rossini. The Structure of Molecular and Surface Platinum Sites Determined by DNP-SENS and Fast MAS ¹⁹⁵Pt Solid-State NMR Spectroscopy. J. Am. Chem. Soc. 2020, 142, 18936-18945. DOI: 10.1021/jacs.0c09101

A. Venkatesh, X. Luan, I. Hung, F. A. Perras, W. Huang, A. J. Rossini. t₁-Noise Eliminated Dipolar Heteronuclear Multiple Quantum Coherence Solid-State NMR Spectroscopy. Phys. Chem. Chem. Phys. 2020, 22, 20815-20828. DOI: 10.1039/D0CP03511D

A full list of publications is available at my Google Scholar Page.