MIDNP · Metal Ions Dynamic Nuclear Polarization: Novel Route for Probing Functional Materials with Sensitivity and Selectivity

Materials with specific electrical, optical or chemical properties often derive their special functions from small perturbations in their composition or structure. Thus, rational design of new functional materials demands sensitive and versatile determination of structural and compositional properties, a very difficult goal not presently available. The overarching goal of this ERC project is to develop a novel route for Magic-Angle Spinning Dynamic Nuclear Polarization (MAS-DNP) as an enabling methodology in materials science, introducing new opportunities for investigating and designing functional materials.Solid State Nuclear Magnetic Resonance (ssNMR) spectroscopy is an excellent probe for local order/disorder, but unfortunately its sensitivity is limited. DNP, a process whereby the large electron spin polarization is transferred to the nuclear spins, had greatly expanded the range of materials systems and questions that can be probed by ssNMR. However, it commonly relies on the use of exogenous nitroxide radicals, thereby limiting its utilization in materials science to nonreactive surfaces. We propose to develop Metal Ions DNP (MIDNP) utilizing paramagnetic dopants as endogenous polarization agents in the bulk. To effectively harness the electron spin polarization of the dopants for higher sensitivity, we will (a) address challenges such as the effect of bonding, spin interactions and relaxation on DNP via a mechanistic study of carefully selected dopants in energy materials; (b) Develop new techniques for NMR spectral assignment and explore alternative DNP mechanisms for paramagnetic solids; (c) Expand the approach for sensitizing the detection of surfaces and interfaces and elucidate the critical role of surface chemistry in the efficacy of energy storage materials.MIDNP will provide a novel, sensitive alternative for probing the structure and composition of new materials and will transform the utilization of ssNMR in the study of functional materials.