B.A. 1987 Ph.D. University of Oxford, 1991 Junior Research Fellow, Balliol College, University of Oxford 1990 Royal Society Postdoctoral Fellow, University of Nijmegen, the Netherlands 1991-1992

Materials Chemistry: Structure and Function We use a wide range of techniques, including solid state NMR and diffraction, to investigate local structure and the role that this plays in controlling the physical properties of a wide range of technologically-important, but disordered, materials. Conventional structural techniques, such as powder and single-crystal X-ray and neutron diffraction, characterize the "long-range" order, giving an average view of a structure; as a system becomes more disordered, these methods become progressively less useful. Even the most disordered system will, however, contain some local order. Solid-state nuclear magnetic resonance (NMR) probes the local environment of a particular nucleus, and is ideally suited to study such materials. Systems currently under investigation include lithium-ion batteries, fuel cell materials, catalysts and molecular sieves. By using a combination of short range (NMR) and long range (XRD) structural techniques, we can build up a detailed structure of the disordered compound - this helps determine how the particular material functions and provides insight as to how it can be improved.

Anionic conductors: We use 17O and 19F magic angle spinning NMR to study oxide and fluoride conduction. By identifying individual crystallographic or interstitial sites in often highly disordered materials, we can determine which anion sites are responsible for ionic conduction and obtain a much deeper understanding of how these materials function as "superionic" conductors. The ionic materials under investigation find potential uses as membranes in solid oxide fuel cells and as oxygen sensors.

Batteries: We use lithium NMR to investigate electrode materials for rechargeable lithium-ion batteries. The mechanism of lithium intercalation and deintercalation are probed by using 6Li/7Li NMR and the effect of this on local structure and electronic and magnetic properties are investigated. The NMR experiments are complemented by diffraction and X-ray absorption methods.

Environmental Chemistry: Our current interests involve the use of NMR to characterize (i) new layered materials designed to sorb high concentrations of pollutants and (ii) natural systems such as the hydrated iron and manganese oxides often found in soil samples; these oxides represent important sorbates for toxic ions such as Pb2+ or H2AsO4-.

Gas Sorption and Catalysis Projects in this area include the study of gas adsorption and reactivity on catalysts and zeolites. We are currently using multinuclear methods to examine nitridation of zeolites, to make materials with higher basicity.

"Nonequilibrium structure of Zn2SnO4 spinel nanoparticles", V. Sepelak, S.M. Becker, I. Bergmann, S. Indris, M. Scheuermann, A. Feldhoff, C. Kubel, M. Bruns, N. Sturzl, A.S. Ulrich, M. Ghafari, H. Hahn, C.P. Grey, K.D. Becker and P. Heitjans, J. Mater. Chem., 22, 3117-3126, (2012). "Isotropic high field NMR spectra of Li-Ion battery materials with anisotropy >1 MHz", I. Hung, L. Zhou, F. Pourpoint, C.P. Grey and Z. Gan, J. Am. Chem. Soc., 134, 1898-1901 (2012). "Crystal structure, physical properties, and electrochemistry of copper substituted LiFePO4 single crystals", S. Upreti, N.A. Chernova, J. Xiao, J.K. Miller, O.V. Yakubovich, J. Cabana, C.P. Grey, V.L. Chevrier, G. Ceder, J.L. Musfeldt, M.S. Whittingham, Chem. Mat., 24, 166-173, (2012). "Nanoparticulate TiO2 B: An anode for lithium-ion batteries", Y. Ren, Z. Liu, F. Pourpoint, A.R. Armstrong, C.P. Grey, P.G. Bruce, Angew. Chem. Int. Ed., 51, 2164-2167, (2012). "Thermal phase transformations in LaGaO3 and LaAlO3 perovskites: An experimental and computational solid-state NMR study", F. Blanc, D.S. Middlemiss, L. Buannic, J.L. Palumbo, I. Farnan and C.P. Grey, Solid State Nucl. Magn. Reson., 42, 87-97, (2012). "7Li MRI of Li batteries reveals location of microstructural lithium", S. Chandrashekar, S.M. Trease, H.J. Chang, L.S. Du, C.P. Grey and A. Jerschow, Nat. Mater., 11, 311-315, (2012). "In situ NMR of lithium ion batteries: Bulk susceptibility effects and practical considerations", N.M. Trease, L. Zhou, H.J. Chang, B.Y. Zhu, C.P. Grey, Solid State Nucl. Magn. Reson., 42,62-70(2012). "Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide", D. Qian, Y. Hinuma, H. Chen, L.S. Du, K.J. Carroll, G. Ceder, C.P. Grey, Y.S. Meng, J. Am. Chem. Soc., (2012). DOI: 10.1021/ja300868e. "Solid-state MAS NMR studies of brønsted Acid sites in zeolite h-mordenite", H. Huo, L. Peng, Z. Gan, C.P. Grey, J. Am. Chem. Soc., 134, 9708-9720, (2012). "Probing cation and vacancy ordering in the dry and hydrated yttrium substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: Implications for proton mobility", L. Buannic, F. Blanc, D.S. Middlemiss, C.P. Grey,
J. Am. Chem. Soc., DOI: 10.1021/ja304712v (2012). "Degradation and (de)lithiation processes in the high capacity battery material LiFeBO", S.H. Bo, F. Wang, Y. Janssen, D.L. Zeng, K.W. Nam, W.Q. Xu, L.S. Du, J. Graetz, X.Q. Yang, Y.M. Zhu, J.B. Parise, C.P. Grey, P.G. Khalifah, J. Mater. Chem., 22, 8799-8809, (2012). DOI: 10.1039/c2jm16436a "Investigation of cation ordering in triclinic sodium birnessite via Na-23 MAS NMR spectroscopy", K.A. Aldi, J. Cabana, P.J. Sideris, C.P. Grey, American Mineralogist, 97, 883-889, DOI: 10.2138/am.2012.3933. (2012). "Structural Modulation in the High Capacity Battery Cathode Material LiFeBO(3)", Y. Janssen, D.S. Middlemiss, S.H. Bo, C.P. Grey, P.G. Khalifah, J. Am. Chem. Soc., 1520-5126, DOI: 10.1021/ja301881c (2012). "Direct Detection of Discharge Products in Lithium-Oxygen Batteries by Solid-State NMR Spectroscopy", M. Leskes, N.E. Drewett, L.J. Hardwick, P.G. Bruce, G.R. Goward, C.P. Grey, Angew Chem. Int. Ed. Engl., 1521-3773, DOI: 10.1002/anie.201202183 (2012). "Pair distribution function analysis and solid state NMR studies of silicon electrodes for lithium ion batteries: Understanding the (De)lithiation mechanisms", B. Key, M. Morcrette, J-M. Tarascon and C.P. Grey, J. Am. Chem. Soc., 133, 503-512, (2011). "LiCoO2 Concaved cuboctahedrons from symmetry-controlled topological reactions" H.L. Chen, L.J. Wu, L.H. Zhang, Y.M. Zhu and C.P. Grey, J. Am. Chem. Soc., 133, 262–270, (2011). "Measuring Brønsted acid site O−H distances in zeolites HY and HZSM-5 with low-temperature 17O-1H double resonance MAS NMR spectroscopy", H. Huo, L.M. Peng and C.P. Grey, J. Phys. Chem. C, 115, 2030–2037, (2011). "High-resolution 27Al MAS NMR spectroscopic studies of the response of spinel aluminates to mechanical action", V. Sepelak, I. Bergmann, S. Indris, A. Feldhoff, H. Hahn, K. Dieter Becker, C.P. Grey and P. Heitjans, J. Mater. Chem., 21, 8332-8337, (2011). "Effect of ball-milling and lithium insertion on the lithium mobility and structure of Li3Fe2(PO4)3", J. Cabana, J. Shirakawa, M. Nakayama, M. Wakihara and C.P. Grey, J. Mater. Chem., 21, 10012-10020, (2011). "Characterization and carbonization of highly oriented poly(diiododiacetylene) nanofibers", L. Luo, C. Wilhelm, C.N. Young, C.P. Grey, G.P. Halada, K. Xiao, I.N. Ivanov, J.Y. Howe, D.B. Geohegan and N.S. Goroff, Macromolecules, 44, 2626-2631, (2011). "Liquid phase aldol condensation reactions with MgO-ZrO2 and shape-selective nitrogen-substituted NaY", W.Q. Shen, G.A. Tompsett, K.D. Hammond, R. Xing, F. Dogan, C.P. Grey, W.C. Conner, S.M. Auerbach and G.W. Huber, Appl. Catal. A-Gen., 392, 57-68, (2011). "C-13 solid state NMR suggests unusual breakdown products in SEI formation on lithium ion electrodes", N. Leifer, M.C. Smart, G.K.S. Prakash, L. Gonzalez, L. Sanchez, K.A. Smith, P. Bhalla, C.P. Grey and S.G. Greenbaum, J. Electrochem. Soc., 158, A471-A480, (2011). "Insight into the local magnetic environments and deuteron mobility in jarosite (AFe3(SO4)2(OD,OD2)6, A = K, Na, D3O) and hydronium alunite ((D3O)Al3(SO4)2(OD)6), from variable-temperature 2H MAS NMR spectroscopy", U.G. Nielsen, I. Heinmaa, A. Samoson, J. Majzlan and C.P. Grey, Chem. Mat., 23,3176-3187, (2011). "Citric acid- and ammonium-mediated morphological transformations of olivine LiFePO4 particles", Z. Lu, H. Chen, R. Robert, B.Y.X. Zhu, J. Deng, L. Wu, C.Y. Chung and C.P. Grey, Chem. Mat., 23, 2848-2859, (2011). "Conversion reaction mechanisms in lithium ion batteries: Study of the binary metal fluoride electrodes", F. Wang, R. Robert, N.A. Chernova, N. Pereira, F. Omenya, F. Badway, X. Hua, M. Ruotolo, R. Zhang, L. Wu, V. Volkov, D. Su, B. Key, M.S. Whittingham, C.P. Grey, G.G. Amatucci, Y. Zhu, J. Graetz, J. Am. Chem. Soc., 133,18828-18836 (2011). "Defects in doped LaGaO3 anionic conductors: Linking NMR spectral features, local environments and defect thermodynamics", F. Blanc, D.S. Middlemiss, Z. Gan, C.P. Grey, J. Am. Chem. Soc., 133, 17662-17672 (2011). "Real-time NMR studies of electrochemical double-layer capacitors", H. Wang, T.K.J. Köster, N.M. Trease, J. Segalini, P.-L. Taberna, P. Simon, Y. Gogotsi and C.P. Grey, J. Am. Chem. Soc., 133, 19270-19273 (2011). "Room-temperature carbonization of poly(diiododiacetylene) by reaction with Lewis bases" L. Luo, D. Resch, C. Wilhelm, C.N. Young, G.P. Halada, R.J. Gambino, C.P. Grey, N.S. Goroff, J. Am. Chem. Soc., 133, 19274-19277 (2011). "Resolving the different silicon clusters in Li12Si7 by 29Si and 6,7Li solid-state NMR spectroscopy", T.K.-J. Köster, E. Salager, A.J. Morris, B. Key, V. Seznec, M. Morcrette, C.J. Pickard and C.P. Grey, Angew. Chem. Int. Ed., 50, (2011). "Energetics of hydrogen/lithium complexes in silicon analyzed using the Maxwell construction", A.J. Morris, C.P. Grey, R.J. Needs and C.J. Pickard, Phys. Rev. B., 84, 224106-1 -5, (2011). "Investigation of the structural changes in Li[NiyMnyCo(1−2y)]O2 (y = 0.05) upon electrochemical lithium deintercalation", D.L. Zeng, J. Cabana, W.S. Yoon and C. P. Grey, Chem. Mater., 22, 1209-1219, (2010). "High rate performance of lithium manganese nitride and oxynitride as negative electrodes in lithium batteries", J. Cabana, C.M. Ionica-Bousquet, C.P. Grey and M. R. Palacín, Electrochem. Commun., 12,315-318, (2010). "MAS NMR study of the metastable solid solutions found in the LiFePO4/FePO4 system", J. Cabana, J. Shirakawa, G.Y. Chen, T.J. Richardson and C.P. Grey, Chem. Mater., 22, 1249-1262, (2010). "Optimizing the synthesis of nitrogen-substituted zeolites", K.D. Hammond, M. Gharibeh, G.A. Tompsett, F. Dogan, A.V. Brown, C.P. Grey, S.M. Auerbach and W.C. Conner, Jr., Chem. Mater., 22, 130-142, (2010). "Investigation of surface structures by powder diffraction: A differential pair distribution function study on arsenate sorption on ferrihydrite", R. Harrington, D.B. Hausner, N. Bhandari, D.R. Strongin, K.W. Chapman, P.J. Chupas, D.S. Middlemiss, C.P. Grey and J.B. Parise, Inorg. Chem., 49, 325-330, (2010). "Solid-state NMR calculations for metal oxides and gallates: Shielding and quadrupolar parameters for perovskites and related phases", D.S. F. Blanc, C.J. Pickard and C.P. Grey, J. Magn. Reson., 204, 1-10, (2010). "Linking local environments and hyperfine shifts: A combined experimental and theoretical 31P and 7Li solid–state NMR study of paramagnetic Fe(III) phosphates", J. Kim, D.S. Middlemiss, N.A. Chernova, B.Y.X. Zhu, C. Masquelier and C.P. Grey, J. Am. Chem. Soc., 132, 16825-16840, (2010). "In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries", R. Bhattacharyya, B. Key, H. L. Chen, A.S. Best, A.F. Hollenkamp and C.P. Grey, Nat. Mater., 9, 504-520 (2010). "Surface science studies of environmentally relevant iron (oxy)hydroxides ranging from the nano to the macro-regime", D.R. Strongin, C.P. Grey, J.B. Parise and J.D. Kubicki, Surf. Sci., 604, 1065-1069, (2010). "2H and 7Li solid-state MAS NMR study of local environments and lithium adsorption on the iron (III) oxyhydroxide, akaganeite (b-FeOOH)," J. Kim and C.P. Grey, Chem. Mater., 22, 5453-5462, (2010). "Chemically modified Ba6Mn24O48 tunnel manganite as a lithium insertion host," E.A. Pomerantseva, T.L. Kulova, D.L. Zeng, A.M. Skundin, C.P. Grey, E.A. Goodilin and Y.D. Tretyakov, Solid State Ionics, 181, 1002-1008, (2010). "Structural complexity of layered-spinel composite electrodes for Li-ion batteries", J. Cabana, C.S. Johnson, X.Q. Yang, K.Y. Chung, W.S. Yoon, S.H. Kang, M.M. Thackeray and C.P. Grey, J. Mater. Res., 25, 1601-1616, (2010). "Probing the local structures and protonic conduction pathways in scandium substituted BaZrO3 by multinuclear solid-state NMR spectroscopy" L. Buannic, F. Blanc, I. Hung, Z.H. Gan and C.P. Grey, J. Mater. Chem., 20, 6322-6332, (2010).

"Spin crossover in the CsFeII[Cr-III(CN)6] Prussian blue analog: Phonons and thermodynamics from hybrid functionals", D.S. Middlemiss, D. Portinari, C.P. Grey , C.A. Morrison and C.C. Wilson, Phys. Rev. B, 81, 184410, (2010).