The University of Liverpool - DEPARTMENT OF CHEMISTRY - Professor Matthew J. Rosseinsky DPhil, FRSC, FRS

Inorganic Materials Chemistry

Our research targets the synthesis of new materials. The motivation for this work is both to discover new physical and chemical properties for enhanced fundamental understanding and to provide improved figures-of-merit for applications in sectors such as energy storage and generation, communications and separation and catalysis. We adopt an approach involving a broad range of synthesis and characterisation methods (including neutron and synchrotron X-ray diffraction), and apply computational methods in collaboration with Dr George Darling to enhance understanding of the new materials. Much of this work is carried out in collaboration with Dr. John Claridge, Professor Andrew Cooper and Professor Paul Chalker (Materials, Liverpool), as well as many UK and international partner groups. Several current research areas are outlined below.

A list of publications to the end of February 2009 is available

Transition metal oxides

Transition metal oxides display exciting and important physical properties such as high temperature superconductivity, colossal magnetoresistance and ferroelectricity. We are developing new chemistry of the transition metal oxides, addressing targets such as lead-free replacements for the widely used ferroelectric lead zirconate titanate and new multiferroic materials where properties such as ferroelectricity and ferromagnetism are coupled in the same material. In addition to conventional ceramic synthesis methods we are developing low-temperature synthesis routes, synthesis of complex oxide materials in nanoparticle form, and the application of high pressure synthesis routes to new transition metal oxides.

High-pressure synthesis (to 70 kbar, 1600 C)	BiTi3/8Fe2/8Mg3/8O3 – a lead-free ferroelectric

Representative publications

High pressure bulk synthesis and characterization of the predicted multiferroic Bi(Fe_1/2Cr_1/2)O₃

M.R. Suchomel, C.I. Thomas, M. Allix, M.J. Rosseinsky, A.M. Fogg, M.F. Thomas

Applied Physics Letters 90, article number 112909, 2007.

A pure bismuth A site polar perovskite synthesized at ambient pressure, C. A. Bridges, M. Allix, M. R. Suchomel, X. J. Kuang, I. Sterianou, D. C. Sinclair, M. J. Rosseinsky, Angewandte Chemie-International Edition 2007, 46, 8785.

Three - Coordinate Metal Centres in Extended Transition Metal Oxides

A. Bowman, M. Allix, D. Pelloquin, M.J. Rosseinsky

Journal of the American Chemical Society, 128, 12606-12607, 2006.

Ba₈ZnTa₆O₂₄: a high-Q microwave dielectric from a potentially diverse homologous series S.M. Moussa, J.B.  Claridge, M.J. Rosseinsky, S. Clarke, R.M. Ibberson, T. Price, D.M. Iddles, D.C. Sinclair

Applied Physics Letters 82, 4537-4539, 2003

The Hydride Anion in an Extended Transition Metal Oxide Array – LaSrCoO₃H_0.7

M.A. Hayward, E.J. Cussen, J.B. Claridge, M. Bieringer, M.J. Rosseinsky, C.J. Kiely, S.J. Blundell, I.M. Marshall and F.L. Pratt

Science 295, 1882-1884, 2002

Materials for solid oxide fuel cells and ceramic gas separation and catalytic membranes

Solid oxide fuel cells require electrodes which conduct both oxide ions and electrons (mixed conductors) and catalyse the reactions at the anode and cathode of the cell, and electrolytes which conduct only oxide ions. Related systems operate with proton conducting electrolytes. Our role is to identify new candidate materials for these properties and understand the chemical and structural factors which contribute to the properties. We have identified new mixed conducting oxides and are now evaluating them in fuel cell assemblies, and have recently reported new highly conducting oxide ion conductors based on interstitial excess oxide ions. This work involves new materials synthesis, characterisation of structures to identify key property-controlling features and evaluation of the electron and ion transport properties.

Representative publications

Observation of Hydride Mobility in the Transition Metal Oxide Hydride LaSrCoO₃H_0.7

C.A. Bridges, F. Fernandez-Alonso, J.P. Goff, M.J. Rosseinsky

Advanced Materials, 18, 3304-3308, 2006

Sr₂MgMoO_6-d: Structure, phase stability, and cation site order control of reduction

C. Bernuy-Lopez, M. Allix, C.A. Bridges, J.B. Claridge, M.J. Rosseinsky

Chemistry of Materials 19, 1035 – 1043, 2007.

Oxygen vacancy ordering phenomena in the mixed-conducting hexagonal perovskite Ba₇Y₂Mn₃Ti₂O₂₀

X.J. Kuang, M. Allix, R.M. Ibberson, J.B. Claridge, H.J. Niu, M.J. Rosseinsky

Chemistry of Materials 19, 2884-2893, 2007.

New materials in thin film form

We are using pulsed laser deposition to assemble new oxide materials from structural sub-components identified from the structure of the target material – the in-situ RHEED monitoring of the deposition of individual layers permits switching between rock salt and perovskite components of the Ruddlesden-Popper structure.

Pulsed laser deposition instrument

Publication

Unit-cell-level assembly of metastable transition-metal oxides by pulsed-laser deposition

L. Yan, H.J. Niu, C.A. Bridges, P.A. Marshall, J. Hadermann, G. van Tendeloo, P.R. Chalker, M.J. Rosseinsky

Angewandte Chemie International Edition 46, 4539-4542, 2007.

Flexible open-framework materials for chiral and gas separation applications

Porous materials with nanometre size openings have applications in the storage of energy gases such as methane and hydrogen, gas separation and purification, delivery of drugs and medical gases, and as catalysts and separation materials. The best-established systems are the aluminosilicate zeolites. We have been involved in developing open-framework materials based on the coordination of organic ligands to metal centres – this has allowed us to show how these molecule-based materials can have a flexible response to guests, opening up to accommodate guests that appear too large based on a static view of the structure. This has produced new modes of hydrogen storage, discovered in work with Professor Mark Thomas at Newcastle, and allowed us to study the course of a chemical reaction that takes place within the pores of a nanoporous material. We have also developed chiral open framework materials and open-frameworks based on amino acid ligands.

Crystal structures of the reagents (left) and products (right) of a substitution reaction taking place within the pores of a flexible open-framework material.

Representative publications

A family of nanoporous materials based on an amino acid backbone

R. Vaidhyanathan, D. Bradshaw, J.N. Rebilly, J.P. Barrio, J. Gould, N.G. Berry, M.J. Rosseinsky Angewandte Chemie International Edition 45, 6495-6499, 2006.

Hysteretic Adsorption and Desorption of Hydrogen by Nanoporous
Metal-Organic Frameworks

X. Zhao, B. Xiao, A. J. Fletcher, K. M. Thomas, D. Bradshaw and  M. J. Rosseinsky

Science, 306, 1012-1015, 2004.

Reversible concerted ligand substitution at alternating metal sites in an extended solid

D. Bradshaw, J.E. Warren, M.J. Rosseinsky

Science 315, 977-980, 2007.

Design, chirality and flexibility in microporous molecule-based materials

D. Bradshaw, J.B. Claridge, E. J. Cussen, T. J. Prior, M. J. Rosseinsky

Accounts of Chemical Research, 38, 273-282, 2005.

Open-framework nanoporous material built from the amino acid aspartate, with predicted location of a chiral diol guest based on docking calculations (Dr. N.G. Berry)

New superconducting materials

Superconducting materials carry electrical current without resistance below their superconducting transition temperature T_c. Our role is to identify new classes of complex systems which are superconducting and understand the chemical and structural basis for this behaviour. The superconducting state is vey demanding to access in a material, and understanding the electronic properties of systems related to the superconductors but with different electronic ground states plays an important part of this work.

We have recently discovered the highest transition temperature molecule-based superconductor (38K Cs₃C₆₀) working with the group of Professor Kosmas Prassides at Durham.

Structure of the 38K superconductor Cs₃C₆₀

Representative publications

Bulk superconductivity at 38 K in a molecular system A.Y. Ganin, Y. Takabayashi, Y. Z. Khimyak, S. Margadonna, A. Tamai, M. J. Rosseinsky, K. Prassides Nature Materials 7, 367, 2008

Methylaminated potassium fulleride, (CH₃NH₂)K₃C₆₀: Towards hyperexpanded fulleride lattices

A.Y. Ganin, Y. Takabayashi, C.A. Bridges, Y.Z. Khimyak, S. Margadonna, K. Prassides, M.J. Rosseinsky

Journal of the American Chemical Society, 128, 14784-14785, 2006.

Chemical Control of Electronic Structure and Superconductivity in Layered Borides and Borocarbides: Understanding the Absence of Superconductivity in Li_xBC
A.M. Fogg, J. Meldrum, G.R. Darling, J.B. Claridge, M.J. Rosseinsky,

Journal of the American Chemical Society 128, 10043-10053, 2006.

The Mott-Hubbard insulating state and orbital degeneracy in the superconducting C₆₀^3- fulleride family

P. Durand, G.R. Darling, Y. Dubitsky, A. Zaopo, M.J. Rosseinsky

Nature Materials 2, 605-610, 2003.

Nanostructured materials

In addition to the deposition of thin oxide films, we are working on the preparation of materials with multiple properties based on functional transition metal oxide nanoparticles.

TEM images of (a) 4.5 nm and (b) 8.5 nm PMAA-PTTM protected Fe₃O₄ nanocrystals and corresponding high-resolution TEM images.

Publication

Direct Coprecipitation Route to Monodisperse Dual-Functionalized Magnetic Iron Oxide Nanocrystals without Size Selection Zhen Li, Bien Tan, Mathieu Allix, Andrew I. Cooper, Matthew J. Rosseinsky, Small 4, 231, 2008.