Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH Using TRLFS and PARAFAC of Excitation Emission Matrices.

The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time.

Control of evolution of porous copper-based metal-organic materials for electroreduction of CO to multi-carbon products.

Electrochemcial reduction of CO to multi-carbon (C) products is an important but challenging task. Here, we report the control of structural evolution of two porous Cu(ii)-based materials (HKUST-1 and CuMOP, MOP = metal-organic polyhedra) under electrochemical conditions by adsorption of 7,7,8,8-tetracyanoquinodimethane (TNCQ) as an additional electron acceptor. The formation of Cu(i) and Cu(0) species during the structural evolution has been confirmed and analysed by powder X-ray diffraction, and by EPR, Raman, XPS, IR and UV-vis spectroscopies.

Evolution of bismuth-based metal-organic frameworks for efficient electroreduction of CO.

Understanding the structural and chemical changes that reactive metal-organic frameworks (MOFs) undergo is crucial for the development of new efficient catalysts for electrochemical reduction of CO. Here, we describe three Bi(iii) materials, MFM-220, MFM-221 and MFM-222, which are constructed from the same ligand (biphenyl-3,3',5,5'-tetracarboxylic acid) but which show distinct porosity with solvent-accessible voids of 49.6%, 33.