Tungsten-niobium oxide bronzes: a bulk and surface structural study

[EN] Materials from the WO3-Nb2O5 system, presenting bronze-type crystal structures, display outstanding functional properties for several applications as thermoelectric materials, lithium-ion battery electrodes, or catalysts. In this work, a series of W-Nb-O oxide bronzes have been synthesized by the hydrothermal method (with Nb/(W + Nb) ratios in the range of 0-1). A combination of bulk and surface characterisation techniques has been applied to get further insights into: (i) the effect of thermal treatments on as-prepared materials and (ii) the surface chemical nature of W-Nb-O oxide bronzes. Thermal treatments promote the following structural changes: (i) loss of emerging long-range order and (ii) the elimination of NH4+ and H2O species from the structural channels of the as-synthesized materials. It has been observed that W-Nb-O bronzes with Nb at% of ca. 50% are able to retain a long-range order after heat-treatments, which is attributed to the presence of a Cs-0.5[W2.5Nb2.5O14]-type structure. Increasing amounts of Nb 5T in the materials (i) promote a phase transition to pseudocrystalline phases ordered along the c-axis; (ii) stabilize surface W s. species (elucidated by XPS); and (iii) increase the proportion of surface Lewis acid sites (as determined by the FTIR of adsorbed CO). Results suggest that pseudocrystalline oxides (with a Nb at% >= 50%) are closely related to NbO2 pentagonal bipyramid-containing structures. The stabilisation of Lewis acid sites on these pseudocrystalline materials leads to a higher yield of heavy compounds, at the expense of acrolein formation, in the gas-phase dehydration of glycerol.The authors would like to acknowledge the Ministerio de Ciencia, Innovacion y Universidades in Spain for the financial support (RTI2018-099668-B-C21 and SEV-2016-0683 projects), and the Electron Microscopy Service at Universitat Politecnica de Valencia for providing facilities and technical support. D. D. also thanks Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669).Delgado-Muñoz, D.; Concepción Heydorn, P.; Trunschke, A.; López Nieto, JM. (2020). Tungsten-niobium oxide bronzes: a bulk and surface structural study. Dalton Transactions. 49(38):13282-13293. https://doi.org/10.1039/d0dt02058c13282132934938D. J. M. Bevan and P.Hagenmuller , Non-Stoichiometric Compounds , Pergamon , 1973Quan, H., Gao, Y., & Wang, W. (2020). 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