resumo
The present study aims to understand the catalysis of the MgH2-Nb2O5 hydrogen storage system. To clarify the chemical interaction between MgH2 and Nb2O5, the mechanochemical reaction products of a composite mixture of MgH2+0.167Nb(2)O(5) was monitored at different time intervals (2, 5, 15, 30, and 45min, as well as 1, 2, 5, 10, 15, 20, 25, and 30h). The study confirms the formation of catalytically active Nb-doped MgO nanoparticles (typically MgxNbyOx+y, with a crystallite size of 4-8nm) by transforming reactants through an intermediate phase typified by Mgm-xNb2n-yO5n-(x+y). The initially formed MgxNbyOx+y product is shown to be Nb rich, with the concentration of Mg increasing upon increasing milling time. The nanoscale end-product MgxNbyOx+y closely resembles the crystallographic features of MgO, but with at least a 1-4% higher unit cell volume. Unlike MgO, which is known to passivate the surfaces in MgH2 system, the Nb-dissolved MgO effectively mediates the Mg-H-2 sorption reaction in the system. We believe that this observation will lead to new developments in the area of catalysis for metal-gas interactions.
palavras-chave
SORPTION KINETICS; NIOBIUM PENTOXIDE; METAL-OXIDES; MAGNESIUM; SYSTEM; NANOCOMPOSITE; NANOPARTICLES; IMPROVEMENT; MGH2/NB2O5; DESORPTION
categoria
Chemistry; Physics
autores
Pukazhselvan, D; Perez, J; Nasani, N; Bdikin, I; Kovalevsky, AV; Fagg, DP
nossos autores
agradecimentos
D.P. acknowledges financial support from Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), grant number SFRH/BPD/88756/2012. D.P. F.acknowledges financial support from the FCT, Fundo Europeu de Desenvolvimento Regional (FEDER) and Programa Operacional Factores de Competitividade (COMPETE), grant number, IF/01344/2014/CP1222/CT0001. A.V.K. acknowledges support from the project CICECO-Aveiro Institute of Materials (ref. UID/CTM/50011/2013). D.P. also thanks Dr. Venkata Ramana for useful discussions.