Influence of W on the reduction behaviour and Brønsted acidity of Ni/TiO2 catalyst in the hydrogenation of levulinic acid to valeric acid: Pyridine adsorbed DRIFTS study

• Published in: Applied catalysis. A, General Vol. 531; pp. 169 - 176
• Main Authors: Kumar, V. Vijay, Naresh, G., Deepa, S., Bhavani, P. Ganga, Nagaraju, M., Sudhakar, M., Chary, K.V.R., Tardio, J., Bhargava, S.K., Venugopal, A.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 05.02.2017; Elsevier Science SA
• Subjects: Brønsted-Lewis acidity; Catalysis; Catalysts; Decomposition; DRIFTS; High temperature; Hydrogenation; Infrared spectra; Levulinic acid; Nitrous oxide; Reduction; Ring opening; Strong interactions (field theory); Studies; Titanium dioxide; Tungsten; Valeric acid; W-Ni/TiO2; X ray photoelectron spectroscopy; γ-Valerolactone; Valeric acid; W-Ni/TiO2; Levulinic acid; DRIFTS; γ-Valerolactone; Brønsted-Lewis acidity
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2016.10.032

[Display omitted] •Strong interaction between W and Ni leads to increased Ni2+/Ni0 ratio on surface.•At ambient H2 pressure levulinic acid was converted to valeric acid over W-Ni/TiO2.•Lewis acid site in combination with Ni0 active for γ-valerolactone.•Brønsted acid sites close to nickel sites are responsible for valeric acid formation. Effect of W on 20wt%Ni/TiO2 catalyst is examined in the hydrogenation of levulinic acid (LA) to valeric acid at ambient H2 pressure. The interaction between W and Ni had a significant influence on the hydrogenation activity and product selectivity. The H2-TPR (temperature programmed reduction) results emphasized a shift in Tmax to very high temperatures due to W species which are in close proximity to Ni particles. The N2O decomposition measurements showed a decrease in N2O uptake with the increase in ‘W’ loadings due to a high ratio of Ni2+/Ni0 species at higher tungsten content. X-ray photoelectron spectra (XPS) demonstrated a shift in binding energy to higher owing to a strong interaction between W and Ni particles by the presence of ionic Ni at the near surface region. The ionic Ni species seems to be involved in the conversion of γ-valerolactone (GVL) to valeric acid (VA). Pyridine adsorbed infrared (IR) spectra revealed an enormous increase in surface Brønsted acidity originated from tungsten interacted Ni/TiO2 are the sites responsible for ring opening of GVL to form VA.