Narayan S. Biradar

Surface synergism of an Ag–Ni/ZrO2 nanocomposite for the catalytic transfer hydrogenation of bio-derived platform molecules

Levulinic acid was completely and selectively converted to GVL, in the presence of formic acid over an Ag–Ni/ZrO2 catalyst. The synergism between Ag and Ni in transfer hydrogenation eliminates the need for external hydrogen, making the process safer. The magnetic nature of the catalyst offers easy recovery for efficient recycling. This approach is standardized for the hydrogenation of several C3–C6 platform molecules in an aqueous medium.

Triple nanocomposites of CoMn2O4, Co3O4 and reduced graphene oxide for oxidation of aromatic alcohols

A composite of reduced graphene oxide (RGO) with oxides of manganese and cobalt together was prepared by a solvothermal method. During synthesis, both the reduction of graphene oxide as well as the growth of nanorod shaped CoMn2O4 and Co3O4 occurred simultaneously having a crystallite size of ~8 nm calculated from X-ray diffraction (XRD). The as-obtained triple nanocomposite material designated as RGO–MnCoO exhibited excellent activity for the liquid phase aerobic oxidation of aromatic alcohols under base-free conditions selectively giving the corresponding aldehydes (>85%). RGO loading was varied in the range of 1–10%, among which 1% RGO–MnCoO showed maximum catalytic activity enhancement of 24% as compared to the bare mixed oxide (MnCo-MO) for the oxidation of vanillyl alcohol. HR-TEM of RGO–MnCoO revealed that it was a composite material having uniform nanotubes of ~25 nm length and 6 nm diameter with a fringe pattern showing the (103) and (004) planes and lattice spaces of 0.26 nm and 0.22 nm, respectively, for the spinel CoMn2O4. The detailed studies on the morphology, size and composition of the as-prepared RGO–MnCoO nanocomposite by XRD, XPS, N2-adsorption/desorption and O2-TPD techniques were used to understand the role of RGO in the enhancement of catalytic activity for oxidation reaction.

Transfer hydrogenation of biomass-derived levulinic acid to γ-valerolactone over supported Ni catalysts

A sustainable process of catalytic transfer hydrogenation (CTH) of levulinic acid (LA) to γ-valerolactone (GVL) was investigated over Ni on various supports (Al2O3, ZnO, MMT and SiO2) in the presence of isopropanol (IPA) as the H-donor. Among these, the montmorillonite (MMT) supported Ni catalyst showed almost complete LA conversion (>99%) and selectivity (>99%) to GVL within 1 h. XRD and XPS results showed that the concentration of the metallic species significantly enhanced (two to four times) in the recovered sample as compared to the freshly prepared Ni/MMT. This was due to the in situ reduction of Ni2+ species present on the catalyst surface, through liberated H2 under the reaction conditions. The strong acid strength of MMT, evidenced by NH3-TPD and py-IR, facilitated the esterification of LA as well as cyclization to GVL. The conversion–selectivity pattern was found to decrease in the IPA–water mixture while, it remained unchanged in the IPA–acetone mixture. Our catalyst could be efficiently recycled up to five times with consistent CTH activity and selectivity to GVL. The plausible mechanism of LA to GVL conversion involves the formation of a levulinate ester with IPA that favours its simultaneous hydrogenation and cyclization in a spontaneous manner to give GVL and regenerating IPA for sustainability.

Single Pot Transfer Hydrogenation and Aldolization of Furfural Over Metal Oxide Catalysts

One pot catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol (FAL) by using hydrogen producing alcohols and simultaneous aldolization of carbonyl compounds produced during CTH, with furfural was achieved over non-noble metal oxides with bifunctional sites. Basic sites of MgO responsible for abstraction of proton showed complete conversion of furfural to give FAL and C8 monomer in a ratio of 3:1, respectively, the later altered to 1:1 by incorporating Al into MgO. Catalyst stability was established by its four cycles study.Graphical Abstract