Chandrashekhar V. Rode

Cu–ZrO2 nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to γ-valerolactone

Several copper based catalysts were prepared, characterized and evaluated for the hydrogenation of levulinic acid and its methyl ester. Among these, nanocomposites of Cu–ZrO2 and Cu–Al2O3 quantitatively catalyzed the hydrogenation of levulinic acid and its methyl ester to give 90–100% selectivity to γ-valerolactone in methanol and water respectively. Both the Cu–ZrO2 and Cu–Al2O3 nanocomposites were prepared by the co-precipitation method using mixed precursors under controlled conditions. XRD results showed that the main active phase of the reduced Cu–ZrO2 catalyst was metallic copper and particle size was found to be of 10–14 nm by HRTEM. The active metal leaching was at a maximum for the Cu–Al2O3 catalyst in a water medium due to the formation of a copper–carboxylate complex that was blue in colour. Surprisingly, copper leaching was completely suppressed in the case of the Cu–ZrO2 catalyst in methanol in spite of the substrate loading was increased from 5 to 20% w/w. The excellent recyclability of the Cu–ZrO2 catalyst with complete LA conversion and >90% GVL selectivity makes it a sustainable process having a commercial potential.

From graphite oxide to highly water dispersible functionalized graphene by single step plant extract-induced deoxygenation†

We report a single step facile synthesis of highly water dispersible functionalized graphene nanosheets by plant extract-induced deoxygenation of graphite oxide (GO). The results of various characterizations reveal that the properties of such plant extract-converted graphene nanosheets (PCGN) are comparable to chemically converted graphene nanosheets (CCG). These results open a green route to the emerging graphene-based technologies.

Reductive Dechlorination of γ-hexachlorocyclohexane using Fe-Pd Bimetallic Nanoparticles

Nanoscale Fe-Pd bimetallic particles were synthesized and used for degradation of lindane (gamma-hexachlorocyclohexane) in aqueous solution. Batch studies showed that 5mg/L of lindane was completely dechlorinated within 5 min at a catalyst loading of 0.5 g/L and the degradation process followed first-order kinetics. GC-MS analysis in corroboration with GC-ECD results showed the presence of cyclohexane as the final degradation product. The proposed mechanism for the reductive dechlorination of lindane involves Fe corrosion-induced hydrogen atom transfer from the Pd surface. The enhanced degradation efficiency of Fe-Pd nanoparticles is attributed to: (1) high specific surface area of the nanoscale metal particles (60 m(2)/g), manyfold greater that of commercial grade micro- or milli-scale iron particles (approximately 1.6m(2)/g); and, (2) increased catalytic reactivity due to the presence of Pd on the surface. Recycling and column studies showed that these nanoparticles exhibit efficient and sustained catalytic activity.

Single pot conversion of furfuryl alcohol to levulinic esters and γ-valerolactone in the presence of sulfonic acid functionalized ILs and metal catalysts

Ionic liquids functionalized with acidic anions, HSO4, ClSO3H, PTSA, TFA (MIm), HSO4 and TFA (NMP) were found to efficiently (99% conversion) catalyze the alcoholysis of furfuryl alcohol (FAL) in the presence of methanol, ethanol, n-butanol and isopropyl alcohol (IPA) to the corresponding levulinic acid esters under mild temperature (90–130 °C) conditions. The extended alkyl chain length of [MIm] using 1,4-butane sultone enhanced the Bronsted acidity of [BMIm-SH][HSO4] catalyst resulting into the highest selectivity of >95% to Me-LA. An increase in both temperature and catalyst concentration increased the furfuryl alcohol conversion and selectivity to levulinate esters. In contrast, an increase in the substrate concentration from 5 to 15% caused a decrease in Me-LA selectivity due to accumulation of intermediate ethers of furfuryl alcohol. Using a combination of [BMIm-SH][HSO4] and 5% Ru/C catalyst, direct conversion of FAL to γ-valerolactone (GVL) is shown for the first time. A complete conversion of FAL with the highest selectivity of 68% to GVL could be achieved under optimum conditions while higher Ru loading enhanced the GVL selectivity to 94% in the hydrogenation step of this tandem approach. Our catalyst system could be efficiently recycled five times retaining the original activity and selectivity levels.

Simultaneous glycerol dehydration and in situ hydrogenolysis over Cu–Al oxide under an inert atmosphere

Among various catalysts screened, the Cu–Al oxide catalyst, prepared by a co-precipitation method, exhibited excellent activity for simultaneous glycerol dehydration and its hydrogenolysis without external hydrogen. Detailed characterization by XRD, XPS, HR-TEM, TPR, etc., showed evidence of Cu2+ in the form of CuO and CuAl2O4, along with Cu0 and Cu1+ species, which are responsible for their multifunctional roles in glycerol APR, dehydration and hydrogenolysis reactions under inert conditions. This catalyst also presented consistent activity for a duration of 400 h for autogeneous hydrogenolysis of refined glycerol with 36% selectivity to 1,2-propanediol (1,2-PDO). Manipulating the temperature and feed flow rate conditions, meant that the selectivity to acetol and 1,2-PDO could be tailored as desired. Substantial enhancement in 1,2-PDO selectivity (75%) was achieved for an aqueous bio-glycerol feed over the same catalyst for 50 h of testing.

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.

Hierarchically nanoperforated graphene as a high performance electrode material for ultracapacitors.

High performance is reported for a symmetric ultracapacitor (UC) cell made up of hierarchically perforated graphene nanosheets (HPGN) as an electrode material with excellent values of energy density (68.43 Wh kg⁻¹) and power density (36.31 kW kg⁻¹). Perforations are incorporated in the graphite oxide (GO) and graphene system at room temperature by using silica nanoparticles as template. The symmetric HPGN-based UC cell exhibits excellent specific capacitance (Cs) of 492 F g⁻¹ at 0.1 A g⁻¹ and 200 F g⁻¹ at 20 A g⁻¹ in 1 M H₂SO₄ electrolyte. This performance is further highlighted by galvanostatic charge-discharge study at 2 A g⁻¹ over a large number (1000) of cycles exhibiting 93% retention of the initial Cs. These property features are far superior as compared to those of symmetric UC cells made up of only graphene nanosheets (GNs), i.e. graphene sheets without perforations. The latter exhibit Cs of only 158 F g⁻¹ at 0.1 A g⁻¹ and the cells is not stable at high current density.

Hydrogen production by the water-gas shift reaction using CuNi/Fe2O3 catalyst

Incorporation of both Cu and Ni together into the crystalline lattice of Fe2O3 results in a significant increase in the catalytic activity and also suppresses the methanation reaction in the high-temperature water-gas shift (HT-WGS) reaction. CuNi/Fe2O3 exhibited the highest CO conversion with negligible CH4 selectivity at the extremely high GHSV of 101 000 h−1 (XCO = 85% at 400 °C). The high activity of CuNi/Fe2O3 catalyst is mainly due to the increase in the lattice strain and the decrease in the binding energy of lattice oxygen. In addition, X-ray photoelectron spectroscopy (XPS) results provide direct evidence for the formation of surface CuNi alloy, which plays a critical role in suppressing the methanation reaction. The detailed characterization by powder X-ray diffraction (XRD), XPS, BET, and H2 temperature-programmed reduction (TPR) techniques was used to understand the role of dopants on host iron oxides in the enhancement of catalytic activity for HT-WGS reaction.

Trigol based reduction of graphite oxide to graphene with enhanced charge storage activity

A triethylene glycol (trigol) based simple approach is reported for the reduction of graphite oxide (GO). This protocol produces high quality graphene which we term as trigol reduced graphene (TRG) and its relevant properties including electrical conductivity and energy storage capacity are comparable to those of graphene obtained by the conventional hydrazine based approach. The achieved specific capacitance for TRG is 130 F g−1 with an energy density value of 18 W h kg−1. This work opens up a new promising synthetic route for the development of graphene and graphene based nanocomposites for various energy related applications.