Phosphomolybdic acid embedded into biomass-derived biochar carbon electrode for supercapacitor applications

In high-performance, clean, safe, and cost-effective ways, supercapacitors are among the most promising ways to store and release nonfossil energy. In recent years, renewable biomass-derived activated carbon has been explored as a potential option for electrode material. It restricts their specific capacitance despite being environment-friendly and possessing intrinsic mechanical strength. In order to overcome this limitation and preserve all other properties, we are infusing polyoxometalate into the activated carbon; this increases specific capacitance with its fast reversible redox behaviour and preserves the carbon's characteristics. Beside suffusing phosphomolybdic acid (PMA) into biomass waste material, such as orange peel-derived activated carbon (OPAC), a new hybrid material (OPAC-PMA) was developed. The nanohybrid design was revealed by structural and morphological research, which showed high interfacial contact, allowing polyanions to redox rapidly. The novel hybrid electrode material (OPAC-PMA) has a capacitance value of 66% higher than the bare OPAC electrode. A further study showed that OPAC-PMA composite showed 88.23% cycle stability in 0.5 M H2SO4 electrolyte at 6 A g−1 for 4000 cycles

Boron-induced controlled synthesis of Co-nano particles over Bx(CN)y matrix for CO hydrogenation in aqueous media

Bx(CN)y supported cobalt nanoparticles have been synthesized by regulating the ratios of melamine and boric acid precursors. The carbonization step is adequate to generate the desired controlled-sized cobalt particles at an auto-reduced state that can eliminate the requirement of promotors (e.g., Pt) for the hydrogen-spillover effect. The presence of nitrogen in support enhances the dispersion of cobalt particles by providing sites for cobalt to nucleate and grow due to the interaction between cobalt and Π electrons from the sp2-N center. Boron in the catalyst system significantly stabilizes the catalyst, thus improving its lifetime. However, the excess of boron promotes the aggregation of cobalt particles; therefore, optimal boron loading is preferable. Moreover, the binding energy calculation of Co6 over the B-doped and undoped C3N4 surface computed through DFT studies shows a reduction in metal-support interaction with the addition of boron, which leads to the aggregation of the cobalt particles with high boron. Overall, the catalyst with the optimized boron and nitrogen-containing support-stabilized cobalt particles is highly efficient in the aqueous phase Fischer-Tropsch synthesis

Steam reforming of isobutanol for the production of synthesis gas over Ni/g-Al2O3 catalysts

Bio-isobutanol has received widespread attention as a bio-fuel and a source of chemicals and synthesis gas as part of an integrated biorefinery approach. The production of synthesis gas by steam reforming (SR) of isobutanol was investigated in a down-flow stainless steel fixed-bed reactor (FBR) over Ni/g-Al2O3 catalysts in the temperature range of 723–923 K. The NiO/g-Al2O3 catalysts were prepared by the wet impregnation method and reduced in the FBR prior to the reaction. The surface area, metal dispersion, crystalline phase, and reducibility of the prepared catalysts were determined using BET, chemisorption, XRD and TPR, respectively. From the TPR studies, the maximum hydrogen consumption was observed in the temperature range of 748–823 K for all the catalysts. The presence of nickel species was confirmed through the characterization of the catalysts using powder XRD. The time-on-stream (TOS) studies showed that the catalysts remained fairly stable for more than 10 h of TOS. The conversion of carbon to gaseous products (CCGP) was increased by increasing the nickel loading on g-Al2O3 and the temperature and by decreasing the weight hourly space velocity (WHSV). The hydrogen yield was increased by increasing the nickel loading on g-Al2O3, the WHSV, the steam-to-carbon mole ratio (SCMR), and the temperature. The selectivity to methane decreased at high reaction temperatures and SCMRs. The selectivity to CO decreased with increasing SCMRs and decreasing temperatures. The work was further extended to the thermodynamic equilibrium analysis of the SR of isobutanol under experimental conditions using Aspen Plus, and the equilibrium results were then compared to the experimental results. A reasonably good agreement was observed between the trends in the equilibrium and the experimental results

Roles of supports (γ-Al2O3, SiO2, ZrO2) and performance of metals (Ni, Co, Mo) in steam reforming of isobutanol

The production of synthesis gas from bio-isobutanol in an integrated biorefinery is a novel approach for its downstream conversion to hydrocarbon fuels and organic chemicals. The present article provides a systematic examination of the structure–activity correlation of various supported transition metal catalysts, xMS (x mmol metal, M (Ni, Co, and Mo) supported on S (Al, Si, and Zr for γ-Al2O3, SiO2, and ZrO2 respectively)) for steam reforming (SR) of bio-isobutanol. The activity of the catalyst was strongly influenced by metal-support interaction as reflected by metal dispersion, metal crystallite size, and extent of bulk metal/metal oxide. The catalytic activity increased in the order of 4.3NiZr < 4.3NiSi < 4.3NiAl and 4.3MoAl < 4.3CoAl < 4.3NiAl. 7.3CoAl exhibited consistent catalytic activity up to 12 h of time-on-stream. The hydrogen yield was boosted with rise of temperature and steam-to-carbon mole ratio (SCMR) with concurrent drop of selectivity to methane. The selectivity to CO reduced with increasing SCMR and decreasing temperature. Furthermore, spent catalysts were characterized to elucidate the effect of metal and support on the nature of coke formed and chemical transformation of the catalyst during SR

Kinetics of hydrodeoxygenation of octanol over supported nickel catalysts: a mechanistic study

The hydrodeoxygenation (HDO) of 1-octanol as a model aliphatic alcohol of bio-oil was investigated in a continuous down-flow fixed-bed reactor over γ-Al2O3, SiO2, and HZSM-5 supported nickel catalysts in the temperature range of 488–533 K. The supported nickel catalysts were prepared by incipient wetness impregnation method and characterized by BET, XRD, TPR, TPD, H2 pulse chemisorption, and UV-vis spectroscopy. Characterization of supported nickel (or nickel oxide) catalysts revealed existence of dispersed as well as bulk nickel (or nickel oxide) depending on the extent of nickel loading and the nature of the support. The acidity of γ-Al2O3 supported nickel catalysts decreased with increasing the nickel loading on γ-Al2O3. n-Heptane, n-octane, di-n-octyl ether, 1-octanal, isomers of heptene and octene, tetradecane, and hexadecane were identified as products of HDO of 1-octanol. The C7 hydrocarbons were observed as primary products for catalysts with active metal sites such as γ-Al2O3 and SiO2 supported nickel catalysts. However, C8 hydrocarbons were primarily formed over acidic catalysts such as pure HZSM-5 and HZSM-5 supported nickel catalyst. The 1-octanol conversion increased with increasing nickel loading on γ-Al2O3, and temperature and decreasing pressure and WHSV. The selectivity to products was strongly influenced by temperature, nickel loading on γ-Al2O3, pressure, and types of carrier gases (nitrogen and hydrogen). The selectivity to C7 hydrocarbons was favoured over catalysts with increased nickel loading on γ-Al2O3 at elevated temperature and lower pressure. A comprehensive reaction mechanism of HDO of 1-octanol was delineated based on product distribution under various process conditions over different catalysts

Polyoxometalates for Nonvolatile Memory Applications

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Role of NiMo Alloy and Ni Species in the Performance of NiMo/Alumina Catalysts for Hydrodeoxygenation of Stearic Acid: A Kinetic Study

The hydrodeoxygenation (HDO) of vegetable oil and fatty acid is extremely important for the sustainable production of diesel-range hydrocarbons. The present work depicts the role of Ni/Mo (mole) in the performance of alumina-supported NiMo catalysts for the HDO of stearic acid. Both Ni and NiMo alloy coexist in the NiMo catalysts depending on the Ni and Mo content. With increasing Ni/Mo (mole), the NiMo alloy content in the catalyst increases with the simultaneous decrease in the Ni content. The activity of NiMo catalysts thus enhances with increasing Ni/Mo (mole). The reaction follows a decarbonylation route over Ni sites and a HDO route over NiMo alloy species. C17 and C18 alkanes are thus observed as the dominating hydrocarbon product over Ni and NiMo alloy-rich catalysts, respectively. The activity of the NiMo catalyst further enhances with increasing reaction temperature and metal (Ni + Mo) loading. The selectivity to alkanes was, however, not affected by metal loading. A suitable kinetic model was further established based on the reaction mechanism to relate the kinetic data

Etherification of Glycerol with Ethanol over Solid Acid Catalysts: Kinetic Study Using Cation Exchange Resin

The etherification of glycerol with ethanol is a novel process to utilise low-value by-product (glycerol) of the biodiesel industry to produce ethers of glycerol suitable for use as fuel additive or solvent. The etherification of glycerol with ethanol was investigated under the liquid phase in a high pressure batch reactor using two different types of commercial solid acid catalyst (zeolites and strongly acidic cation exchange resin (CER)). The CER showed superior catalytic activity over H-beta zeolite. The diethyl ether was observed as major product at high ethanol-to-glycerol mole ratio. The product selectivity diverted towards ethers of glycerol with decreasing ethanol-to-glycerol mole ratio. Among ethers of glycerol, glycerol monoethyl ether was the major product of the reaction. The reaction mechanism for etherification of glycerol with ethanol was delineated based on experimental observations. The reaction rate increased with increasing catalyst loading and temperature without affecting selectivity to the products significantly. The apparent activation energy of glycerol and ethanol was 25.1 and 26.6 kcal/mol, respectively. An empirical kinetic model was developed to correlate experimental data at different temperatures. The conversion of the reactants calculated from the kinetic model matched reasonably with experimental data

Synthesis And Characterization Of Graphene Oxide –Polyoxometalate Composite Material For Device Applications

Polyoxometalates (POMs) consisting of clusters of d-block transition metals and oxygen atoms represent an important class of water soluble polynuclear nanomaterial. The tuneable size, structure and elemental composition of POM draws considerable attention for the development of functional composite materials of desired chemical and electronic properties.[1] Graphene can be the promising support for POMs due to its low band gap energy and fast electron transport properties. These properties of grapheme facilitates transport of electrons of POMs rapidly and effectively.[2] In the present investigation, graphene oxide (GO) and reduced graphene oxide (rGO) have been used as a support for POM-graphene composites for semiconductor, hydrogen production applications.[2] The deposition of POM on graphene oxide sheets were carried out through electron transfer interaction and electrostatic interaction between POM and GO sheets. ...

Synthesis, characterization, structural, redox and electrocatalytic proton reduction properties of cobalt polypyridyl complexes

A monoanionic amido pentadentate ligand bpaqH (2-(bis(pyridin-2-ylmethyl)amino)-N-(quinolin-8-yl)acetamide) and its corresponding cobalt(III) chloro complex [Co(bpaq)Cl]Cl: 1 and aqua derivative [Co(bpaq)(OH2)](ClO4)2: 2 were successfully synthesized and fully characterized by different analytical and spectroscopic techniques such as FT-IR, 1H NMR, UV–vis spectroscopy, ESI mass spectra. The structures of 1 and 2 have been determined by the single-crystal X-ray diffraction. Spectral and redox properties were investigated along with free ligand under electrochemical conditions. Both complexes performed proton reduction activity under soluble, diffusion-limited conditions in acetonitrile with acetic acid as an external proton source with overpotentials of 0.412 V for 1 and 0.394 V for 2. The stability of the catalysts was inspected by the time-dependent UV–vis spectroscopy; 1 and 2 were found to be highly stable in the absence and presence of acetic acid. There was no significant spectral change before and after the controlled potential electrolysis suggesting no change in molecular integrity during electrocatalysis