Electro-Oxidation Reaction of Methanol over La2-xSrxNi1-y(Mn/Fe/Co)yO4+δ Ruddlesden-Popper Oxides.

Solution combustion-synthesized Ruddlesden-Popper oxides La1.4Sr0.6Ni0.9(Mn/Fe/Co)0.1O4+δ were explored for the methanol electro-oxidation reaction. With optimal doping of Sr2+ in the A site and Co2+ in the B site, Ni3+ with t2g6 dx2-y21 configuration in La1.4Sr0.6Ni0.9Co0.1O4+δ exhibited a tetragonal distortion with compression in axial bonds and elongation in equatorial bonds. This structural modification fostered an augmented overlap of dz2 orbitals with axial O 2p orbitals, leading to a heightened density of states at the Fermi level. Consequently, this facilitated not only elevated electrical conductivity but also a noteworthy reduction in the charge transfer resistance. These effects collectively contributed to the exceptional methanol oxidation activity of La1.4Sr0.6Ni0.9Co0.1O4+δ, as evidenced by an impressive current density of 21.4 mA cm-2 and retention of 95% of initial current density even after 10 h of prolonged reaction. The presence of Ni3+ further played a pivotal role in the creation of NiOOH, a crucial intermediate species, facilitated by the presence of surface oxygen vacancies. These factors synergistically enabled efficient methanol oxidation. In summary, our present study not only yields substantial insights but also paves the way for a novel avenue to fine-tune the activity of Ruddlesden-Popper oxides for the successful electro-oxidation of methanol.

Zeolite-Based Sorbent for CO2 Capture: Preparation and Performance Evaluation.

In this work, zeolite-based sorbents were developed from gasified rice husk. CO2 capture capacity of the sorbents was examined at various temperatures and pressures employing a fixed-bed flow reactor and simulated flue gas. Various physicochemical properties such as thermal stability, pore size distribution, morphology, chemical composition, etc. of the in-house-developed materials were characterized in detail and were also compared with two commercially available zeolites. Tetra-ethylenepentamine was impregnated in the in-house-developed zeolite supports to investigate its suitability to improve the CO2 adsorption capacity. The effects of reactor pressure, temperature, Si/Al ratio, and amine loading on CO2 uptake capacity were examined. A declining trend in CO2 adsorption capacity was observed with the increase in adsorption temperature and amine loading. At 30 °C, zeolite-Y (designated as Z-Y-3, silica to alumina ratio of 2.25) sample exhibited maximum adsorption capacity, and the obtained values were around 114 and 190 mg CO2/g sorbent under atmospheric and 5 bar pressure, respectively. It was also observed that the presence of alkali metal ions influenced the adsorption capacity of the zeolites. The study inferred that the adsorbent was efficient and promising for multiple adsorption-desorption cycles without much deterioration of the capture capacity.

Morphologically tuned CuO-ZnO-CeO2 catalyst for CO2 hydrogenation to methanol.

Morphologically modified composite CuO-ZnO-CeO2 catalysts were synthesized using a single-step hydrothermal technique. The study highlights the influence of solvent on the structural and physico-chemical properties of the catalysts. Various techniques, such as XRD, FE-SEM, BET, XPS, and H2-TPR, were used to analyze the catalyst properties. Among the synthesized materials, the catalyst, prepared with a N,N-dimethyl formamide (DMF)-to-metal nitrates ratio of 20 (named as CZC-1), showed enhanced active sites in the form of surface features such as nanowire-like morphology, large surface area, low crystallite size, increased oxygen vacancies, and high CuO dispersion. A bench-scale fixed-bed flow reactor was used to examine the catalytic performance of the catalysts. At 225 °C reactor temperature, 30 bar reactor pressure, and with a space velocity of 6000 cm3 gcat-1 h-1, the CZC-1 catalyst showed 13.6% CO2 conversion and 74.1% methanol selectivity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis confirmed the carbonate-formate-methoxy reaction pathway for methanol formation using the CZC-1 catalyst.

One-Step Conversion of n-Butanol to Aromatics-free Gasoline over the HZSM-5 Catalyst: Effect of Pressure, Catalyst Deactivation, and Fuel Properties as a Gasoline.

Sustainable production of gasoline-range hydrocarbon fuels from biomass is critical in evading the upgradation of combustion engine infrastructures. The present work focuses on the selective transformation of n-butanol to gasoline-range hydrocarbons free from aromatics in a single step. Conversion of n-butanol was carried out in a down-flow fixed-bed reactor with the capability to operate at high pressures using the HZSM-5 catalyst. The selective transformation of n-butanol was carried out for a wide range of temperatures (523-563 K), pressures (1-40 bar), and weight hourly space velocities (0.75-14.96 h-1) to obtain the optimum operating conditions for the maximum yields of gasoline range (C5-C12) hydrocarbons. A C5-C12 hydrocarbons selectivity of ∼80% was achieved, with ∼11% and 9% selectivity to C3-C4 paraffin and C3-C4 olefins, respectively, under optimum operating conditions of 543 K, 0.75 h-1, and 20 bar. The hydrocarbon (C5-C12) product mixture was free from aromatics and primarily olefinic in nature. The distribution of these C5-C12 hydrocarbons depends strongly on the reaction pressure, temperature, and WHSV. These olefins were further hydrogenated to paraffins using a Ni/SiO2 catalyst. The fuel properties and distillation characteristics of virgin and hydrogenated hydrocarbons were evaluated and compared with those of gasoline to understand their suitability as a transportation fuel in an unmodified combustion engine. The present work further delineates the catalyst stability study for a long time-on-stream (TOS) and extensive characterization of spent catalysts to understand the nature of catalyst deactivation.

Heat Management in Supersonic/Hypersonic Vehicles Using Endothermic Fuel: Perspective and Challenges.

In this study, an in-depth analysis has been performed on various technoengineering aspects of hydrocarbon cracking under supercritical conditions toward developing an endothermic fuel. The paper is segregated into several sections with specific emphasis. The major areas covered in this work include physicochemical characteristics of different endothermic fuels, supercritical pyrolysis of hydrocarbon fuels, phenomena of coking, and its suppression from an application viewpoint. The influence of various parameters (e.g., temperature, pressure, catalysts, space-time, etc.) on fuel conversion, endothermicity, and coke propensity has been emphasized in detail. The typical value of endothermic heat sink capacity for different fuels consisting of C8 to C15 hydrocarbons ranges from 500 to 1150 kJ/kg over temperature and pressure ranges of 550-750 °C and 25-55 bar, respectively. The effectiveness of various additives/initiators in improving endothermicity has been screened for wide ranges of temperature and pressure. Physicochemical properties like distillation characteristics, hydrocarbon composition, °API gravity, and sulfur content of different hydrocarbon fuels are compared in a single window. Most of the findings are abridged meticulously with relevant tables and plots. Toward the end, we have highlighted the critical issues/challenges on the experimental findings and prospective.

Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids.

The kinetics of epoxidation of cottonseed oil by peroxyacetic acid generated in situ from hydrogen peroxide and glacial acetic acid in the presence of liquid inorganic acid catalysts were studied. It was possible to obtain up to 78% relative conversion to oxirane with very less oxirane cleavage by in situ technique. The rate constants for sulphuric acid catalysed epoxidation of cottonseed oil were in the range 0.39-5.4 x 10(-6)L mol(-1)s(-1) and the activation energy was found to be 11.7 kcal mol(-1). Some thermodynamic parameters such as enthalpy, entropy, and free energy of activation were determined to be of 11.0 kcal mol(-1), -51.4 cal mol(-1)K(-1) and 28.1 kcal mol(-1), respectively. The order of effectiveness of catalysts was found to be sulphuric acid>phosphoric acid>nitric acid>hydrochloric acid. Acetic acid was found to be superior to formic acid for the in situ cottonseed oil epoxidation.