Bimetallic platinum–ruthenium nanoparticles immobilized on reduced graphene oxide-TiO2 (RGO-TiO2) support for ethanol electro oxidation in acidic media

The present work addresses the potentialities of Pt–Ru nanoparticles deposited on a graphene oxide (RGO) and TiO₂ composite support towards electrochemical oxidation of ethanol in acidic media relevant for fuel cell applications. To immobilize platinum–ruthenium bimetallic nanoparticles on to an RGO-TiO₂ nanohybrid support a simple solution-phase chemical reduction method is utilized. An examination using electron microscopy and energy dispersive X-ray spectroscopy (EDS) indicated that Pt–Ru particles of 4–8 nm in diameter are dispersed on RGO-TiO₂ composite support. The corresponding Pt–Ru/RGO-TiO₂ nanocomposite electrocatalyst was studied for the electrochemical oxidation of ethanol in acidic media. Compared to the commercial Pt–Ru/C and Pt/C catalysts, Pt–Ru/RGO-TiO₂ nanocomposite yields higher mass-specific activity of about 1.4 and 3.2 times, respectively towards ethanol oxidation reaction (EOR). The synergistic boosting provided by RGO-TiO₂ composite support and Pt–Ru ensemble together contributed to the observed higher EOR activity and stability to Pt–Ru/RGO-TiO₂ nanocomposite compared with other in-house synthesized Pt–Ru/RGO, Pt/RGO and commercial Pt–Ru/C and Pt/C electrocatalysts. Further optimization of RGO-TiO₂ composite support provides opportunity to deposit many other types of metallic nanoparticles onto it for fuel cell electrocatalysis applications.     

Electrosynthesis of eco-friendly electrocatalyst based nickel-copper bimetallic nanoparticles supported on poly-phenylenediamine with highest current density and early ethanol oxidation onset potential

Bimetallic catalysts have been investigated as the most efficient materials to accelerate the chemical transformations at the anode in Direct Ethanol Fuel Cells. A comparative study is presented here to synthesize Ni–Cu bimetallic nanoparticles for the ethanol oxidation reaction on three conducting polymers: poly-ortho-phenylenediamine, poly-meta-phenylenediamine, and poly-para-phenylenediamine. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Electrochemical Impedance Spectroscopy (EIS) were used to analyze the modified electrodes. A series of bimetallic Ni–Cu nanoparticles with tunable ratios were successfully synthesized by simply changing the concentrations of Nickel and Copper. It has been confirmed that the best Ni/Cu molar ratio was 25% in the aspect of catalytic performance. The electrocatalyst exhibited an excellent catalytic activity with an anodic current of 70.5 mA cm^?2 at the lowest onset potential of 0.39 V with impressive stability. Ni₄Cu₁/PpPD should be considered as a good alternative to noble metal anode catalyst.     

甲苯+乙醇+1-癸基-3-甲基咪唑醋酸盐物系等压气液相平衡数据的测定及关联

在常压下测定了甲苯+乙醇+1-癸基-3-甲基咪唑醋酸盐([C_(10)MIM][OAc])三元物系的等压气液相平衡数据,使用Aspen软件中NRTL模型对三元气液相平衡数据进行关联,通过计算得到方程参数。实验结果表明,[C_(10)MIM][OAc]的加入对甲苯有显著的盐析效应,[C_(10)MIM][OAc]摩尔分数越大效果越明显,当[C_(10)MIM][OAc]摩尔分数达到0.15时甲苯-乙醇的共沸现象完全消失。由NRTL模型计算出[C_(10)MIM][OAc]打破甲苯-乙醇体系共沸的最小摩尔分数为0.139 7。[C_(10)MIM][OAc]可以用作分离甲苯-乙醇共沸体系的萃取剂。     

改性氧化钛对羟乙基乙二胺水溶液解吸CO2的强化

羟乙基乙二胺（AEE）水溶液的CO₂循环吸收量高（1.2molCO₂/molAEE），吸收速度快，稳定性好，但解吸速度慢、解吸量少（0.8mol CO₂/mol AEE）是限制该技术广泛应用的主要原因。本文通过向AEE水溶液中添加质量分数为0.05%～0.20%的改性氧化钛（TiO₂-MWCNT和TiO₂-OH）强化AEE的解吸能力。CO₂循环吸收（40℃）-解吸（120℃）实验结果表明改性氧化钛的添加比氧化钛强化CO₂解吸效果更好，强化顺序为TiO₂-MWCNT＞TiO₂-OH；其对应的最大解吸速率分别为0.093L/min（质量分数0.15%）和0.083L/min（质量分数0.20%），相对于AEE水溶液，分别提高了32.9%和18.6%；其对应的最大解吸量分别为0.92molCO₂/molAEE（质量分数0.15%）和0.88molCO₂/molAEE（质量分数0.20%），分别提高了12.2%和9.7%；其对应的CO₂循环吸收量分别是0.95molCO₂/molAEE（质量分数0.15%）和0.89molCO₂/molAEE（质量分数0.15%），分别提高了18.75%和11.25%；5次循环吸收解吸实验结果表明改性氧化钛强化CO₂解吸效果稳定，具有较强的化学稳定性。对反应后的改性氧化钛进行XRD、BET、FTIR和SEM表征，结果表明改性氧化钛具有较强的结构稳定性。TiO₂-MWCNT和TiO₂-OH在促进有机胺溶液解吸CO₂方面具有一定的工业应用潜力。     

Software for Simulation of Second‐Generation Ethanol Production by a Simultaneous Saccharification and Fermentation Process

Environmental impacts associated with the consumption of fossil fuels and the need to generate power through renewable resources demands the usage of alternative materials. The objective is the production of clean energy from materials like lignocellulosic biomass to produce second‐generation (2G) ethanol. A software in the Matlab program is elaborated to simulate the simultaneous saccharification and fermentation (SSF) process of lignocellulosic biomass for the 2G ethanol production in batch reactors. Studying the effects of the process variables, it was found that the higher interference is caused by cellulose concentration. Higher concentrations of the product in batch processes are obtained with the maximum cellulose concentrations, cells, and enzyme.     

Controllability Analysis of Process Alternatives for Biobutanol Purification

Biobutanol has characteristics similar to petroleum fuel and is considered as a superior biofuel compared to ethanol. The development of technologies for biobutanol production by fermentation has resulted in higher final biobutanol concentrations together with less energy‐intensive separation and purification techniques. These new technological developments have the potential to provide a production process for biobutanol that is economically viable in comparison to the petrochemical pathway for its production. The control properties of four different possible process designs for biobutanol purification are analyzed. The results, using the singular value decomposition technique, indicated that the scheme where only biobutanol flow is purified, and both ethanol and acetone leaving the purification process mixed with water and biobutanol traces, showed the best control properties.     

Bimetallic PtPd nanoparticles relying on CoNiO2 and reduced graphene oxide as a most operative electrocatalyst toward ethanol fuel oxidation

Of late, fuel cells have drawn great attentions owing to high-energy demands, fossil fuel depletion and worldwide environmental pollution. Direct ethanol fuel cell (DEFC) constituted as one of the most promising sources of green energy, howbeit the ethanol oxidation reaction (EOR) sluggish kinetic is one of the essential challenges toward the commercialization of DEFCs. Herein, we introduce bimetallic catalyst on CoNiO₂ modified reduced graphene oxide (rGO) to completely exploit the advantages of nano-surface structures as well as the reduction of Pt and Pd loading in fuel cells. With the combined advantages of PtPd, CoNiO₂ and rGO, a significant enhancement in electrocatalytic behavior, stability and CO poisoning tolerance of PtPd have been observed. Regarding the implications, PtPd/CoNiO₂/rGO is greatly preferable than Pt/CoNiO₂/rGO and Pd/CoNiO₂/rGO in terms of high electroactive surface area (ECSA), electro-catalytic activity, and lower onset potential (E_ons) towards the EtOH oxidation in alkaline media. Furthermore, the chronoamperometry curve (CA) illustrated 77% after 3600 s which is dramatically soared compared with the other electrodes (≤40%), demonstrating the high stability of the PtPd bimetallic nanoparticle electrocatalyst. Ultimately, PtPd/CoNiO₂/rGO nanocomposite is found to be an excellent anode electrocatalyst for application in DEFCs.     

Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff{\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (2) dehydrogenation of ethanol to acetaldehyde ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{CHO+H}}_{\mathrm{2}}), (3) esterification of acetic acid with ethanol ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+CH}}_{\mathrm{3}}\mathrm{COOH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (4) dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+O}}_{\mathrm{2}}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}\mathrm{O}). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.     

Effects of Plant Growth Hormones on Mucor indicus Growth and Chitosan and Ethanol Production

The objective of this study was to investigate the effects of indole-3-acetic acid (IAA) and kinetin (KIN) on Mucor indicus growth, cell wall composition, and ethanol production. A semi-synthetic medium, supplemented with 0–5 mg/L hormones, was used for the cultivations (at 32 °C for 48 h). By addition of 1 mg/L of each hormone, the biomass and ethanol yields were increased and decreased, respectively. At higher levels, however, an inverse trend was observed. The glucosamine fraction of the cell wall, as a representative for chitosan, followed similar but sharper changes, compared to the biomass. The highest level was 221% higher than that obtained without hormones. The sum of glucosamine and N-acetyl glucosamine (chitin and chitosan) was noticeably enhanced in the presence of the hormones. Increase of chitosan was accompanied by a decrease in the phosphate content, with the lowest phosphate (0.01 g/g cell wall) being obtained when the chitosan was at the maximum (0.45 g/g cell wall). In conclusion, IAA and KIN significantly enhanced the M. indicus growth and chitosan production, while at the same time decreasing the ethanol yield to some extent. This study shows that plant growth hormones have a high potential for the improvement of fungal chitosan production by M. indicus.     

The control of paracetamol particle size and surface morphology through crystallisation in a spray dryer

The parameters governing the crystallisation of paracetamol using various conventional techniques has been extensively studied, however the factors influencing the drug crystallisation using spray drying is not as well understood. The aim of this work was to investigate the crystallisation of an active pharmaceutical ingredient through evaporative crystallisation using a spray dryer to study the physicochemical properties of the drug and to use semi-empirical equations to gain insight into the morphology and particle size of the dried powder. Paracetamol solutions were spray dried at various inlet temperatures ranging from 60 °C to 120 °C and also from a series of inlet feed solvent compositions ranging from 50/50% v/v ethanol/water to 100% ethanol and solid-state characterisation was done. The size and morphology of the dried materials were altered with a change in spray drying parameters, with an increase in inlet temperature leading to an increase in particle Sauter mean diameter (from 3.0 to 4.4 µm) and a decrease in the particle size with an increase in ethanol concentration in the feed (from 4.6 to 4.4 µm) as a result of changes in particle density and atomised droplet size. The morphology of the dried particles consisted of agglomerates of individual crystallites bound together into larger semi-spherical agglomerates with a higher tendency for particles having crystalline ridges to form at higher ethanol concentrations of the feed.