Catalytic methanolysis and hydrolysis of hydrazine-borane with monodisperse Ru NPs@nano-CeO2 catalyst for hydrogen generation at room temperature

Herein, we report metal catalyzed methanolysis and hydrolysis of hydrazine-borane as a fast hydrogen generation system under mild conditions. To the best of our knowledge, this is the first report that a monodisperse Ru NPs@nano-CeO₂ catalyst can achieve a complete conversion of N₂H₄BH₃ to H₂ with the assistance of both methanolysis and hydrolysis reactions. In order to achieve hydrolysis and methanolysis effectively, monodisperse Ru NPs@nano-CeO₂ catalyst have been prepared by modifying the chemical reduction method which is a very simple and efficient method in room conditions. The synthesized Ru NPs@nano-CeO2 catalyst showed excellent catalytic activity, stability, and selectivity in the production of hydrogen by both hydrolysis and methanolysis of the hydrazine-borane. The results reported here also includes (i) identification of the prepared catalyst by using analytical techniques such as XRD, XPS, TEM, HR-TEM, (ii) determination of stoichiometry for methanolysis and hydrolysis reactions, (iii) determination of rate constants and laws for methanolysis and hydrolysis reactions, (iv) determination of kinetic parameters such as enthalpy, entropy and activation energy for methanolysis and hydrolysis reactions.     

Poly(acrylic acid)-modified silica nanoparticles as a nonmetal catalyst for NaBH4 methanolysis

In the present work, a SiO₂@PAA catalyst for NaBH₄ methanolysis composed of silica nanoparticles modified with poly(acrylic acid) has been developed. The morphology and composition of the prepared SiO₂@PAA catalyst were analyzed with transmission electron microscopy, Fourier transform-infrared spectroscopy, x-ray photoelectron spectroscopy and thermogravimetric analysis. This catalyst showed excellent catalytic performance for methanolysis of NaBH₄. The NaBH₄ methanolysis reaction catalyzed by SiO₂@PAA showed an average hydrogen generation rate 5.5 times as high as the reaction catalyzed by unmodified SiO₂ and 10.6 times as high as the uncatalyzed reaction, respectively. The activation energy for methanolysis of NaBH₄ catalyzed by this SiO₂@PAA catalyst was 24.03 kJ/mol. Moreover, although the catalytic activity of SiO₂@PAA catalyst partially lost after being used, it could be restored after being regenerated by washing with diluted hydrochloric acid solution.     

Transesterification of Canola Oil to Biodiesel Using CaO/Talc Nanopowder as a Mixed Oxide Catalyst

A series of heterogeneous catalysts including different molar ratios of CaO/talc was synthesized to study the transesterification reaction of canola oil and methanol under different reaction conditions. Characterization and kinetic results revealed that the activity of this catalyst was enhanced due to the increase of CaO/talc molar ratio value leading to an improvement in the biodiesel production. Moreover, the effect of various parameters on the activity of the undertaken catalysts was studied in order to determine the optimum process conditions. Leaching measurements and the durability of the CaO/talc catalyst under several reaction cycles were evaluated and proved it to be a stable catalyst.     

PET Recycling – Contributions of Crystallization to Sustainability

Polyethylene terephthalate (PET) is one of the most common thermoplastic polymers and its durability has become a major environmental concern. The current public debate on plastic debris also triggered the revision of PET recycling technologies. This Research Article focuses on the chemical recycling of PET by means of methanolysis. The process degrades PET into two main reaction products, dimethyl terephthalate (DMT) and ethylene glycol (EG). Subsequent separation by distillation combined with crystallization removes critical impurities and non-PET components from co-polymers, providing monomers of high purity needed for re-polymerization purposes.     

A novel Microcystis aeruginosa supported manganese catalyst for hydrogen generation through methanolysis of sodium borohydride

In this study, Microcystis Aeruginosa (MA)- microalgae species was used for the first time as a support material with metal ions loading to fabricate a highly efficient catalyst for the hydrogen generation through methanolysis of sodium borohydride (NaBH₄). Microalgae was pre-treated with hydrochloric acid (3 M HCl) for 24 h at 80 °C. Subsequently, different metal ions (Mn, Co, and Mo) were loaded to the pre-treated samples. Finally, metal-loaded samples were subjected to burning in oven to fabricate the catalyst. Primarily, manganese metal was selected based on the best metal performance. Afterwards, different metal loading ratios, burning temperatures and burning times were evaluated to synthesize the optimal MA-HCl-Mn catalyst. Results showed the optimal conditions as Mn ratio, burning temperature and time as 50%, 500 °C and 45 min, respectively. To characterize the catalyst, FTIR, SEM-EDX, XRD, XPS and TEM analyses were performed. Hydrogen generation via methanolysis was performed at various NaBH4 ratio of 1–7.5% while changing concentrations from 0.05 to 0.25 g catalysts with diverge temperatures of (30, 40, 50 and 60 °C). The maximum hydrogen generation rate (HGR) by this novel catalyst was found as 4335.3, 5949.9, 7649.4 and 8758.9 mLmin⁻¹gcat⁻¹, respectively. Furthermore, the activation energy was determined to be 8.46 kJ mol⁻¹.     

Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane

Ammonia borane (AB) is an intriguing molecular crystal material with extremely high hydrogen density. In the present study, we prepared ruthenium (Ru) nanoparticles immobilized in montmorillonite (MMT) and examine its catalytic effect on the methanolysis reaction of AB. The Ru/MMT catalyst was prepared by cation-exchange method followed by hydrogen reduction at elevated temperatures. Property examinations found that the Ru/MMT catalyst was highly effective and robust for promoting the methanolysis reaction of AB. For example, the methanolysis system employing Ru/MMT catalyst exhibited an average hydrogen generation rate of 29 L min⁻¹ g⁻¹ (Ru). The catalyst at its twentieth usage retained 95% of its initial activity and ensured 100% conversion of AB. Kinetics studies found that the methanolysis reaction of AB employing Ru/MMT catalyst follows first-order kinetics with respect to AB concentration and catalyst amount, respectively.     

Transesterification of castor oil: Effect of the acid value and neutralization of the oil with glycerol

This paper evaluates the production of methyl esters from castor oil and methanol after neutralization of castor oil with glycerol. The reaction was carried out under atmospheric pressure and ambient temperature in a batch reactor, employing potassium hydroxide as catalyst. Results showed high yield of castor oil into methyl esters after neutralization of castor oil with glycerol. The highest yield observed was of 92.5% after 15 min of reaction. The best operating condition was obtained applying an alcohol to oil molar ratio of 6.0 and 0.5% w/w of catalyst.     

Kinetics of sunflower oil methanolysis catalyzed by calcium oxide

The methanolysis of sunflower oil was studied in the presence of CaO previously calcined at various temperatures and the optimal temperature for CaO calcination was determined. The sigmoidal process kinetics was explained by the initial triglyceride (TG) mass transfer controlled region, followed by the chemical reaction controlled region in the latter reaction period. The TG mass transfer limitation was due to the small available active specific catalyst surface, which was mainly covered by adsorbed molecules of methanol. In the later phase, the adsorbed methanol concentration decreased, causing the increase of both the available active specific catalyst surface and the TG mass transfer rate, and the chemical reaction rate become smaller than the TG mass transfer rate.     

Production of metal-free catalyst from defatted spent coffee ground for hydrogen generation by sodium borohyride methanolysis

In the present study, defatted spent coffee ground (DSCG) treated with different acids was used as a metal-free catalyst for the first time. The aim of undertaken work is to demonstrate that DSCG can be used as a green catalyst to produce hydrogen through methanolysis of sodium borohydride. To produce hydrogen by the sodium borohydride methanolysis (NaBH₄), DSCG was pretreated with different acids (HNO₃, CH₃COOH, HCl). According to the superior acid performance, acetic acid was selected and then different concentrations of the chosen acid were evaluated (1M, 3M, 5M, and 7M). Subsewuently, different temperatures (200, 300, 400 and 500 °C) and burning times (30, 45, 60 and 90 min) for the optimization of DSCG-catalyst were tested. The experiments with the use of CH₃COOH treated DSCG-catalyst reveal that the optimal acid concentration was 1M CH₃COOH and the burning temperatures and time were 300 °C and 60 min, respectively. FTIR, SEM, ICP-MS and CHNS elemental analysis were carried out for a through characterization of the catalyst samples. In this study, the experiments were carried out with 10 ml methanol solution contained 0.025 g NaBH₄ with 0.1 g catalyst at 30 °C unless otherwise stated. The effect of NaBH₄ concentration was investigated with use of 1%, 2.5%, 5%, and 7.5% NaBH₄, while the influence of catalyst concentration was discovered with the use of 0.05, 0.1, 0.15, and 0.25 g catalyst. Different temperatures were chosen (30, 40, 50 and 60 °C) to explore the hydrogen production performance of the catalyst. In addition, the maximum hydrogen production rate through methanolysis reaction of NaBH₄ by this catalyst was found to be 3171.4 mL min⁻¹gcat⁻¹. Also, the activation energy was determined to be 25.23 kJ mol⁻¹.     

Transition metal nanoparticle catalysts in releasing hydrogen from the methanolysis of ammonia borane

Ammonia borane (H₃N·BH₃, AB) is one of the promising hydrogen storage materials due to high hydrogen storage capacity (19.6% wt), high stability in solid state as well as in solution and nontoxicity. The methanolysis of AB is an alternative way of releasing H₂ due to many advantages over the hydrolysis such as having high stability against self releasing hydrogen gas. Here we review the reports on using various noble or non-noble metal(0) catalysts for H₂ release from the methanolysis of AB. Ni(0), Pd(0), and Ru(0) nanoparticles (NPs), stabilized as colloidal dispersion in methanol, are highly active and long lived catalysts in the methanolysis of AB. The catalytic activity, lifetime and reusability of transition metal(0) NPs show significant improvement when supported on the surface of solid materials. The supported cobalt, nickel, copper, palladium, and ruthenium based catalysts are quite active in H₂ release from the methanolysis of AB. Rh(0) NPs are highly active catalysts in releasing H₂ from the methanolysis of AB when confined within the void spaces of zeolite or supported on oxide nanopowders such as nanosilica, nanohydroxyapatite, nanoalumina or nanoceria. The oxide supported Rh(0) NPs can provide high activity with turnover frequency values as high as 218 min⁻¹ and long lifetime with total turnover values up to 26,000 in generation of H₂ from the methanolysis of AB at 25 °C. When deposited on carbon the bimetallic AgPd alloy nanoparticles have the highest activity in releasing H₂ through the methanolysis of AB.