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.     

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.     

Apricot Kernel shell waste treated with phosphoric acid used as a green,metal-free catalyst for hydrogen generation from hydrolysis of sodium borohydride

In this study, grinded apricot kernel shell (GAKS) biobased waste was used for the first time as a cost-effective, efficient, green and metal-free catalyst for hydrogen generation from the hydrolysis reaction of sodium borohydride (NaBH₄). For the hydrogen production by NaBH₄ hydrolysis reaction, GAKS was treated with various acids (HCl, HNO₃, CH₃COOH, H₃PO₄), salt (ZnCl₂) and base (KOH). As a result, the phosphoric acid (H₃PO₄) demonstrated better catalytic activity than other chemical agents. The hydrolysis of NaBH₄ with the GAKS-catalyst (GAKS_cat) was studied depending on different parameters such as acid concentration, furnace burning temperature and time, catalyst amount, NaBH₄ concentration and hydrolysis reaction temperature. The obtained GAKS_cat was characterized by ICP-MS, elemental analysis, TGA, XRD, FT-IR, Boehm, TEM and SEM analyses and was evaluated for its catalytic activity in the hydrogen production from the hydrolysis reaction of NaBH₄. According to the results, the optimal H₃PO₄ percentage was found as 15%. The maximum hydrogen generation rate from the hydrolysis of NaBH₄ with the GAKS_cat was calculated as 20,199 mL min⁻¹ g_cat⁻¹. As a result, it can be said that GAKS treated with 15% H₃PO₄ as a catalyst for hydrogen production is an effective alternative due to its high hydrogen production rate.     

A novel cost-effective catalyst from orange peel waste protonated with phosphoric acid for hydrogen generation from methanolysis of NaBH4

In this study, orange peel (OP), one of the organic wastes, was first used as a metal-free catalyst for the production of hydrogen from sodium boron hydride (NaBH₄). In order to prepare an orange peel catalyst (OP–H₃PO₄-Cat) with the best catalytic activity, experiments were carried out on pure orange peel with different acid types, different burning temperatures and different burning times. As a result of these experiments, it was determined that OP-H₃PO₄-Cat treated with 30% H₃PO₄ and burned at 400 °C for 45 min had the best catalytic activity. The OP-H₃PO₄-Cat material was characterised by several techniques such as FTIR, XRD and SEM. As a result, the hydrogen generation rates (HGR) at 30 °C and 60 °C in the methanolysis reaction of 2.5% NaBH₄ catalysed by OP-H₃PO₄-Cat were found as 45,244 and 61,892 mLmin^?1g.cat^?1, respectively. The activation energy of OP-H₃PO₄-Cat catalyst was calculated as 12.47 kJmol^-1.     

A highly active Co-B catalyst for hydrogen generation from sodium borohydride hydrolysis

Co-B catalysts were prepared by the chemical reduction of CoCl₂ with NaBH₄ for hydrogen generation from borohydride hydrolysis. The catalytic properties of the Co-B catalysts were found to be sensitive to the preparation conditions including pH of the NaBH₄ solution and mixing manner of the precursors. A Co-B catalyst with a very high catalytic activity was obtained through the formation of a colloidal Co(OH)₂ intermediate. The ultra-fine particle size of 10 nm accounted for its super activity for hydrogen generation with a maximum rate of 26 L min⁻¹ g⁻¹ at 30 °C. The catalyst also changed the hydrolysis kinetics from zero-order to first-order.     

The use of metallurgical waste sludge as a catalyst in hydrogen production from sodium borohydride

In this study, the metallurgic sludge which contained oil and was obtained as waste of grinding, sharpening and milling parts was used in the production of hydrogen (H₂) from sodium borohydride (NaBH₄). The hydrolysis of NaBH₄ with the metallurgic sludge catalyst was investigated depending on several parameters such as sodium hydroxide (NaOH) concentration, catalyst amount, NaBH₄ concentration and temperature. The obtained metallurgic sludge catalyst was characterized by the XRD, FT-IR and SEM techniques and was evaluated for its activity in the H₂ generation from NaBH₄ hydrolysis. The maximum H₂ production rate from the hydrolysis of NaBH₄ with the metallurgic sludge catalyst was calculated as 9366 ml min⁻¹.g_cat⁻¹. The value of activation energy was found as 48.05 kJ mol⁻¹.     

A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst

In this study, activated carbon is produced from defatted hazelnut bagasse at different activation conditions. The catalytic activities of activated carbons are evaluated for NaBH₄ methanolysis and electrooxidation. These materials are characterized by N₂ adsorption-desorption, FTIR, SEM-EDS and XPS and results show that these materials are prepared successfully. N₂ adsorption-desorption results reveal that activated carbon (FH3-500) has the highest BET surface area as 548 m²/g, total pore volume as 0.367 cm³/g and micropore volume as 0.205 cm³/g. On the orher hand, as a result of hydrogen production studies, FH3-500 activated carbon catalyst has the highest initial hydrogen production rate compared to other materials. At 50 °C, this metal-free activated carbon catalyst has a high initial hydrogen production rate of 13591.20 mL/min.g_cat, which is higher than literature values. Sodium borohydride electrooxidation measurements reveal that FH2-500 also has the highest electrocatalytic activity and stability. Hazelnut pulp-based activated carbons are firstly used as a metal-free catalyst in the methanolysis and electrooxidation of sodium borohydride, and its catalytic activity is good as a metal-free catalyst. The results show that the hazelnut pulp-based activated carbon catalyst is promising as a metal-free catalyst for the methanolysis and electrooxidation of sodium borohydride.     

Acetic acid, a relatively green single-use catalyst for hydrogen generation from sodium borohydride

Acid-catalyzed hydrolysis of sodium borohydride (NaBH₄) has been studied (reactivity and kinetics) at high acid concentration (0.32 M). A mineral (hydrochloric acid, HCl) and an organic benign (acetic acid, CH₃COOH) acid have been chosen. Our study has three distinct objectives, namely: (i) combining the simplicity of the storage of solid NaBH₄ with the simplicity of the aqueous solution of acid; (ii) showing CH₃COOH can be as reactive as HCl in specific well-chosen operating conditions; and (iii) emphasizing the relative greenness of the CH₃COOH-based process. All of these objectives have been fulfilled and show that CH₃COOH is a benign relatively green acid catalyst of choice for catalyzing hydrogen generation from NaBH₄, the acid–water–NaBH₄ system being quite simple.     

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.     

Influence of process parameters on enhanced hydrogen generation via semi-methanolysis and semi-ethanolysis reactions of sodium borohydride using phosphoric acid

The sodium borohydride(NaBH₄) semi-methanolysis and semi-ethanolysis reactions to produce hydrogen are investigated using phosphoric acid(H₃PO₄) for the first time. The NaBH₄ concentration, H₃PO₄ concentration, and temperature parameters on these semi-alcoholysis reactions are evaluated. The normalized hydrogen generation rates (HGRs) obtained from the NaBH₄ semi-methanolysis and semi-ethanolysis acidified using 0.5 M H₃PO₄ are 11684 and 9981 ml min⁻¹ g⁻¹, respectively. Moreover, the completion times of these semi-methanolysis and semi-ethanolysis reactions with 0.5 M H₃PO₄ acid concentration are 0.10 and 0.116 min, respectively. Kinetic studies with the power-law model are evaluated. The activation energies(Ea) obtained for the NaBH₄ semi-methanolysis and semi-ethanolysis using 0.5 M H₃PO₄ are 9.08 and 32.47 kJ mol⁻¹, respectively.     

Indirect hydrolysis of sodium borohydride: Isolation and crystallographic characterization of methanolysis and hydrolysis by-products

The use of sodium borohydride as a means for hydrogen generation has focused on the base-stabilized hydrolysis reaction, while literature for the methanolysis of sodium borohydride remains scarce. Sodium borohydride methanolysis is an alternative for hydrogen production from sodium borohydride and has a number of advantages over hydrolysis reactions in terms of by-product handling. Previous studies have shown that the presence of water in methanol significantly retards the rate of hydrogen evolution from NaBH₄. This article reports the production of hydrogen from NaBH₄ using rigorously dried methanol. In addition, the solid-state structure of the methanolysis by-product is reported, which lends pertinent information for its hydrolysis for methanol recovery. Also reported is the solid-state structure of the hydrolysis by-product.     

Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH₄) in fuel cell fields. In this study, hydrogen production from alkaline NaBH₄ via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200–400 °C, but a high calcination temperature above 500 °C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co–B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH₄, and the hydrogen generation rate increases for lower NaBH₄ concentrations and decreases after reaching a maximum at 10 wt.% of NaBH₄.     

Nickel modified dolomite in the hydrogen generation from sodium borohydride hydrolysis

Hydrogen is expected to play an important role as an energy carrier in the world's future energy systems, as it is environmentally friendly and flexible in use. Hydrolysis of NaBH₄ is a promising and effective method, especially for fuel cells and other portable devices, thanks to hydrogen release. Therefore, catalyst research is of great importance in the development of this technology. In this study, Ni/Dolomite catalyst was synthesized by wet impregnation method and used in hydrolysis process. Additionally, the effects of reaction temperature (30–60 °C), nickel content (10–40 wt%), catalyst amount (25–125 mg), NaOH concentration (0.10–0.75 M), and an initial amount of NaBH₄ (25–125 mg) on hydrogen yield were investigated. Eventually, the catalyst with 40 wt% Ni content was assigned as the most suitable catalyst, attaining H₂ production of 100% with a rate of 88.16 mL H₂/g_cat.min at 60 °C with 5 mL of 0.25 M NaOH, NaBH₄, and Ni/Dolomite catalyst (100 mg).     

Aluminum chloride for accelerating hydrogen generation from sodium borohydride

The present research paper reports preliminary results about the utilization of anhydrous aluminum chloride (AlCl₃) for accelerating hydrogen generation through hydrolysis of aqueous solution of sodium borohydride (NaBH₄) at 80 °C. To the best of our knowledge, AlCl₃ has never been considered for that reaction although many transition metal salts had already been assessed. AlCl₃ reactivity was compared to those of AlCl₃·6H₂O, AlF₃, CoCl₂, RuCl₃ and NiCl₂. With AlCl₃ and a NaBH₄ solution having a gravimetric hydrogen storage capacity (GHSC) of 2.9 wt.%, almost 100% hydrogen was generated in few seconds, i.e., with a hydrogen generation rate (HGR) of 354 L min⁻¹ g⁻¹(Al). This HGR is one of the highest rates ever reported. Higher HGRs were obtained by mixing AlCl₃ with CoCl2, RuCl₃ or NiCl₂. For example, the system RuCl₃:AlCl₃ (50:50 mass proportion) showed a HGR > 1000 L min⁻¹ g⁻¹(Ru:Al). The hydrolysis by-products (once dried) were identified (by XRD, IR and elemental analysis) as being Al(OH)₃, NaCl and Na₂B(OH)₄Cl and it was observed that even in situ formed Al(OH)₃ has catalytic abilities with HGRs of 5 L min⁻¹ g⁻¹(Al). All of these preliminary results are discussed, which concludes that AlCl₃ has a potential as accelerator for single-use NaBH₄-based storage system.     

Ethylene glycol as an alternative solvent approach for very efficient hydrogen production from sodium borohydride with phosphoric acid and acetic acid catalysts

For the first time, phosphoric acid (H₃PO₄) and acetic acid (CH₃COOH) catalysts were used for efficient hydrogen (H₂) production from sodium borohydride (NaBH₄) ethylene glycolysis reaction. In this experimental study, the effects of ethylene glycol/water ratio, ethylene glycol/acid ratio, NaBH₄ concentration, acid concentration, and temperature were investigated. These ethylene glycol/water ratio experiments showed that the use of water alongside ethylene glycol negatively affects H₂ production. The hydrogen generation rate (HGR) values obtained for this ethylene glycolysis reaction with 1 M H₃PO₄ and 1 M CH₃COOH catalysts are 5800 and 4542 mLmin^-1, respectively. Also, the completion times of ethylene glycolysis reactions with these acids are 8 and 10 s, respectively. The n value obtained for ethylene glycolysis reactions according to the power-law kinetic model was 0.50. The activation energies obtained with H₃PO₄ and CH₃COOH catalysts were 24.45 kJ mol^?1and 33.23 kJ mol^?1, respectively.     

Fluorinated cobalt for catalyzing hydrogen generation from sodium borohydride

The present paper reports preliminary results relating to a search for durable cobalt-based catalyst intended to catalyze the hydrolysis of sodium borohydride (NaBH₄). Fluorination of Co [Suda S, Sun YM, Liu BH, Zhou Y, Morimitsu S, Arai K, et al. Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts. Appl Phys A 2001; 72: 209–12.] has attracted our attention whereas the fluorination of Co boride has never been envisaged so far. Our first objective was to compare the reactivity of fluorinated Co with that of Co boride. We focused our attention on the formation of Co boride from fluorinated Co. Our second objective was to show the fluorination effect on the reactivity of Co. Our third objective was to find an efficient, durable Co catalyst. It was observed a limited stabilization of the Co surface by virtue of the fluorination, which made the formation of surface Co boride more difficult while the catalytic activity was unaltered. The fluorination did not affect the number of surface active sites. Nevertheless, it did not prevent the formation of Co boride. The fluorination of Co boride was inefficient. Hence, fluorination is a way to gain in stabilization of the catalytic surface but it is quite inefficient to hinder the boride formation. Accordingly, it did not permit to compare the reactivity of Co boride with that of Co.     

Synergistic effect on hydrolytic sodium borohydride adding waste Al for hydrogen generation

Synergistic effect of sodium borohydride (NaBH₄) mixed with waste aluminum in hydrolytic system were investigated to improve the hydrogen generation (HG) efficiency. The alkaline aqueous originated from NaBH₄ hydrolysis impels the passive aluminum hydroxide film of Al surface to be dissolved, thus, mutual effect of HG amount increasing by 88% and 50% for Al powder and waste Al can, respectively. To add acid catalyst in the mutual mixture system prompts to significantly accelerate HG rate from 100 ml/min˙g to 400 ml/min˙g but raising temperature is not obviously found. It is speculated that exothermic effect dominates the NaBH₄ hydrolytic reaction and eliminates the temperature effect. In this study, the mutual hydrolyzed reaction of NaBH₄ and waste Al provides ecofriendly environment, low cost and enables to achieve higher HG rate and further uses for portable/mobile fields.     

Performance of g-C3N4 nanoparticles by EDTA modification and protonation for hydrogen release from sodium borohydride methanolysis

Here, for the first time, a metal-free catalyst was synthesized by ethylenediamine tetra-acetic acid (EDTA) modification of the carbon nitride (g-C₃N₄) sample and protonation of the obtained sample. The catalyst was used for the production of H₂ from the methanolysis of sodium borohydride (NaBH₄). The EDTA modification and protonation of the g-C₃N₄ sample was confirmed by XRD, FTIR, SEM-EDX, and TEM analyses. During the hydrogen generation, NaBH₄ concentration effect, catalyst amount effect, temperature effect and catalyst reusability were investigated. The HGR value obtained with 2.5% NaBH₄ using 10 mg catalyst was 7571 mL min^?1g^?1. The activation energy (Ea) for the g–C₃N₄–EDTA-H catalyst was found to be 32.2 kJ mol^?1 The reusability of the g–C₃N₄–EDTA-H catalyst shows a catalytic performance of 72% even after its fifth use.