Catalytic hydrolysis of sodium borohydride solution for hydrogen production using thermal plasma synthesized nickel nanoparticles

In the present study nickel nanoparticles were synthesized by thermal plasma route. In this method we obtained highly crystalline almost spherical nanoparticles with maximum number of particles having size around 30–50 nm. These nanoparticles were thoroughly characterized and employed as a catalyst for hydrogen production using hydrolysis of sodium borohydride (NaBH₄). The effect of initial concentration of NaBH₄, pH and temperature of solution on the rate of hydrogen production was investigated. Nickel nanoparticles exhibits first order reaction with respect to NaBH₄ concentration at elevated temperatures. After hydrolysis, the nickel nanoparticles showed presences of B–O and B–OH species on the nickel surface. The catalyst was found to be stable during 5 sequential cycles of test.     

Kinetics of hydrolysis of sodium borohydride for hydrogen production in fuel cell applications: A review

Hydrogen generation from the hydrolysis of sodium borohydride (NaBH₄) solution has drawn much attention since early 2000s, due to its high theoretical hydrogen storage capacity (10.8 wt%) and potentially safe operation. However, hydrolysis of NaBH₄ for hydrogen generation is a complex process, which is influenced by factors such as catalyst performance, NaBH₄ concentration, stabilizer concentration, reaction temperature, complex kinetics and excess water requirement. All of these limit the hydrogen storage capacities of NaBH₄, whose practical application, however, has not yet reached a scientific and technical maturity. Despite extensive efforts, the kinetics of NaBH₄ hydrolysis reaction is not fully understood. Therefore, better understanding of the kinetics of hydrolysis reaction and development of a reliable kinetic model is a field of great importance in the study of NaBH₄ based hydrogen generation system. This review summarizes in detail the extensive literature on kinetics of hydrolysis of aqueous NaBH₄ solution.     

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.     

Effects of crystallinity and morphology of solution combustion synthesized Co3O4 as a catalyst precursor in hydrolysis of sodium borohydride

Solution combustion synthesized (SCS) cobalt oxide (Co₃O₄) powder has been studied as a catalyst precursor for the hydrolysis of sodium borohydride (NaBH₄). Synthesis is completed in less than two minutes and results indicate SCS is capable of reproducibly synthesizing 98.5–99.5% pure Co₃O₄ nano-foam materials. SCS materials demonstrate an as-synthesized specific surface area of 24 m² g⁻¹, a crystallite size of 15.5 nm, and fine surface structures on the order of 4 nm. Despite having similar initial surface areas and sample purities, SCS-Co₃O₄ outperforms commercially available Co₃O₄ and elemental cobalt (Co) nano powders when used as a catalyst precursor for NaBH₄ hydrolysis. Hydrogen generation rates (HGR) using 0.6 wt% NaBH₄ in aqueous solution at 20 °C were observed to be 1.24 ± 0.2 L min⁻¹ g_cat⁻¹ for SCS nano-foam Co₃O₄ compared to 0.90 ± 0.09 and 0.43 ± 0.04 L min⁻¹ g_cat⁻¹ for commercially available Co₃O₄ and Co, respectively. The high catalytic activity of SCS-Co₃O₄ is attributed to its nano-foam morphology and crystallinity. During the hydrolysis of NaBH₄, the SCS-Co₃O₄ converts in-situ to an amorphous active catalyst with a specific surface area of 92 m² g⁻¹ and exhibits a honeycomb type morphology.     

Synthesis of Ni/TiO2 catalyst by sol-gel method for hydrogen production from sodium borohydride

Hydrogen is a sustainable, renewable and clean energy carrier that meets the increasing energy demand. Pure hydrogen is produced by the hydrolysis of sodium borohydride (NaBH₄) using a catalyst. In this study, Ni/TiO₂ catalysts were synthesized by the sol-gel technique and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) methods. The effects of Ni loading ratio (20–40%), catalyst amount (75–200 mg), the concentration of sodium hydroxide (NaOH, 0.25–1 M), initial amount of NaBH₄ (75–125 mg) and the reaction temperature (20–60 °C) on hydrogen production performance were examined. The hydrogen yield (100%) and hydrogen production rate (110.87 mL/g_cat.min) were determined at the reaction conditions of 5 mL of 0.25 M NaOH, 100 mg NaBH₄, 100 mg Ni/TiO₂, 60 °C. Reaction order and activation energy were calculated as 0.08 and 25.11 kJ/mol, respectively.     

Sustainable hydrogen production by catalytic hydrolysis of alkaline sodium borohydride solution using recyclable Co-Co2B and Ni-Ni3B nanocomposites

In this article, we report Co-Co₂B and Ni-Ni₃B nanocomposites as catalyst for hydrogen generation from alkaline sodium borohydride. Kinetic studies of the hydrolysis of sodium borohydride with Co-Co₂B and Ni-Ni₃B nanocomposites reveal that the concentration of NaBH₄ has no effect on the rate of hydrogen generation. Hydrolysis was found to be first order with respect to the concentration of catalyst. The catalytic activity of Co-Co₂B was found to be much higher than that of Ni-Ni₃B as inferred from the activation energies 35.245 KJ/mol and 55.810 kJ/mol, respectively. Co-Co₂B nanocomposites were found to be more magnetic than Ni-Ni₃B. These catalysts showed superior recyclability with almost the similar catalytic activities for several hydrolytic cycles supporting the principles of sustainability. Co-Co₂B catalyst showed hydrogen generation rate of about 4300 mL/min/g which is comparable to most of the reported good catalysts till date.     

Ruthenium nanoparticles supported in the network of HES-p(AMPS) IPN hydrogel as efficient catalyst for hydrogen production from the hydrolysis of ethylenediamine bisborane

In this study, Ru(0) nanoparticles supported in 2-hydroxyethyl starch-p-(2-Acrylamido-2-methyl-1-propanesulfonic acid) interpenetrating polymeric network (HES-p(AMPS) IPN) were synthesized as hydrogel networks containing hydroxyethyl starch, which is a natural polymer with oxygen donor atoms. The structure and morphology of the prepared HES-p(AMPS) IPN hydrogel and Ru@HES-p(AMPS) IPN catalyst were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), X-ray diffraction (XRD), and transmission electron microscope (TEM). Ru@HES-p(AMPS) IPN was used as catalyst for hydrogen production from the hydrolysis of ethylenediamine bisborane (EDAB). The activation parameters for the hydrolysis reaction of EDAB catalyzed by Ru@HES-p(AMPS) IPN were calculated as E_a = 38.92 kJ mol⁻¹, ΔH^# = 36.28 kJ mol⁻¹, and ΔS^# = −111.85 J mol⁻¹ K⁻¹, respectively. The TOF for the Ru@HES-p(AMPS) IPN catalyst was 2.253 mol H₂ (mol Ru(0) min)⁻¹. It was determined that Ru@HES-p(AMPS) IPN, a reusable catalyst, still had 81.5% catalytic activity after the 5th use.     

Cobalt nanoparticles packaged into nitrogen-doped porous carbon derived from metal-organic framework nanocrystals for hydrogen production by hydrolysis of sodium borohydride

Efficient safe transportation and generation of hydrogen are the key technologies for the hydrogen economy development in future. Sodium borohydride (NaBH₄) features highly volumetric density and environmentally benign hydrolysis products, which making it a promising candidate for chemical hydrogen storage. Cobalt nanoparticles packaged into nitrogen-doped porous carbon were successfully prepared by pyrolysis of MOFs. The addition of Zn in MOFs as a “fence” expanded the distance of adjacent Co atoms in space and simultaneously, the leaving Zn²⁺ sites generated free N sites during pyrolysis. These are beneficial to reduce the sizes of Co nanoparticles and enhance the dispersity of active sites. The modification method allows the cobalt nanoparticles to be uniformly and finely confined within the porous carbon. Contributed by highly dispersed Co nanoparticles and confinement effect, the catalyst showed excellent catalytic activity with hydrogen production rate of 1807 mL (H₂) min⁻¹·g_Co ⁻¹ and lower activation energy (20 kJ/mol) than ever reported. The stability test confirmed that deactivation of catalyst occurred due to deposition of borate species at the surface of catalyst. This observation may provide an idea to modify and upgrade stability of catalyst.     

Exergy and energy analysis of hydrogen production by the degradation of sodium borohydride in the presence of novel Ru based catalyst

Chemically possible hydrogen storage material of the most important and widely used metal hydride compound is sodium borohydride. A current research issue is the development of systems that allow regulated hydrogen generation employing appropriate catalysts for the creation of hydrogen gas from the hydrolysis of sodium borohydride (NaBH₄). In this study, controlled hydrogen production from alkali solution of NaBH₄ was aimed. On hydrogen generation rate (HGR), the effects of NaBH₄ and alkaline solution concentrations, catalyst quantity, and temperature were examined. Considering the energy and exergy analysis, which have gained importance in the international arena in recent years, in this study, the exergy energy analysis of the environment in which the sodium borohydride solution is located was performed. The best one of the Ru-based catalysts synthesized in different atomic ratios was determined as 90:10 RuCr. The surface characterization of the obtained catalyst was carried out using scanning electron microscope (SEM-EDX) and X-ray diffractometer (XRD). In the kinetic calculations, the activation energy was calculated as 35,024 kj/mol and the reaction ordered n was found to be 0,65. By applying exergy and energy analysis to the hydrogen production step, the energy and exergy efficiency of the system were found to be 24% and 7%, respectively.     

Effect of iron content on the hydrogen production kinetics of electroless-deposited CoNiFeP alloy catalysts from the hydrolysis of sodium borohydride,and a study of its feasibility in a new hydrolysis using magnesium and calcium borohydrides

The effect of Fe content in electroless-deposited CoNi-Fe_x-P alloy catalysts (x = 5.5–11.8 at.%) from the hydrolysis of NaBH₄ is investigated in alkaline sodium borohydride solution. The electroless-deposited CoNiFe_5.5-P and CoNiFe_7.6-P alloy catalysts are composed of flake-like micron particles; however, with an increase in Fe content to 11.8 at.%, the flake-like morphology is changed to a spherical shape and the crystal structure of the electroless-deposited CoNiFeP catalyst is transformed from FCC to BCC. Among all the CoNi-Fe_x-P alloy catalysts, the CoNi-Fe_x-P (x = 7.6 at.%) catalyst has the highest hydrogen production rate of 1128 ml min⁻¹ g⁻¹_catalyst in alkaline solution containing 1 wt% NaOH + 10 wt% NaBH₄ at 303 K. For the optimized catalyst, the activation energy of the hydrolysis of NaBH₄ is calculated to be 54.26 kJ mol⁻¹. Additionally, in this work, we report a new hydrolysis using Mg(BH₄)₂ and Ca(BH₄)₂. As a result, the Mg(BH₄)₂ is stored unstably in an alkaline solution, whereas the Ca(BH₄)₂ is stored stably. When optimizing the hydrogen production kinetics from the hydrolysis of Ca(BH₄)₂, the rate is 784 ml min⁻¹ g⁻¹_catalyst in 10 wt% NaOH + 3 wt% Ca(BH₄)₂ solution.     

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.     

Preparation,characterization, and properties of Pt/Al2O3/cordierite monolith catalyst for hydrogen generation from hydrolysis of sodium borohydride in a flow reactor

High-purity hydrogen can be generated by hydrolysis of sodium borohydride and used for operating portable proton exchange membrane fuel cells. The monolith supported catalyst is suitable for practical NaBH₄-based hydrogen generation system due to its simple reactor structure miniaturizing for small size applications and easy separation from the spent solution. In the present study, a structured catalyst was prepared by wash-coating the Al₂O₃ sol over the wall of cordierite monolith followed by depositing Pt using incipient wet impregnation method; then the monolithic catalysts were characterized by XRF, XRD, SEM, HRTEM and XPS. The catalytic activity of the Pt-based monolithic catalyst towards hydrolysis of NaBH₄ was tested using a flow reactor under ambient conditions in an autothermal manner. The characterization results show that Pt nanoparticles are highly dispersed on the surface of the Al₂O₃-coated layer. A continuous and stable hydrogen generation can be obtained by feeding the reactant (10 wt% NaBH₄–5 wt % NaOH) into the tube reactor loaded with the monolithic catalyst at feed rates of 0.5–2.0 mL min⁻¹.     

Synergistic enhancement of biohydrogen production by supplementing with green synthesized magnetic iron nanoparticles using thermophilic mixed bacteria culture

The production of biohydrogen can be improved by focusing on the nutrients needed by fermentative bacteria like iron. Iron reacts with the [Fe-Fe]-hydrogenase enzyme within the mixed bacteria culture for optimum hydrogen release. Iron nanoparticles (NPs) are attractive due to its unique properties and high reactivity. It can be produced through green synthesis, a more eco-friendly and relatively lower cost process, by using iron salt as precursor and green coconut shell extracted by deep eutectic solvent (DES) as reducing agent. The coconut shell extract consists of phytochemicals that help in producing polydisperse magnetic iron oxide nanoparticles at ～75 nm in size. The addition of optimum concentration of 200 mg Fe/L magnetic iron NPs resulted in the maximum cumulative hydrogen production, glucose utilization and hydrogen yield of 101.33 mL, 9.12 g/L and 0.79 mol H₂/mol glucose respectively. Furthermore, the kinetic analysis on Gompertz model using the optimum magnetic iron NPs concentration showed that the hydrogen production potential (P) and hydrogen production rate (R_m) increased to 50.69 mL and 3.30 mL/h respectively and the lag phase time reduced about 7.12 h as compared with the control experiment (0 mg Fe/L). These results indicated the positive effects of magnetic iron NPs supplementation on fermentative biohydrogen production of mixed bacteria culture and proved the feasibility of adding the magnetic iron NPs as the micronutrient for enhancement of such hydrogen production system.