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.     

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.     

Optimization of synthesis parameters for catalytic performance of Ni–B catalysts using response surface methodology

Hydrogen production through hydrolysis of sodium borohydride (NaBH₄) by using metal catalysts is promising for fuel cell applications. Nickel (Ni) and its alloys are favorable due to their high catalytic activity, relatively low cost and availability. In present study, the effects of temperature, pH, reduction rate and reducing agent concentration, which significantly affect the catalyst performance, were investigated using the response surface methodology (RSM). A mathematical model was derived according to results which were obtained from four-level orthogonal Taguchi L16 (4⁴) experimental design used for the optimization of multiple parameters in the process. From the RSM analyses, that compatible with the predicted experimental results, maximum hydrogen generation rate (HGR) 49.81 L min^?1 g_cat^?1 was obtained temperature of 278.12 K, pH of 5.52, reducing agent concentration of 85.96 NaBH₄.water^?1 and reduction rate of 6.82 mL min^?1. Analysis of variance reveals that both pH and rate of reduction have significant effect than the temperature on the HGR.     

Development of highly efficient and reusable Ruthenium complex catalyst for hydrogen evolution

Herein, we report an efficient, environmentally friendly and stable catalyst development to hydrogen evolution from sodium borohydride hydrolysis. For this purpose, Ruthenium complex catalyst successfully fabricated via 5-Amino-2,4-dichlorophenol-3,5-ditertbutylsalisylaldimine ligand and RuCl₃·H₂O salt. Ru complex catalyst was identified with X-Ray Diffraction Analysis, Infrared Spectroscopy, Elemental Analysis, Transmission electron microscopy, Scanning Electron Microscope and Brunauer-Emmett-Teller Surface Area Analysis. According to the analysis results, it was confirmed that Ru complex catalyst was successfully synthesized. Ru complex was used as a catalyst in NaBH₄ hydrolysis. The kinetic performance of Ru complex catalyst was evaluated at various reaction temperatures, various sodium borohydride concentration, catalyst concentration and sodium hydroxide concentration in hydrogen evolution. The apparent activation energy for the hydrolysis of sodium borohydride was determined as 25.8 kJ mol^?1. With fully conversion, the promised well durability of Ru complex was achieved by the five consecutive cycles for hydrogen evolution in sodium borohydride hydrolysis The hydrogen evolution rates were 299,220 and 160,832 mL H₂ g_cat^?1 min^?1 in order of at 50 °C and 30 °C. Furthermore, the proposed mechanism of Ru complex catalyzed sodium borohydride hydrolysis was defined step by step. This study provides different insight into the rational design and utilization and catalytic effects of ruthenium complex in hydrogen evolution performance.     

Co−O−P composite nanocatalysts for hydrogen generation from the hydrolysis of alkaline sodium borohydride solution

In recent years, catalytic hydrolysis of sodium borohydride is considered to be a promising approach for hydrogen generation towards fuel cell devices, and highly efficient and noble-metal-free catalysts have attracted increasing attention. In our present work, Co₃O₄ nanocubes are synthesized by solvothermal method, and then vapor-phase phosphorization treatment is carried out for the preparation of novel Co−O−P composite nanocatalysts composed of multiple active centers including Co, CoO, and Co₂P. For catalyst characterization, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and X-ray photoelectric spectroscopy (XPS) are conducted. Optimal conditions for catalyst preparation and application were investigated in detail. At room temperature (25 °C), maximum hydrogen generation rate (HGR) is measured to be 4.85 L min⁻¹ g⁻¹ using a 4 wt% NaBH₄ − 8 wt% NaOH solution, which is much higher than that of conventional catalysts with single component reported in literature. It is found that HGR remarkably increases with the increasing of reaction temperature, and apparent activation energy for catalytic hydrolysis of NaBH₄ is calculated to be 63 kJ mol⁻¹. After reusing for five times, the Co−O−P composite nanocatalysts still retains 78% of the initial activity.     

Synthesis of novel biocatalyst from organic waste protonated with acid treatment for hydrogen production

In this research study, orange peel-based biocatalysts developed from different acid protonation were used as a metal-free catalyst for hydrogen production from sodium borohydride (NaBH₄). In order to prepare the orange peel-based biocatalyst with higher catalytic activity, experiments were conducted with pure orange peel, different acid molar concentrations, and calcination temperatures. The physical morphology, surface texture, and chemical interaction were thoroughly analyzed by XRD, FTIR Raman, FESEM, BET, and TGA. As a result of the experiment, it was determined that the highly acid-treated biocatalyst (40% H₃PO₄, 40% H₂SO₄, 40% HCl) and calcinated at 450 °C for 1 h had higher catalytic activity. As a result, bio-hydrogen production at 35 °C and 70 °C methanolysis with 3% NaBH₄ catalyzed by a mixture of acid-treated catalysts were found as 46,213 and 63,842 ml min⁻¹g.cat⁻¹, respectively. However, with the increase of molar concentration of biocatalyst with 40% individual acid prolonged samples, the HGR rates will not have a satisfactory value in comparison with the 40% mixture of the acid-treated catalyst due to less number of active sites.     

Fabrication and characterization of poly(tannic acid) coated magnetic clay decorated with cobalt nanoparticles for NaBH4 hydrolysis: RSM-CCD based modeling and optimization

Hydrogen generation from sodium borohydride (NaBH₄) hydrolysis in the presence of metal catalysts is a frequently used and encouraging method for hydrogen storage. Metal nanoparticle-supported catalysts are better recyclability and dispersion than unsupported metal catalysts. In this study, the synthesis and characterization of a polymer-supported catalyst for hydrogen generation using NaBH₄ have been investigated. For the synthesis of polymeric material, first of all, kaolin (KLN) clay has been magnetically rendered by using the co-precipitation method (Fe₃O₄@KLN) and then coated with poly tannic acid (PTA@Fe₃O₄@KLN). Then, the catalyst loaded with cobalt (Co) nanoparticles have been obtained with the NaBH₄ reduction method (Co@PTA@Fe₃O₄@KLN). The surface morphology and structural properties of the prepared catalysts have been determined using methods such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS) and vibrating sample magnetometer (VSM). The optimization of the most important variables (NaBH₄ amount, NaOH amount, catalyst amount, and metal loading rate) affecting the hydrolysis of NaBH₄ using the synthesized polymeric catalysts was carried out using response surface methodology (RSM). Depending on the evaluated parameters, the desired response was determined to be hydrogen production rate (HGR, mL/g min). HGR was 1540.4 mL/g_cat. min. in the presence of the Co@PTA@Fe₃O₄@KLN at optimum points obtained via RSM (NaBH₄ amount 0.34 M, NaOH amount 7.9 wt%, catalyst amount 3.84 mg/mL, and Co loading rate 6.1%). The reusability performance of the catalyst used in hydrolysis of NaBH₄ was investigated under optimum conditions. It was concluded that the catalyst is quite stable.     

Phosphorus doped carbon nanodots particles based on pomegranate peels for highly active dehydrogenation of sodium borohydride in methanol

Here, the carbon nanodots were successfully synthesized from pomegranate peels (PPCD). This obtained PPCD was treated by a hydrothermal process with phosphoric acid for P doping (P doped PPCD) and used as a metal-free catalyst to obtain hydrogen(H₂) from sodium borohydride (NaBH₄) methanolysis for the first time. The characteristics of the samples obtained by ultraviolet, fluorescence, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and Inductively coupled plasma mass spectrometry (ICP-MS) analyses were examined. NaBH₄ concentration effect, temperature effect and catalyst reusability experiments were carried out. Using 10 mg of the catalyst with 2.5% NaBH₄, an HGR value of 13000 mL min^?1g^?1 was obtained. The activation energy (Ea) for the P-doped PPCD catalyst was 30.96 kJ mol^?1.     

Highly efficient and reactivated electrocatalyst of ruthenium electrodeposited on nickel foam for hydrogen evolution from NaBH4 alkaline solution

Cyclic life of catalyst for hydrolysis of sodium borohydride is one of the key issues, which hinder commercialization of hydrogen generation from sodium borohydride (NaBH₄) solution. This paper is aimed at promoting the cyclic life of Ru/Ni foam catalysts by employing an electro-deposition method. The effect of hydrolysis parameters on hydrolysis of sodium borohydride was studied for improving the catalytic performance. It is found that the hydrogen generation rate (HGR) of the hydrolysis reaction catalyzed by Ru/Ni foam catalyst can reach as high as 23.03 L min^?1 g^?1 (Ru). The Ru/Ni foam catalyst shows good catalytic activity after a cycleability test of 100 cycles by rinsing with HCl, which is considered as more effective method than rinsing with water for recovering the performance of Ru/Ni foam catalyst.     

Spirulina Platensis microalgae strain modified with phosphoric acid as a novel support material for Co–B catalysts: Its application to hydrogen production

Spirulina platensis is defined as the dried biomass of cyanobacteria in commercial use and is biomass with high carbon content. Spirulina platensis microalgae strain supported-CoB catalysts to produce hydrogen from sodium borohydride (NaBH₄) were prepared for the first time. The Spirulina platensis microalgae strain was modified with phosphoric acid (H₃PO₄) to proton. Then, the supported catalyst was performed to produce hydrogen from NaBH₄ hydrolysis. The optimum H₃PO₄ concentration, optimum Co amount, and optimum impregnation time of the H₃PO₄ with the microalgae strain were investigated. The maximum hydrogen production rate for the 30% CoB catalyst supported on microalgae strain treated with H₃PO₄ was found to be 3940 mL min⁻¹g⁻¹catalyst. X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer–Emmett–Teller (BET), and scanning electron microscope (SEM) analysis were performed for characterization of CoB catalyst supported on Spirulina microalgae strain. After four consecutive uses, the performance and conversion values of this catalyst were investigated. At the same time, the effect of temperature on the hydrogen production from this hydrolysis reaction was examined. The activation energy with the CoB catalyst supported on Spirulina microalgae strain was calculated as 35.25 kJ mol⁻¹. According to the kinetic model of a power law, n value was found as 0.25 for kinetic studies.     

A study on hydrogen generation from NaBH4 solution using Co-loaded resin catalysts

Hydrogen production via chemical processes has gained great attention in recent years. In this study, Co-based complex catalyst obtained by adsorption of Co metal to Amberlite IRC-748 resin and Diaion CR11 were tested for hydrogen production from alkaline NaBH₄ via hydrolysis process. Their catalytic activity and microstructure were investigated. Process parameters affecting the catalytic activity, such as NaOH concentration, Co percentage and catalyst amount, as well as NaBH₄ concentration and temperature were investigated. Furthermore, characteristics of these catalysts were carried out via SEM, XRD and FT-IR analysis. Hydrogen production rates equal to 211 and 221 ml min⁻¹ g_cat⁻¹ could be obtained with Amberlite IRC-748 resin and Diaion CR11 Co based complex catalysts, respectively. The activation energies of the catalytic hydrolysis reaction of NaBH₄ were calculated as 46.9 and 59.42 kJ mol⁻¹ for Amberlite IRC-748 resin and Diaion CR11 based catalysts respectively kJ mol⁻¹ from the system consisting of 3% Co, 10 wt% NaBH₄ and 7 wt% NaOH as well as 50 mg catalyst dosage. It can be concluded that Co-based resins as catalysts for hydrogen production is an effective alternative to other catalysts having higher 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.     

Hydrogen generation from NaBH4 hydrolysis catalyzed by cobalt (0)-Deposited cross-linked polymer brushes: Optimization with an experimental design approach

Proposing a novel catalyst that achieves catalytic hydrolysis of metal hydrides is an important stage in developing a hydrogen storage system. In this study, a cross-linked gel brush-cobalt (0) composite (Co@P4VP_GB@PMC) has been synthesized to obtain hydrogen from NaBH₄ solution. The morphology, structure, and composition of the obtained catalyst have been characterized by, FTIR, SEM, EDX, BET, XRD, ICP-MS and XPS. The parameters that significantly affect the hydrolysis of NaBH₄ (such as NaBH₄ concentration, NaOH amount, catalyst amount, and temperature) have been investigated using response surface methodology (RSM), an optimization method that has gained increasing importance in recent years. The hydrogen generation rate (HGR) was 4499 mL/min g_cat for Co@P4VP_GB@PMC when the NaBH₄ amount was 241.52 mM, NaOH amount 5 wt%, catalyst amount 10.55 mg and temperature 58.9 °C. Moreover, the apparent activation energy (E_a) for the catalytic hydrolysis reaction has been 41.27 kJmol^-1 obtained under optimum conditions. Additionally, the Co@P4VP_GB@PMC catalyst displayed significant reusability performance for up to five cycles without major loss of its activity. Compared with metal catalysts, this new cross-linked polymer gel brush-cobalt catalyst has excellent potential applications for hydrogen production by hydrolysis of metal hydrides due to its simple synthesis, low cost, and the easy availability of raw materials.     

Preparation of CoB catalysts supported on raw and Na-exchanged bentonite clays and their application in hydrogen generation from the hydrolysis of NaBH4

The aim of this work is to prepare CoB catalysts supported on raw bentonite (CoB/bentonite) and Na-exchanged bentonite (CoB/Na-bentonite) by the impregnation and chemical reduction method. The prepared catalysts were characterized using X-ray diffractometry (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. The activities of the catalysts were tested in the hydrolysis reaction of sodium borohydride (NaBH₄) in a semi-batch system. The volume of the evolved hydrogen gas was determined by a water displacement method. The effects of catalyst amount, NaOH (a base stabilizer) concentration, NaBH₄ concentration and solution temperature on the hydrogen generation rate were investigated. The maximum hydrogen generation rates were determined as 921.94 mL/min.g_cat for CoB/bentonite and 1601.45 mL/min.g_cat for CoB/Na-bentonite when the 5 wt % NaBH₄ and 10 wt % NaOH solutions were used at 50 °C. The activation energies (E_a) of the hydrolysis reaction over CoB/bentonite and CoB/Na-bentonite were determined as 55.76 and 56.61 kJ/mol, respectively.     

Solution combustion synthesized cobalt oxide catalyst precursor for NaBH4 hydrolysis

In this paper we report the solution combustion synthesis of cobalt oxide nanofoam from solutions of cobalt nitrate and glycine and subsequent use as an effective catalyst precursor for NaBH₄ hydrolysis. The catalytic activity results show that the hydrogen generation rate (HGR) at room temperature was much higher for the solution combustion synthesized material than for commercial Co₃O₄ nanopowder, though their specific surface areas were comparable (∼26–32 m²/g). Using a 0.6 wt.% aqueous solution of NaBH₄ at 20 °C and a 5 wt.% catalyst precursor loading, a HGR of 1.93 L min⁻¹ g_cat⁻¹ was achieved for solution combustion synthesized Co₃O₄. In contrast, at the same conditions, for commercial Co₃O₄ and elemental Co powders HGRs of 0.98 and 0.49 L min⁻¹ g_cat⁻¹ were achieved respectively. This type of synthesis is amenable to many complex metal oxide catalysts as well, such as LiCoO₂, which have also been shown to be good catalyst precursors for hydrolysis of NaBH₄.     

Metal-organic frameworks (MOFs) and MOFs-derived CuO@C for hydrogen generation from sodium borohydride

Hydrogen gas has been considered as one of the promising sources of energy. Thus, several strategies including the hydrolysis of hydrides have been reported for hydrogen production. However, effective catalysts are highly required to improve the hydrogen generation rate. Two dimensional metal-organic frameworks (copper-benzene-1,4-dicarboxylic, CuBDC), and CuBDC-derived CuO@C were synthesized, characterized and applied as catalysts for hydrogen production using the hydrolysis and methanolysis of sodium borohydride (NaBH₄). CuBDC, and CuO@C display hydrogen generation rate of 7620, and 7240 mlH₂·g_cat⁻¹· min⁻¹, respectively for hydrolysis. While, CuBDC offers hydrogen generation rate of 9060 mlH₂·g_cat⁻¹· min⁻¹ for methanolysis. Both catalysts required short reaction time, and showed good recyclability. The materials may open new venues for efficient catalyst for energy-based applications.     

Highly active and stable CeO2 supported nickel-complex catalyst in hydrogen generation

Cerium oxide supported 5-Amino-2,4-dichlorophenol-3,5-ditertbutylsalisylaldimine-Nickel complex for the first time was used to produce H₂ from hydrolysis of sodium borohydride. Cerium oxide supported Nickel complex catalyzed hydrolysis system was studied depend on temperature, concentration of sodium hydroxide, amount of Cerium oxide supported Ni complex catalyst, concentration of Ni complex and concentration of sodium borohydride. Cerium oxide supported Ni(II) complex display highly effective catalytic activity in sodium borohydride hydrolysis reaction. The obtained Cerium oxide supported Ni(II) complex catalyst was characterized by using Fourier Transform Infrared Spectroscopy, Scanning Electron Microscope, Transmission Electron Microscope, Brunauer-Emmett-Teller Surface Area Analysis, X-Ray Diffraction Analysis techniques. The catalyst stability was tested, even the fifth recycle the catalytic activity was maintained at 100%. Additionally the proposed Cerium oxide supported-Ni (II) complex catalyzed sodium borohydride hydrolysis mechanism was determined carefully. The experimental results showed that Cerium oxide supported Ni (II) complex catalyst accelerate sodium borohydride hydrolysis with 43,392 and 19,630 mL H₂ g_cat^?1 min^?1 hydrogen production rates at 50 °C and 30 °C respectively and 20,587 kJ mol^?1 activation energy.     

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.     

Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride

Porous carbon nanostructures are promising supports for stabilizing the highly dispersed metal nanoparticles and facilitating the mass transfer during the reaction, which are critical to achieve the high efficiency of hydrogen generation from sodium borohydride dehydrogenation. Herein, the catalytically active porous architectures are simply prepared by using 2-methylimidazole and melamine as reactive sources. The structural and compositional characterizations reveal the coexistence of metallic cobalt and N-doped carbon in porous architectures. Electron microscopy observations indicate that the synthesized products are smartly constructed from the carbon nanosheets with densely dispersed Co nanoparticles. Due to the notable structural features, the prepared Co@NC-600 sample presents the highly efficient activity for catalytic hydrolysis of NaBH₄ with a hydrogen generation rate of 2574 mL min⁻¹ g_cat⁻¹ and an activation energy of 47.6 kJ mol⁻¹. The catalytically active metallic Co and suitable support-effect of N-doped carbon are responsible for catalytic dehydrogenation.     

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.