Very fast H2 production from the methanolysis of NaBH4 by metal‐free poly(ethylene imine) microgel catalysts

The polyethyleneimine (PEI) microgels prepared via microemulsion polymerization are protonated by hydrochloric acid treatment (p‐PEI) and quaternized (q‐PEI) via modification reaction with methyl iodide and with bromo alkanes of different alkyl chain lengths such as 1‐bromoethane, 1‐bromobutane, 1‐bromohexane, and 1‐bromooctane. The bare p‐PEI and q‐PEI microgels are used as catalysts directly without any metal nanoparticles for the methanolysis reaction of sodium borohydride (NaBH₄). Various parameters such as the protonation/quaternization reaction on PEI microgels, the amount of catalyst, the amount of NaBH₄, and temperature are investigated for their effects on the hydrogen (H₂) production rate. The reaction of self‐methanolysis of NaBH₄ finishes in about 32.5 min, whereas the bare PEI microgel as catalyst finishes the methanolysis of NaBH₄ in 22 min. Surprisingly, it is found that when the protonated PEI microgels are used as catalyst, the same methanolysis of NaBH₄ is finished in 1.5 min. The highest H₂ generation rate value is observed for protonated PEI microgels (10 mg) with 8013 mL of H₂/(g of catalyst.min) for the methanolysis of NaBH₄. Moreover, activation parameters are also calculated with activation energy value of 23.7 kJ/mol, enthalpy 20.9 kJ/mol, and entropy ?158 J/K.mol. Copyright © 2016 John Wiley & Sons, Ltd.     

Catalytic activity of metal-free amine-modified dextran microgels in hydrogen release through methanolysis of NaBH4

Polymeric microgels were prepared from dextran (Dex) by crosslinking linear natural polymer dextran with divinyl sulfone (DVS) with a surfactant-free emulsion technique resulting in high gravimetric yield of 78.5 ± 5.3% with wide size distribution. Dex microgels were chemically modified, and then used as catalyst in the methanolysis of NaBH₄ to produce H₂. The chemical modification of Dex microgel was done on epichlorohydrin (ECH)-reacted Dex microgels with ethylenediamine (EDA), diethylenetriamine (DETA), and triethylenetetraamine (TETA) in dimethylformamide (DMF) at 90°C for 12 hours. The modified dextran-TETA microgels were protonated using treatment with hydrochloric acid (HCl) and m-Dex microgels-TETA-HCl was found to be a very efficient catalyst for methanolysis of NaBH₄ to produce H₂. The effects of reaction temperature and NaBH₄ concentration on H₂ generation rates were investigated and m-Dex microgels-TETA-HCl catalyst possessed excellent catalytic performances with 100% conversion and 80% activity at end of 10 consecutive uses and was highly re-generatable with simple HCl treatment. Interestingly, m-Dex microgels-TETA-HCl catalyst can catalyze NaBH₄ methanolysis reaction in a mild temperature range 0 to 35°C with E_a value of 30.72 kJ/mol and in subzero temperature range, −20 to 0°C with E_a value of 32.87 kJ/mol, which is comparable with many catalysts reported in the literature.     

Can fool's gold “pyrite” become real gold as a catalyst for clean-energy H2 production?

The natural, most abundant sulfide mineral of pyrite was modified using polyethyleneimine (PEI) for use as a catalyst in H₂ release reactions from NaBH₄ in methanol. The catalytic performances of pyrite, pyrite-PEI, and protonated pyrite-PEI (pyrite-PEI+) were compared and the hydrogen generation rate (HGR) values of 795 ± 26, 2883 ± 190, and 4320 ± 188 mL H₂/(g of catalyst x min)⁻¹ were measured for H₂ production from NaBH₄ methanolysis. The effect of methanol:water mixture at various ratios, the amount of catalyst, the concentration of NaBH₄, and temperature on H₂ production from NaBH₄ in methanol catalyzed by pyrite-PEI⁺ were investigated. The activation energies for pyrite-PEI, and pyrite-PEI⁺ catalyzed H₂ release reactions were calculated as 47.2 and 36.8 kJ/mol, respectively. It was found that the activity % for the pyrite-PEI⁺ catalyst decreased to 76.2 ± 2.7% after five consecutive uses with 100% conversion for each re-use study. Furthermore, the re-generation of pyrite-PEI⁺ catalyst after the 5th usage was readily ensured by HCl treatment to completely recover and further increase the activity% of the catalyst. Therefore, pyrite was shown to be a useful re-generable and economic green catalyst for H₂ production in many potential applications.     

PDMA cryogel beads as a catalyst for hydrogen generation from NaBH4 alcoholysis

Poly[2-(dimethylamino)ethyl methacrylate] cryogel beads were prepared under cryogenic conditions via free radical polymerization and used as a catalyst in the production hydrogen (H₂) from NaBH₄ by alcoholysis. The efficiency of the catalyst was investigated in the range of 0–40 °C by both methanolysis and ethylene glycolysis reactions, and its reuse was tested. Accordingly, it was observed that the methanolysis reaction was faster than the ethylene glycolysis reaction. When the hydrogen generation rate (HGR) values between 0 and 40 °C were compared, it was concluded that the methanolysis reaction rate increased from 1550 to 4800 mL.min⁻¹g⁻¹ and the ethylene glycolysis reaction rate increased from 923 to 3551 mL.min⁻¹g⁻¹. In the alcoholysis reaction catalyzed by PDMA cryogel beads, the activation energy was calculated as 19.34 and 22.77 kJ.mol⁻¹ for the methanolysis and ethylene glycolysis reactions, respectively. After six repetitions, the catalyst activity was calculated over 50% for NaBH₄ methanolysis and ethylene glycolysis.     

Metal nanoparticle-embedded super porous poly(3-sulfopropyl methacrylate) cryogel for H2 production from chemical hydride hydrolysis

Poly(3-sulfopropyl methacrylate) (p(SPM)) cryogel was prepared under cryogenic conditions (T = −18 °C) and used as template for in situ metal nanoparticle preparation of Co, Ni and Cu. These metal nanoparticle-containing super macroporous cryogel composites were tested for H₂ production from hydrolysis of sodium borohydride (NaBH₄) and ammonia borane (AB). It was found that amongst p(SPM)-M (M: Co, Ni, and Cu) composite catalyst systems, the catalytic performances of Co- and Ni-containing p(SPM) cryogel composite catalyst systems were the same, however in hydrolysis of NH₃BH₃, the order of performance of the catalysts was Co > Ni > Cu. Interestingly, p(SPM)-Co cryogel composite demonstrated better catalytic performances in salt environments e.g., faster H₂ production rate in sea and tap water compared to DI water, and almost no effect of ionic strength of the solution medium was observed, but the salt types were found to affect the H₂ generation rate. Other parameters that affect H₂ production rate such as metal type, temperature, water source, salt concentration, amount of metal nanocatalyst and reusability were investigated. It was found that the hydrogen generation rate (HGR) was increased to 2836 ± 90 from 1000 ± 53 (ml H₂)(g of Co min)⁻¹ by multiple loading and reduction cycles of Co catalyst. Also, it was found that TOF values are highly temperature dependent, and increased to 15.1 ± 0.8 from 2.4 ± 0.1 (mol H₂)(mol catalyst min)⁻¹ by increasing the temperature from 30 to 70 °C. The activation energy, activation enthalpy and activation entropy were determined as 40.8 kJ (mol)⁻¹, 37.23 kJ (mol K)⁻¹, and −170.87 J (mol K)⁻¹, respectively, for the hydrolysis reaction of NaBH₄ with p(SPM)-Co catalyst system, and 25.03 kJ (mol)⁻¹, 22.41 kJ (mol K)⁻¹, and −182.8 J (mol K)⁻¹, respectively, for AB hydrolysis catalyzed by p(SPM)-Co composite system.     

Insight into the role of solvents in enhancing hydrogen production: Ru-Co nanoparticles catalyzed sodium borohydride dehydrogenation

Ru-Co nanoparticles prepared in nano-size by combustion derived of citric acid used sol-gel technique followed by calcination process at 450 °C. The external and internal properties of nano-sized catalyst were characterized by XRD, XPS, SEM, TEM, ICP-OES, and N₂ sorption techniques. The characterization results proved that nano-sized catalyst was mixture of cubic Co₃O₄ (18 nm) and tetragonal RuO₂ (40 nm) crystals with mesoporous structure (12.64 m²g^-1). Insight into the role of solvents for enhancing hydrogen production from Ru-Co nanoparticles catalyzed sodium borohydride (NaBH₄, SBH) was systematically studied by altering the dehydrogenation medium with water or methanol. The reaction kinetic performance of nano-sized catalyst was evaluated by performing both hydrogen generation reactions at various reaction temperatures, initial SBH concentration, and catalyst dosage to evaluate the hydrogen generation activity. Ru-Co nanoparticles exhibited exclusive catalytic performance for hydrogen generation by hydrolysis and methanolysis of SBH. The apparent activation energies (E_a) for the catalytic hydrolysis and methanolysis of SBH over Ru-Co nanoparticles were determined to be 20.02 kJ mol⁻¹ and 54.38 kJ mol⁻¹, respectively. Furthermore, Ru-Co nanoparticles also performed satisfied stability for both hydrolysis and methanolysis reactions. Beside both hydrogen generation was achived with fully conversion of SBH, Ru-Co nanoparticles promised good recyclability for at least 5 cycle for methanolysis of SBH.     

Aboundent oxygen defects in CoFe-LDH derivatives for enhanced photo-thermal synergistic catalytic hydrogen production from NaBH4

Two-dimensional catalysts, which are sensitive to visible light and have a photothermal effect, can be used to catalyse the release of H₂ from sodium borohydride (NaBH₄) are being actively explored in energy saving systems. In this work, oxygen vacancy enriched two-dimensional CoFe-layered double hydroxide (CoFe-LDH) derivatives (named as CoFe-x °C, x = 200–500) have been explored for NaBH₄ hydrolysis catalyzed by photo-thermal synergy without external heat source. The CoFe-300 °C presents its initial hexagonal lamellar structure and has the highest concentration of oxygen vacancy. These unique properties guarantee its excellent photo-thermal synergistic catalytic performance, achieving hydrogen production rate of 1877.5 mmol g⁻¹ h⁻¹, and maintains high efficiency after 5 cycles. This enhanced photo-thermal synergistic catalytic mechanism is the •OH (generated from h⁺ and H₂O) attacks BH₄⁻ (absorbed on O_v sites) to produce H₂, the heat from photothermal conversion accelerates the adsorption ability and attacking rate. This study opens a new strategy for the synergistic photo-thermal catalytic hydrolysis of NaBH₄.     

Monodispersed p(2-VP) and p(2-VP-co-4-VP) particle preparation and their use as template for metal nanoparticle and as catalyst for H2 production from NaBH4 and NH3BH3 hydrolysis

The monodispersed poly(2-vinyl pyridine) (p(2-VP)) and poly(2-vinyl pyridine-co-4-vinyl pyridine) (p(2-VP-co-4-VP)) particles of different compositions were synthesized by a surfactant-free emulsion polymerization system using divinyl benzene (DVB) as cross-linker. The diameter of p(2-VP) and p(2-VP-co-4-VP) particles were measured between 370 and 530 nm. Co, Ni and Cu metal nanoparticles were prepared inside these microgels after quaternization with HCl and loading of metal salts, such as CoCl₂, NiCl₂, and CuCl₂, in ethyl alcohol followed by reduction with NaBH₄. The prepared metal nanoparticles within these particles were used as catalyst for H₂ production via hydrolysis of NaBH₄ and NH₃BH₃. Various parameters of the polymeric microgels such as template, metal types, reuse, the amount of NaOH, and temperature were investigated. From hydrolysis reactions the activation energy (E_a), enthalpy (ΔH), and entropy (ΔS) were calculated for Co metal nanoparticles as catalyst for the NaBH₄ hydrolysis reaction in the temperature range of 0–50 °C. The activation parameters of NaBH₄ hydrolysis catalyzed by Co nanoparticle composite systems were calculated as 46.44 ± 1.1 kJ mol⁻¹ for E_a, 36.39 ± 6.5 kJ mol⁻¹ for ΔH and −170.56 ± 20.1 kJ mol⁻¹ K⁻¹ for ΔS.     

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.     

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.     

Metal ion-imprinted hydrogel with magnetic properties and enhanced catalytic performances in hydrolysis of NaBH4 and NH3BH3

Metal ion-imprinted (IIH) poly(2-acrylamido-2-methyl-1-propansulfonic acid) p(AMPS) hydrogels were prepared by using a free-radical polymerization technique in the presence of metal ions (M = Co (II) or Ni (II)). Using metal ion-imprinted hydrogels (IIHs), and non-metal ion-imprinted (NIH) hydrogels as template for the preparation of Co and Ni catalyst systems, the hydrolysis kinetics of NaBH₄ and NH₃BH₃ were investigated. The catalytic performances of IIHs and NIHs were compared in terms of effect on hydrolysis kinetics of NaBH₄ and NH₃BH_3. To increase the amounts of Co nanoparticles within p(AMPS) hydrogel for better catalytic activity, several reloading and reduction cycles of Co (II) ions were carried out, and the prepared p(AMPS)-Co composite catalyst systems were tested for hydrogen generation from the hydrolysis of NaBH₄. As the number of Co (II) loading and reduction cycles increased, the amount of metal catalysts and the catalytic performance of composites increased. Kinetics studies were carried out on three times Co (II) ion loaded and reduced p(AMPS)-Co catalyst systems (containing 36.80 mg/g Co). Three time Co (II)-loaded catalyst systems provided very fast hydrolysis kinetics for NaBH₄, and provided magnetic field responsive behavior. The hydrolysis reaction of NaBH₄ was completed within 50 s, under the described conditions at 60 °C. It was demonstrated that the synthesized catalyst systems can be used ten times repetitively without significant loss of catalytic activity (86.5%).     

Metal nanoparticles supported on polyacrylamide water beads as catalyst for efficient generation of H2 from NaBH4 methanolysis

Water beads made from polyacrylamide polymer p-(AAm) were decorated with high efficient metal nanoparticles by inexpensive, fast, simple, and environmental friendly method. These water beads balls were kept in the metal salt solutions for 4 h; to adsorb the metals ions from these aqueous solutions. The metal ions decorated on the p-(AAm) water beads were converted to metal nanoparticles by its reduction with aqueous solution of NaBH₄. The prepared materials p-(AAm) loaded with MNPs (M@p-(AAm)) were characterized by ATR-FTIR, XRD, XPS, FESEM, and EDS which show the successful preparation of MNPs over the surface and within p-(AAm). Afterwards the M@p-(AAm) were investigated as a catalyst for the generation of hydrogen from the methanolysis of NaBH₄. The Ag@p-(AAm) show good catalytic activity for NaBH₄ methanolysis reaction as compared to the other loaded MNPs. In addition, different parameters which effecting H₂ generation were also investigated such as; MNPs types, catalyst amount and temperature of the reaction. Low activation energy (Ea) of 21.37 ± 0.67 kJ mol⁻¹, was calculated for NaBH₄ methanolysis reaction at temperature ranging from 5.0 °C to 35 °C. Moreover, the catalyst reusability was also studied and found no decrease in percent conversion, however percent efficiency was decreases about 37% after completion of four cycles.     

Superporous P(2-hydroxyethyl methacrylate) cryogel-M (M:Co,Ni, Cu) composites as highly effective catalysts in H2 generation from hydrolysis of NaBH4 and NH3BH3

Highly porous p(2-hydroxyethyl methacrylate) p(HEMA) cryogels were synthesized via cryopolymerization technique and used as template for Co, Ni, and Cu nanoparticle preparation, then as composite catalyst systems in H₂ generation from hydrolysis of both NaBH₄ and NH₃BH₃. Due to their highly porous and open microstructures, p(HEMA)-Co cryogel composites showed very effective performances in H₂ production from hydrolysis of both chemical hydrides. The characterization of p(HEMA) cryogels, and their metal composites was determined via various techniques including swelling experiments, digital camera images, SEM and TEM images, AAS and TGA measurements. The effect of various parameters on the hydrolysis reaction of NaBH₄ such as metal types, concentration of chemical hydrides, amounts of catalyst, alkalinity of reaction medium and temperature were investigated in detail. It was found that Co nanoparticles are highly active catalysts in H₂ generation reactions from both hydrides. The hydrogen generation rate (HGR) of p(HEMA)-Co was 1596 (mL H₂) (min)⁻¹ (g of Co)⁻¹ which is quite good in comparison to reported values in the literature. Furthermore, kinetic parameters of p(HEMA)-Co metal composites such as energy, enthalpy and entropy were determined as Ea = 37.01 kJmol⁻¹, ΔH# = 34.26 kJmol⁻¹, ΔS# = −176,43 Jmol⁻¹ K⁻¹, respectively.     

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.     

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.     

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.     

Poly (acrylic acid)/polysaccharides IPN derived metal free catalyst for rapid hydrogen generation via NaBH4 methanolysis

Polymeric catalysts have displayed great performance for catalytic hydrogen generation. However, the reported metal free polymeric catalysts for NaBH₄ methanolysis are mainly limited to coating strategy where the catalytic activity fade after few cycles. Herein, we report an interpenetrating polymer network (IPN) strategy for rapid and highly recyclable NaBH₄ catalytic methanolysis to produce hydrogen (H₂) gas. In this study, we prepared poly(acrylic acid)/polysaccharide IPN via Pickering tempted polymerization. The hydrogen generation performance was studied employing different parameters where maximum HGR of 8182 mL H₂ min^?1 g^?1 of CAP. The activation energy Ea, enthalpy and entropy were calculated to be 62.99 kJ mol^?1, 32.25 kJ mol and ?130.92 J mol K^?1, respectively. Above all, CAP kept cyclic performance to 100% even at the 7th cycle. We confirmed the reproducibility of approach with other natural polysaccharides. This was due to strong chain entanglement of IPN synthesis which forces the active sites to stay in place during cyclic catalysis reaction. Thus, the IPN strategy ensures longer catalyst life for catalytic methanolysis of NaBH₄ for H₂ generation.     

Magnetic dendritic KCC-1 nanosphere-supported cobalt composite as a separable catalyst for hydrogen generation from NaBH4 hydrolysis

The introduction of magnetism into a catalyst can greatly optimize its separation performance. In the present work, a kind of magnetically separable catalysts for promoting NaBH₄ hydrolysis have been fabricated by anchoring cobalt nanoparticles on magnetic dendritic KCC-1 nanospheres composed of magnetic Fe₃O₄ core and fibrous shell. The fabricated catalysts were characterized with various characterization methods, including absorption spectroscopy (AAS), scanning electron microscopy (SEM), high-resolution transmission electronic microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and Fourier transform infrared (FT-IR), etc. This kind of catalysts exhibit high catalytic activity for promoting the hydrolysis of NaBH₄ under alkaline conditions, giving a hydrogen generation rate and activation energy of 3.83 L min⁻¹ g_Co⁻¹ (30 °C) and 53.63 kJ mol⁻¹, respectively. After used for 5 cycles, the catalyst showed 36.5% catalytic activity reserved. Most importantly, the magnetism of the catalyst made it easily separated and recycled from the solution after the reaction completed. The development of this kind of catalysts could provide a promising option for catalyzing NaBH₄ hydrolysis for portable hydrogen production from.     

Optimisation of sepiolite clay with phosphoric acid treatment as support material for CoB catalyst and application to produce hydrogen from the NaBH4 hydrolysis

Herein, the CoB catalyst supported on the sepiolite clay treated with phosphoric acid was utilized to produce hydrogen from the NaBH₄ hydrolysis. In order to analyse the performance of the phosphoric acid treated sepiolite clay supported-CoB catalyst, the NaBH₄ concentration effect, phosphoric acid concentration effect, phosphoric acid impregnation time effect, CoB catalyst percentage effect, and temperature effect were studied. In addition, XRD, XPS, SEM, TEM, BET, and FTIR analysis were performed for characterization of Co–B catalyst supported on the acid-treated sepiolite. The completion time of this hydrolysis reaction with Co–B (20%) catalyst supported on the sepiolite treated by 5 M phosphoric acid was approximately 80 min, whereas the completion time of this hydrolysis reaction with acid-free sepiolite-supported Co–B (20%) catalyst was approximately 260 min. There is a five-fold increase in the maximum production rate. The maximum hydrogen production rates of this hydrolysis reaction at 30 and 60 °C were found as 1486 and 5025 ml min⁻¹g⁻¹_catalyst, respectively. Activation energy was found as 21.4 kJ/mol. This result indicates that the acid treatment on sepiolite is quite successful. The re-usability of NaBH₄ hydrolysis reaction by CoB catalyst supported on sepiolite treated phosphoric acid for successive five cycles of NaBH₄ at 30 °C was investigated.