Metal-organic framework derived Ni/Mo2C/Mo2TiC2Tx@NC as an efficient electrocatalyst for enhanced hydrogen production

Metal-organic framework's (MOF) shortcomings, such as poor conductivity, poor stability, and easy aggregation, impede its development in various application fields. Ni/Mo₂C/Mo₂TiC₂T_x@NC, a high-performance electrocatalyst for hydrogen evolution reaction, was prepared by incorporating a Mo₂TiC₂T_x MXene conductive matrix into MOF (namely C–Y). The Ni/Mo₂C/Mo₂TiC₂T_x@NC electrocatalyst demonstrates a remarkable HER ability with an overpotential of 105 and 134 mV and Tafel slope of 58 and 75 mV dec⁻¹ at a current density of 10 mA cm⁻² in 0.5 M H₂SO₄ and 1.0 M KOH, respectively. The outperformed HER activity of Ni/Mo₂C/Mo₂TiC₂T_x@NC catalyst is ascribe to the introduction of conductive Mo₂TiC₂T_x MXene as a carrier to improve the poor conductivity of MOF, the synergistic effect of Ni and Mo₂C nanoparticles, and the protective effect of the carbon layer. The work not only provides an experimental approach to address the problem of poor conductivity of MOF, but also provides a high-performance electrocatalyst for HER reactions. By utilizing MOFs and MXene as the precursor and the conducting carrier, our work provides some experimental reference for fabrication of multi-component inexpensive electrocatalysts.     

Pd (II) decorated conductive two-dimensional chromium-pyrazine metal-organic framework for rapid detection of hydrogen

The utilization of H₂ for versatile application has demanded highly selective, low cost and rapid hydrogen sensors that are proficient in sensing H₂ near flammability limit. In this report, Cr^IIICl₂(pyrazine)₂ MOF with negatively charged pyrazine linkers in its structure is used for the stabilization of Pd (II) via charge transfer interactions. This material design turned an innocent MOF into selective hydrogen sensor that can respond (through decrease in resistance under dynamic sensing setup) to H₂ in 5–7 s with a detection range of 0.25%–1% H₂ concentration. A correlation of H₂ sensing characteristics and the structure-property relationship is established using density functional theory (DFT) calculations. The calculations suggested that near fermi level in Pd^II@CrPy, the bandwidth increases upon interaction with H₂ thereby the phase space for electron delocalization increases leading to better carrier mobility. This new approach not only yields novel sensing properties but also enables limited usage of precious metal to develop cost-effective sensors.     

2-Dimensional metal-organic framework derived N-doped carbon immobilized Pd nanoparticles for hydrogen release from formic acid

Hydrogen release from formic acid is a significant energy supply route. However, the current catalysts suffer from low catalytic efficiency and stability. Herein, a porous N-doped carbon material with high N content (16.87%) and a large surface area (1544 m²·g^?1) were designed using a 2-dimensional metal-organic framework and etching agent potassium chloride. Due to its high N content and large surface area, ultrafine Pd particles are uniformly distributed on the porous N-doped carbon support, which effectively enhances excellent reactivity and enables a TOF value of 2365 h^?1 under additive-free conditions. The research also revealed that the strong interaction between Pd particles and pyridinic-N species can significantly slow metal agglomeration. Hence, the Pd/NC_ZIF-L (KCl) displayed good activity even after 10 cycling experiments, and it is a particularly competitive catalyst for hydrogen release from formic acid.     

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.     

Molybdenum disulfide decorated palm oil waste activated carbon as an efficient catalyst for hydrogen generation by sodium borohydride hydrolysis

Development of cost-effective catalyst material with enhanced activity for hydrogen generation is highly desirable for hydrogen powered portable applications. In this work, molybdenum disulfide (MoS₂) incorporated on palm oil waste activated carbon (POAC) was used as a novel catalyst for enhanced hydrogen production by sodium borohydride (NaBH₄) hydrolysis. Hydrothermally synthesized MoS₂/POAC catalyst composite was characterized by SEM, EDX, XRD, FTIR, Raman, TGA and Surface area analysis. Characterization studies revealed the uniform and complete synthesis of MoS₂ nanoparticles on the POAC surface with crystallite size of 18.2 nm. The catalyst composite showed enhancement in thermal stability and reduction in specific surface area as compared with POAC. Hydrogen generation investigations showed ideal weight ratio of composite catalyst as 10:1 (w/w of POAC: MoS₂) and optimal catalyst to feed weight ratio as 0.07. MoS₂/POAC catalyst with 10 wt% of POAC loading recorded the maximum catalytic activity of 1170.66 mL/g min with lower activation energy of 39.1 kJ/mol. The catalyst composite exhibited virtuous reusability with a 28% loss in activity for nine cycle regeneration run. Thus, MoS₂/POAC catalyst system is highly attractive for commercial applicability and is a potential candidate for enhanced hydrogen production through NaBH₄ hydrolysis.     

CeO2 supported multimetallic nano materials as an efficient catalyst for hydrogen generation from the hydrolysis of NaBH4

Nowadays, there is still no suitable method to store large amounts of energy. Hydrogen can be stored physically in carbon nanotubes or chemically in the form of hydride. In this study, sodium borohydride (NaBH₄) was used as the source of hydrogen. However, an inexpensive and useful catalyst (Co–Cr–B/CeO₂) was synthesized using the NaBH₄ reduction method and its property was characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), x-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) measurements. The optimized Co–Cr–B/CeO₂ catalyst exhibited an excellent hydrogen generation rate (9182 mLg_metal⁻¹min⁻¹) and low activation energy (35.52 kJ mol⁻¹). The strong catalytic performance of the Co–Cr–B/CeO₂ catalyst is thought to be based on the synergistic effect between multimetallic nanoparticles and the effective charge transfer interactions between the metal and the support material.     

Crown-like Zn0.5Cd0.5S/M-TiO2 composites derived from metal-organic frameworks for photocatalytic hydrogen production

Photocatalytic hydrogen production has been recognized as one of the most desirable approaches to overcome the worldwide energy and environmental issues. Here, novel sea urchin-like Zn_0.5Cd_0.5S and mesoporous TiO₂ (M-TiO₂) are designed, and a series of crown-like Zn_0.5Cd_0.5S/M-TiO₂ composites with different contents of M-TiO₂ are synthesized by hydrothermal method. The optimum hydrogen production rate of composites reaches 180.4 mmolh^?1g^?1 with the AQE up to 48.9% at 420 nm, which is 3.5 and 216 times that of pure Zn_0.5Cd_0.5S and the M-TiO₂, respectively. The outstanding performance of optimized Zn_0.5Cd_0.5S/M-TiO₂ composite prepared in this work exceeds most reported Cd-S-based catalysts. The improvement on the photocatalytic performance of composites is mainly due to the enlarged specific surface area, the exposure of more active sites, and the enhancement of the electron-hole separation efficiency.     

A highly efficient Co (0) catalyst derived from metal-organic framework for the hydrolysis of ammonia borane

A Co (0) catalyst is synthesized by the reduction of a metal-organic framework (MOF) precursor Co₂(bdc)₂(dabco) (bdc = 1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane). The amorphous catalyst exhibits highly efficient activity in the hydrolysis of ammonia borane (AB). The dehydrogenation of a 0.32 M aqueous AB solution completes in 1.4 min under room temperature. The porous structure in the MOF is proposed to play a key role. The catalytic effective Co (0) sites are stabilized by the organic molecules, which used to coordinate to Co (II) in the MOF precursor. This work implies that MOFs, with their large surface area and ample pore structures, may serve as ideal precursors for highly efficient heterogeneous catalysts.     

Synthesis of cobalt-doped catalyst for NaBH4 hydrolysis using eggshell biowaste

In the present study, a cobalt-doped catalyst was prepared from chicken eggshell powder (CEP) biowaste to be used in the hydrolysis of sodium borohydride (NaBH₄). In the presence of the prepared catalyst (CEP_cat), possible effects of the parameters of NaOH concentration (%), catalyst amount (g), NaBH₄ concentration (%), process temperature (^oC) and reusability affecting the hydrolysis of sodium borohydride were examined. The CEP_cat obtained was characterized with FT-IR, TGA, XRD, SEM and EDX analyses. The hydrogen generation rate (HGR) was determined as 432 mL g_Co⁻¹ min⁻¹ in the presence of 1 g CEP_cat, a CoO/CaO ratio of 10/90 and 1% NaBH₄ concentration. The activation energy of the NaBH₄ hydrolysis reaction was calculated as 16.78 kJ mol⁻¹. After 16 reuses of the CEP_cat there was no significant decrease in the hydrogen volume. Compared to the first use while there was an increase in the HGR. These results showed that the CEP_cat prepared has a significant advantage over other catalysts for use in NaBH₄ hydrolysis.     

Cobalt nanoparticles supported on magnetic core-shell structured carbon as a highly efficient catalyst for hydrogen generation from NaBH4 hydrolysis

A novel recyclable cobalt nanocatalyst, supported on magnetic carbon with core-shell structure, was successfully synthesized by using wetness impregnation-chemical reduction method for hydrogen generation from hydrolysis of NaBH₄. The resultant nanocomposite was characterized to determine the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy), TEM (transmission electron microscopy), etc. The results demonstrated that amorphous cobalt nanoparticles were homogeneously surrounded on the surface of the support due to having abundant hydrophilic groups (such as aldehyde and hydroxyl groups) on the surface of carbon layer for the effective immobilization of metal ions. The supported catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH₄ at room temperature. The total rate of hydrogen generation and activation energy were calculated to be 1403 ml H₂ g_cat^?1 min^?1 and 49.2 kJ mol^?1, respectively, which were comparable to the values of most cobalt-based catalyst reported for hydrogen production from hydrolysis of NaBH₄. Additionally, reusability test revealed that the hydrogen in NaBH₄ substrate could be completely released within 25 min with a minimum hydrogen generation rate of 832 ml H₂ g_cat^?1 min^?1 even after five runs of hydrolytic reaction, implying the as-prepared Co/Fe₃O₄@C composite could be considered as a promising candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells).     

Protection and confinement effect of carbon on Co/CoxOy nano-catalyst for efficient NaBH4 hydrolysis

The hydrolysis of sodium borohydride (NaBH₄) over catalysts is a promising method to produce hydrogen. Although Co-based catalysts exhibit high activity for NaBH₄ hydrolysis, they are still far from satisfying practical applications, especially their poor durability in alkaline media. Herein, a carbon shell structure was designed and synthesized to improve the stability of the mixture of Co⁰ and Co_xO_y nanofilms (Co/Co_xO_y@C) during NaBH₄ hydrolysis via a facile polymerization-pyrolysis strategy with Co/Co_xO_y nanofilms as the precursor. As a result, the Co/Co_xO_y@C catalyst can achieve a remarkable H₂ generation rate of 4348.6 mL min^?1 g_Co^?1 with a low activation energy of 43.6 kJ mol^?1, which is superior to most previously reported catalysts. Moreover, the catalyst shows high stability with an H₂ generation-specific rate of 79% after five cycles. The excellent performance of carbon substrate can well prevent the agglomeration of Co-based nanoparticle and improve the corrosion resistance of the active Co to BO₂^? and OH^?. This work would widen the road for the preparation of nanoconfined catalysts, which has prospective application potentials for H₂ production from NaBH₄ hydrolysis.     

Controllable hydrogen production from NaBH4 hydrolysis promoted by acetic acid

Numerous catalysts have been widely investigated for accelerating hydrogen production from NaBH₄ hydrolysis. However, these catalysts are usually complicated in structures, costly in fabrication, and hazardous for environment. In this work, cheap and environment-friendly acetic acid, CH₃COOH, is employed to promote NaBH₄ hydrolysis to produce hydrogen in a considerable rate. The experimental results demonstrate that the addition of suitable amount of CH₃COOH into NaBH₄ solutions stabilized with NaOH could dramatically accelerate the hydrolysis reaction. Additionally, the start/stop of NaBH₄ hydrolysis could be controlled by adding acid or base into the solution to realize “go-as-you-please” on-site hydrogen production.     

Improved design of metal-organic frameworks for efficient hydrogen storage at ambient temperature: A multiscale theoretical investigation

A multiscale theoretical technique is used to examine the combination of different approaches for hydrogen storage enhancement in metal-organic frameworks at room temperature and high pressure by implementation lithium atoms in linkers. Accurate MP2 calculations are performed to obtain the hydrogen binding sites and parameters for the following grand canonical Monte Carlo (GCMC) simulations. GCMC calculations are employed to obtain the hydrogen uptake at different thermodynamic conditions. The results obtained demonstrate that the combination of different approaches can improve the hydrogen uptake significantly. The hydrogen content reaches 6.6 wt% at 300 K and 100 bar satisfying DOE storage targets (5.5 wt%).     

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.     

Pd nanoparticles anchoring to core-shell Fe3O4@SiO2-porous carbon catalysts for ammonia borane hydrolysis

A modified Stöber method is applied to synthesize the magnetic core-shell Fe₃O₄@SiO₂ particles, followed by compositing a series of porous glucose-derived carbon with ZnCl₂ as etchant. Then, ultrafine Pd nanoparticles (NPs) are successfully anchored to the resulting Fe₃O₄@SiO₂-PC composites with an in-situ reduction strategy. The particle sizes of Pd NPs are mainly centered in the range of 2.3–4.3 nm in the as-prepared Pd/Fe₃O₄@SiO₂-PC catalysts, owning a hierarchical porous structure with high specific surface area (S_BET = 626.0 m² g⁻¹) and large pore volume (V_p = 0.61 cm³ g⁻¹). Their catalytic behavior for the hydrogen generation from ammonia borane (AB) hydrolysis is investigated in details. The corresponding apparent activation energy is as low as 28.4 kJ mol⁻¹ and the reaction orders with AB and Pd concentrations are near zero and 1.10 under the present conditions, respectively. In addition, the magnetic catalysts, which could be easily separated out by a magnet, are still highly active even after nine runs, revealing their excellent reusability.     

Metal-Schiff Base complex catalyst in KBH4 hydrolysis reaction for hydrogen production

It is the first study to synthesize Co(II)-Schiff Base complex and to use it like a catalyst for potassium borohydride hydrolysis reaction to hydrogen production. Co(II)-complex is synthesized with CoCl₂·6H₂O and 5-Amino-2,4-dichlorophenol-3,5-di-tert-butylsalisylaldimine ligand. KBH₄ hydrolysis reaction is studied according as percentage of KBH₄, percentage of KOH, amount of Co-Schiff Base complex catalyst and temperature effects. Co-Schiff Base complex is highly effective catalyst and initial rates (R_o) of KBH₄ hydrolysis reaction were 61220.00 and 99746.67 mL H₂. g⁻¹ cat. min⁻¹ at 30 °C and 50 °C. Furthermore this study includes the kinetic calculations and for this reaction calculated activation energy is 17.56 kJ mol⁻¹.     

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.     

Co-P nanoparticles supported on dandelion-like CNTs-Ni foam composite carrier as a novel catalyst for hydrogen generation from NaBH4 methanolysis

We used the chemical vapor deposition method to prepare dandelion-like CNTs-Ni foam composite carrier, and then the electroless plating method was used to deposit Co-P nanoparticles on the CNTs of the CNTs-Ni foam. The CNTs-Ni foam and Co-P/CNTs-Ni foam were characterized by BET, SEM, XRD, XPS, and EDS. The results showed that CNTs were uniformly and densely grown in situ on the surface of Ni foam and were further successfully coated with Co-P nanoparticles. The Co-P/CNTs-Ni foam catalysts still maintained the dandelion-like structure and reached a maximum hydrogen production rate of 2430 mL min⁻¹ g⁻¹ at 25 °C. Furthermore, the Co-P/CNTs-Ni foam catalysts also exhibit a remarkable cycling performance and low activation energy (49.94 kJ mol⁻¹) for the methanolysis of sodium borohydride.     

MOF-derived NiSe2 nanoparticles grown on carbon fiber as a binder-free and efficient catalyst for hydrogen evolution reaction

It is challenging to grow inexpensive cathode material with superior catalytic properties for hydrogen evolution reaction (HER). Metal-organic frameworks (MOFs) have emerged as powerful platforms to synthesize efficient and ultrastable catalysts for hydrogen production. In this research, NiSe₂ nanoparticles were derived from Ni-based MOF, which grown in situ on carbon fiber (NiSe₂/C/CF) through pyrolysis and selenization processes. NiSe₂/C/CF displays a higher HER performance than that of Ni/C/CF and Ni-MOF-74/CF. Notably, the NiSe₂/C/CF electrode gives a low overpotential of 209 mV, a Tafel slope of 74.1 mV/dec, and outstanding stability with slight decay after operating for 12 h. The high HER catalytic activity of NiSe₂/C/CF is mainly ascribed to the emerging effects of NiSe₂ nanoparticles and three-dimensional conductive substrate CF, facilitating active moieties exposure and electron transfer during the electrocatalytic process. Therefore, this work illustrates a novel approach for the preparation of transition metal chalcogenides as low-cost and stable catalysts for HER.