Metal-free catalysts with phosphorus and oxygen doped on carbon-based on Chlorella Vulgaris microalgae for hydrogen generation via sodium borohydride methanolysis reaction

Metal-free catalysts (C–KOH–P) containing phosphorus (P) and oxygen (O) prepared by the modification with phosphoric acid (H₃PO₄) of activated carbon (C–KOH) obtained by activation of Chlorella Vulgaris microalgae with potassium hydroxide (KOH) were investigated for the hydrogen (H₂) generation reaction from methanolysis of sodium borohydride (NaBH₄). Elemental analysis, XRD, FTIR, ICP-MS, and nitrogen adsorption were used to analyze the characteristics of metal-free catalysts. The results showed that groups containing O and P were attached to the carbon sample. In the study, the hydrogen production rates (HGR) obtained with metal-free C–KOH and C–KOH–P catalysts were 3250 and 10,263 mL/min/g, respectively. These HGR values are better than most values obtained for many catalysts presented in the literature. Besides, relatively low activation energy (Ea) of 27.9 kJ/mol was obtained for this metal-free catalyst. The C–KOH–P metal-free catalyst showed ideal reusability with 100% conversion and a partial reduction in the H₂ production studies of NaBH₄ methanolysis after five consecutive uses.     

Very efficient dehydrogenation of methanolysis reaction with nitrogen doped Chlorella Vulgaris microalgae carbon as metal-free catalysts

In this study, nitrogen (N) doped metal-free catalysts were obtained as a result of nitric acid (HNO₃) activation of carbon sample (C–KOH–N), which was obtained based on Chlorella Vulgaris microalgae by KOH activation (C–KOH). These catalysts have been effectively used to produce hydrogen (H₂) from the sodium borohydride (NaBH₄) methanolysis reaction. Compared to the C–KOH catalyst, the catalytic activity for C–KOH–N showed a seven-fold improvement. Hydrogen generation rate (HGR) values obtained for the NaBH₄ methanolysis reaction for C–KOH and C–KOH–N metal-free catalysts were 3250 and 20,100 mL min^?1 g^?1. The catalysts were characterized using various analytical techniques such as XPS, XRD, SEM, FTIR, BET, and elemental analysis. This work can provide a new alternative strategy to produce specific heteroatom-doped metal-free carbon catalysts for environmentally friendly conversion to produce H₂ efficiently.     

Oxygen and nitrogen-doped metal-free microalgae carbon nanoparticles for efficient hydrogen production from sodium borohydride in methanol

Here, the oxygen(O) and nitrogen(N) doped metal-free carbon synthesis including potassium hydroxide (KOH) activation of Spirulina Platensis microalgae, followed by nitric acid (HNO₃) activation is reported for the first time. Oxygen and nitrogen-doped metal-free catalysts were investigated for efficient hydrogen (H₂) production from methanolysis of sodium borohydride (NaBH₄). Compared to the catalyst obtained with the KOH activation, the catalytic activity for O and N doped metal-free showed about a four-fold improvement. The catalysts were analysed by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), nitrogen adsorption, elemental analysis and Fourier-transform infrared spectroscopy (FTIR). The effects of temperature, NaBH₄ amounts, catalyst loading and reusability experiments on the catalytic performance of obtained metal-free catalysts by H₂ release from NaBH₄ methanolysis were performed. This study can provide a new alternative strategy to produce specific metal-free carbon catalysts doped heteroatom for environmentally friendly conversion to produce H₂ efficiently.     

ZnFe2O4@ZnFe2S4 core-shell nanosheet on Ni foam as efficient and novel electrocatalyst for oxygen generation

Due to the augmentation of societies and the need for more energy, attention to clean and renewable energy has increased. One of these alternative energies was the use of water splitting. Since the oxidation reaction of water suffers from a delayed reaction, it is important to use efficient and low-cost electrocatalysts in the process. In this work we report the synthesis of ZnFe₂O₄@ZnFe₂S₄ by the hydrothermal method. Here, we successfully synthesize the ZnFe₂O₄@ZnFe₂S₄ core-shell nanosheet on Ni Foam via a novel and facile process for oxygen evolution reactions (OER). The metal-based electrode made of ZnFe₂O₄@ZnFe₂S₄ is efficient for the electrochemical reaction of water oxidation due to its electrical strength and high catalytic activity. The catalyst is calcined at 400 °C and characterized by XRD, FESEM, TEM, EDS, MAP and RAMAN techniques. The electrolysis of water using ZnFe₂O₄@ZnFe₂S₄/NF a current density of 5 mA cm^?2 can be achieved by cell voltage of 1.45 V (vs. RHE) volts in a solution of 1 M KOH. The catalyst synthesized to reach 5 mA cm^?2 in oxygen evolution reaction only has 222 mV overpotentials.     

3D hierarchical network NiCo2S4 nanoflakes grown on Ni foam as efficient bifunctional electrocatalysts for both hydrogen and oxygen evolution reaction in alkaline solution

The development of cost-effective and high-efficiency electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) still remains highly challenging. Exposing as many active sites as possible is the key method to improve activity of HER and OER performance. In this communication, we demonstrate a novel 3D hierarchical network NiCo₂S₄ nanoflake grown on Ni foam (NiCo₂S₄-NF) as a highly efficient and stable electrochemical catalyst. The NiCo₂S₄-NF exhibits overpotentials as low as 289 and 409 mV at 100 mA cm^?2, superior long-term durability during a 20 h measurement, and a low Tafel slope of 89 and 91 mV dec^?1 for HER and OER in 1.0 M NaOH solution. The outstanding performance is owe to the inherent activity of ultrathin NiCo₂S₄ nanoflakes and the special structure of NiCo₂S₄-NF that can provide a huge number of exposed active sites, accelerate the transfer of electrons, and facilitate the diffusion of electrolyte simultaneously.     

Double doping of V and F on Co3O4 nanoneedles as efficient electrocatalyst for oxygen evolution

Rationally designing high-activity catalyst for oxygen evolution reaction (OER) is of primary importance due to its sluggish kinetic process in water splitting. Herein, we report a metallic (V) and nonmetallic (F) double doping in Co₃O₄ with nanoneedles structure, which is synthesized through facile oil bath and annealing. Electrochemical measurements show that the Co₃O₄ dopped with fluorine and vanadium (F_0.2-V-Co₃O₄-350) only needs a low overpotential of 320 mV to afford a current density of 10 mA cm^?2, which is superior to commercial RuO₂. The excellent electrocatalytic performance can be attributed to double doping of vanadium and fluorine which have strong electron absorption effect to optimize the density of electrons in Co₃O₄. Besides, nanoneedles structure can enlarge exposure of active sites. And its great durability is evaluated through 2000 cycles CV test. Furthermore, the optimal ratio of fluorine to vanadium and different annealing temperatures of the target catalyst are explored reasonably.     

H2 production from CH4 decomposition: Regeneration capability and performance of nickel and rhodium oxide catalysts

Nickel–lanthanum (LaNiO₃) and nickel–rhodium–lanthanum (LaNi_0.95Rh_0.05O₃) perovskite-type oxide precursors were synthesized by different methodologies (co-precipitation, sol–gel and impregnation). They were reduced in an H₂ atmosphere to produce nickel and rhodium nanoparticles on the La₂O₃ substrate. All samples were tested in the catalytic decomposition of CH₄. Methane decomposed into carbon and H₂ at reaction temperatures as low as 450 °C—no other reaction products were observed. Conversions were in the range of 14–28%, and LaNi_0.95Rh_0.05O₃ synthesized by co-precipitation was the most active catalyst. All catalysts maintained sustained activity even after massive carbon deposition indicating that these deposits are of the nanotube-type, as confirmed by transmission electron microscopy (TEM). The reaction seems to occur in a way that a nickel or rhodium crystal face is always clean enough to expose sufficient active sites to make the catalytic process continue. The samples were subjected to a reduction–oxidation–reduction cycle and in situ analyses confirmed the stability of the perovskite structure. All diffraction patterns showed a phase change around 400 °C, due to reduction of LaNiO₃ to an intermediate La₂Ni₂O₅ structure. When the reduction temperatures reach 600 °C, this structure collapses through the formation of Ni⁰ crystallites deposited on the La₂O₃. Under oxidative conditions, the perovskite system is recomposed with nickel re-entering the LaNiO₃ framework structure accounting for the regenerative capability of these solids.     

High performance of bulk Mo2N and Co3Mo3N catalysts for hydrogen production from ammonia: Role of citric acid to Mo molar ratio in preparation of high surface area nitride catalysts

Hydrogen production from ammonia decomposition was studied using a series of unsupported high surface area molybdenum nitride (Mo₂N) and cobalt promoted molybdenum nitride (3%Co-Mo₂N) catalysts prepared with citric acid (CA) as a chelating agent. To elucidate the influence of citric acid amount in preparation conditions on the structure and catalytic activity, we prepared catalysts with different citric acid to Mo molar ratios i.e. CA/Mo = 1, 2, 3 and 4. The catalytic activity was evaluated in the temperature range of 300–600 °C at atmospheric pressure. The catalytic activity of the tested samples has changed in the following order of CA/Mo atomic ratio of 1 < 2 < 3 > 4. Therefore, the catalyst prepared by using CA/Mo ratio = 3 showed the highest catalytic activity. BET, XRD, XPS, SEM and TEM-EDS techniques were been used to characterize the catalysts. The increased activity of Mo₂N-3:1 and 3%Co-Mo₂N-3:1 catalysts was due to increased surface area, decreased particle size and increased relative proportions of Mo₂N and Co₃Mo₃N phases. The ammonia conversion for 3%Co-Mo₂N catalyst was increased from 75 to 97% at 550 °C with the increase of CA/Mo ratio from 1 to 3. This enrichment of activity in 3%Co-Mo₂N-3:1 catalyst is due to increased dispersion of Co₃Mo₃N microstructure on γ-Mo₂N platelets confirmed by SEM and TEM results. No deactivation was observed for any catalysts investigated in this study for ammonia decomposition.     

Comparative XPS study of Rh/Al2O3 and Rh/TiO2 as catalysts for NaBH4 hydrolysis

The catalysts Rh/Al₂O₃ and Rh/TiO₂ for hydrogen production from NaBH₄ were prepared by deposition technique from RhCl₃ reduced by NaBH₄ and were studied by XPS and TEM. It was found that the RhCl₃/Al₂O₃ system is more stable comparing to RhCl₃/TiO₂ which starts to decompose by weak heat treatment. It was shown that NaBH₄ reduced RhCl₃/TiO₂ (Al₂O₃) to supported metal Rh nanoparticles in both cases. In the case of Rh/TiO₂ SMSI effect it was found after RT reduction. The SMSI (Strong Metal-Support Interaction) effect gave an explanation for the difference of activity between Rh/TiO₂ and Rh/Al₂O₃ catalysts in hydrolysis reaction of NaBH₄.     

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.     

Promotional effect of alkaline earth over Ni-La2O3 catalyst for CO2 reforming of CH4: Role of surface oxygen species on H2 production and carbon suppression

Alkaline earth elements (Mg, Ca and Sr) on Ni-La₂O₃ catalyst have been investigated as promoters for syngas production from dry CO₂ reforming of methane (DRM). The catalysis results of DRM performance at 600 °C show that the Sr-doped Ni-La₂O₃ catalyst not only yields the highest CH₄ and CO₂ conversions (∼78% and ∼60%) and highest H₂ production (∼42% by vol.) but also has the lowest carbon deposition over the catalyst surface. The XPS, O₂-TPD, H₂-TPR and FTIR results show that the excellent performance over the Sr-doped Ni-La₂O₃ catalyst is attributed to the presence of a high amount of lattice oxygen surface species which promotes C-H activation in DRM reaction, resulting in high H₂ production. Moreover, these surface oxygen species on the Ni-SDL catalyst can adsorb CO₂ molecules to form bidentate carbonate species, which can then react with the surface carbon species formed during DRM, resulting in higher CO₂ conversion and lower carbon formation.