Electrodeposited nickel–iron–carbon–molybdenum film as efficient bifunctional electrocatalyst for overall water splitting in alkaline solution

Designing and synthesizing of efficient and inexpensive bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is one of the current research topics. In this study, NiFeCMo film in nickel mesh substrate is prepared by one-step direct-current electrodeposition method. The obtained NiFeCMo film shows the excellent electrocatalytic activity, which only requires overpotentials of 254 mV for HER and 256 mV for OER to drive current density of 10 mA cm⁻², with corresponding Tafel slopes of 163.9 and 60.3 mV·dec⁻¹ in 30% KOH medium, respectively. Moreover, NiFeCMo film only needs a low cell voltage of 1.61 V to drive current density of 10 mA cm⁻² in an alkaline electrolyzer. Such remarkably HER and OER properties of NiFeCMo alloy is attributed to the increased effective electrochemically active surface area and the synergy effect among Ni, Fe, C and Mo.     

Electrodeposition of NiMoCu coatings from roasted nickel matte in deep eutectic solvent for hydrogen evolution reaction

It is attractive to design and develop a low-cost and environment friendly material preparation route for the catalysts used in alkaline hydrogen evolution reaction. Mineral reconstruction in chlorination roasting and electrodeposition in deep eutectic solvent have been combined in this work. The electrodeposition of NiMoCu coatings from roasted nickel matte precursor in choline chloride (ChCl)-urea deep eutectic solvent (DES) has been investigated. Cyclic voltammetry (CV) implies that the electrodeposition process of NiMoCu coatings in ChCl-urea DES consists of a one-step reaction of Ni(II), a two-step reaction of Cu(II) and Ni/Mo inductive co-deposition. The hydrogen evolution performance parameters of deposited NiMoCu coatings have been systematically studied in alkaline solution by linear sweep voltammetry (LSV), and the electrochemical surface area (ECSA) has been tested by CV. The hydrogen evolution kinetics of deposited NiMoCu coatings has been further investigated by electrochemical impedance spectroscopy (EIS). Owing to its high electrochemical surface area, the NiMoCu coating deposited on Ni foam at −1.2 V can deliver a current density of 10 mA cm⁻² at an overpotential of 93 mV in 1 M KOH. It is suggested that NiMoCu coating can be a promising candidate for water splitting in alkaline solution.     

Dry reforming of methane for hydrogen production over NiCo catalysts: Effect of NbZr promoters

Ni/Al₂O₃, NiCo/Al₂O₃MgO and NiCo/Al₂O₃MgO/NbZr nanocatalysts were prepared by the sol-gel technique with citric acid and tested in the dry reforming of methane (DRM). In this paper, the effects of Nb and Zr addition as promoters in Al₂O₃MgO supported catalysts on the physicochemical characteristics and the reaction performance in the DRM were investigated. The NbZr promoters are expected to enhance the activity and performance of the catalyst due to its high thermal stability and also improvement in the metal dispersion of the catalyst. The catalysts samples were characterized by FESEM, BET, XRD, TEM, H₂-TPR and CO₂-TPD techniques. FESEM results demonstrated that NiCo/Al₂O₃MgO/NbZr has more uniform and well-dispersion of metal than NiCo/Al₂O₃MgO. The BET results unravel that the addition of NbZr promoters increase the surface area of the synthesized catalyst due to the high surface area of the promoters. There is a formation of MgAl₂O₄ spinel-type solid solution proved by the XRD and CO₂-TPD analysis due to the interaction between alumina lattice and magnesium metal which has high resistance to carbon formation. The DRM reaction is performed in the tubular furnace reactor at 1073.15 K, 1 atm and a CH₄/CO₂ ratio of unity. The sol-gelled NiCo/Al₂O₃MgO/NbZr was found to be the most proper choice for DRM which illustrates much higher conversion (86.96% for CH₄ conversion and 87.84% for CO₂ conversion) compared to the other catalysts. This is due to the strong interaction between active metals and supports, resistance to coke formation and higher stability in DRM reaction.     

Trimetallic nanoparticles: Synthesis,characterization and catalytic degradation of formic acid for hydrogen generation

PdAgFe, FePdAg and FeAgPd trimetallic nanoparticles were synthesized by seedless and step-wise simultaneous chemical reduction of Fe³⁺, Ag⁺ and Pd²⁺ by using hydrazine in presence of cetyltrimethylammonium bromide and used as a catalyst for the degradation of formic acid. The effects of nanoparticle composition, presence of sodium format (promoter), [catalyst], [formic acid] and temperature play key roles in the hydrogen generation. The Ba(OH)₂ trap experiment and water displacement technique were used to determine the generation of CO₂ and H₂, respectively. The decomposition of formic acid followed complex-order kinetics with respect to [formic acid]. It was found that FeAgPd showed a maximum catalytic activity (turn over frequency) of 75 mol H₂ per mol catalyst per h. The activation energy (E_a = 51.6 kJ/mol), activation enthalpy (ΔH = 48.9 kJ/mol) and activation entropy (ΔS = −151.0 JK^-1 mol⁻¹) were determined and discussed for the catalytic reaction. The reusability of the FeAgPd at 50 °C shows an efficient degree of activity for six consecutive catalytic cycles.     

One-pot synthesis of PdZnO/C by microwave sintering method as an efficient electro catalyst for ethanol oxidation reaction

The PdZnO/C catalytic material for ethanol oxidation reaction is prepared by microwave heating-glycol reduction method. PdZnO is well polymerized and dispersed on XC72. The results demonstrate that PdZnO/C has better electro catalytic activity and stability for ethanol oxidation reaction than Pd/C at room temperature. ZnO/C shows no catalysis for ethanol oxidation. The oxidation peak potential of PdZnO/C electrode is shifted negatively to 0.21 V. The current density of PdZnO/C electrode is 145 mA cm⁻², while that of the Pd/C electrode is 60 mA cm⁻². Moreover, single cell discharge test shows that discharge voltage of the PdZnO/C electrode reaches to 0.41 V at 30 mA cm⁻². In summary, ZnO as a co-catalyst significantly improves the activity of PdZnO/C catalyst for ethanol oxidation reaction.     

Computer-aided prediction of structure and hydrogen storage properties of tetrakis(4-aminophenyl)silsesquioxane based covalent-organic frameworks

With the aid of computer simulation, we have designed four covalent-organic frameworks based on tetrakis(4-aminophenyl)silsesquioxane (taps-COFs) and their hydrogen storage properties were predicted with grand canonical Monte Carlo (GCMC) simulation. The structural parameters and physical properties were investigated after the geometrical optimization. The accessible surface for H₂ molecule (5564.68–6754.78 m²/g) were estimated using the numerical Monte Carlo integration and the pore volume (4.06–10.74 cm³/g) was evaluated by the amounts of the containable nonadsorbing helium molecules at low pressures and room temperature. GCMC simulation reveals that at 77 K, tapsCOF1 has the highest gravimetric H₂ adsorption capacity of 51.43 wt% and tapsCOF3 possesses the highest volumetric H₂ adsorption capacity of 58.51 g/L. Excitedly, at room temperature of 298 K, the gravimetric hydrogen adsorption capacities of tapsCOF1 (8.58 wt%) and tapsCOF2 (8.20 wt%) have exceeded the target (5.5 wt%) of onboard hydrogen storage system for 2025 set by the U.S Department of Energy.     

Exploration of Ti substitution in AB2-type YZrFe based hydrogen storage alloys

To improve the hydrogen storage properties of YZrFe alloys, the alloying with Ti was carried out to obtain Y_0.7Zr_(0.3-x)Ti_xFe₂ (x = 0.03, 0.09, 0.1, 0.2) alloys by different processes. It was expected that Ti would substitute Zr and decrease the lattice constant of YFe₂-based C15 Laves phase. All YZrTiFe quaternary alloys consist of the main Y(Zr)Fe₂ phase and the minor YFe₃ phase. Despite the large solubility of Ti in Zr or Zr in Y, the Ti incorporation into YZrFe alloys results in the inhomogeneity of Y and the segregation of Ti, and thus decreases the hydrogen storage capacity. Only the alloy Y_0.7Zr_0.27Ti_0.03Fe₂ containing very few Ti shows the substitution of Ti to Zr and the resultant improvement in the dehydriding equilibrium pressure.     

High-performance FeCoP alloy catalysts by electroless deposition for overall water splitting

At present, it is difficult for electrocatalytic electrode materials with high-Performance to be prepared at low cost and large area under mild conditions. Therefore, we adopt a facile electroless plating method to deposit the FeCoP alloys on the nickel foam (NF) with different areas of 1 cm², 4 cm², 8 cm² and 16 cm². The FeCoP/NF catalysts exhibit extraordinary catalytic activity for the oxygen evolution reaction (OER) in alkaline media and are comparable to the state-of-the-art IrO₂ in 1.0 M KOH, capable of yielding a current density of 10 mA cm⁻² at an overpotential of only 250 mV. Furthermore, the FeCoP/NF catalysts show efficient activity towards the hydrogen evolution reaction (HER) with an overpotential of 163 mV at j = 10 mA cm⁻² as well. Remarkably, when used as both the anode and cathode, a low potential of 1.68 V (vs. RHE) is required to reach the current density of j = 10 mA cm⁻², making the FeCoP/NF alloys as an active bifunctional electrocatalyst for overall water splitting. The FeCoP/NF alloy catalysts with high catalytic activity, facile preparation and low cost would provide a new pathway for the design and large-scale application of high-performance bifunctional catalysts for electrochemical water splitting.     

Carbon-supported phosphatized CuNi nanoparticle catalysts for hydrazine electrooxidation

Developing non-noble metal catalysts with high performance to reduce the cost of hydrazine fuel cells is urgent. Herein, in this study, a series of carbon-supported phosphatized CuNi catalysts (P-Cu_xNi_y/C) are designed for hydrazine oxidation reaction (HzOR) via high temperature phosphating process. Among them, the PCu₂Ni/C is found to be a promising candidate for hydrazine electrooxidation. Electrochemical measurement results indicate that the PCu₂Ni/C catalyst exhibits higher catalytic activity and stability for HzOR in comparison with PCuNi/C, PCuNi₂/C, Cu₂Ni/C, Cu/C and Ni/C catalysts. Additionally, HzOR kinetics are also investigated, and it proves that hydrazine electrooxidation on PCu₂Ni/C is a diffusion controlled irreversible process. Meanwhile, physical characterization reveals that the catalysts have doped phosphorus successfully. All results demonstrate that as-prepared PCu₂Ni/C catalyst is a promising electrocatalyst for direct hydrazine fuel cells.     

Effect of LiCe(BH4)3Cl with a high Li ion conductivity on the hydrogen storage properties of LiMgNH system

The effect of LiCe(BH₄)₃Cl on the hydrogen storage properties of Mg(NH₂)₂2LiH system was studied systematically, which has a high Li ion conductivity. The hydrogen desorption temperatures for LiMgNH system shift to lower temperatures by 0.05LiCe(BH₄)₃Cl doping with the onset temperature of dehydrogenation decreasing by 40 °C and the peak temperature decreasing by 30 °C. The Mg(NH₂)₂2LiH–0.03LiCe(BH₄)₃Cl composite exhibits an improved comprehensive hydrogen storage properties, which can reversibly store about 5.0 wt% hydrogen at 160 °C, and released hydrogen as much as 8.6 times faster than that of the Mg(NH₂)₂2LiH composite at 160 °C. The results indicated that the LiCe(BH₄)₃Cl-containing sample exhibited much better cycling properties than that of Mg(NH₂)₂2LiH sample. XRD and FTIR results show that the structure of LiCe(BH₄)₃Cl does not change before and after hydrogen absorption/desorption, indicating it plays the catalytic effect. The hydrogen desorption activation energy of Mg(NH₂)₂2LiH doped with 0.03LiCe(BH₄)₃Cl was reduced by 37.5%. The rate-controlling step of desorption shifted from the diffusion to the chemical reaction by the addition of LiCe(BH₄)₃Cl, indicating that the diffusion rates of small ions like H⁺, Li⁺ and Mg²⁺ in LiMgNH system are significantly enhanced, which could be well explained by the improved ionic conductivity of LiCe(BH₄)₃Cl doped sample.     

Flame synthesis of nitrogen,boron co-doped carbon as efficient electrocatalyst for oxygen reduction reaction

The flame synthesis provides a simple low-cost method to produce novel carbon materials. In this study, N, B co-doped carbon (NBC) materials have been prepared by flame synthesis. Among many as-prepared samples, the NBC catalyst which prepared under carbonization temperature of 1000 °C for 3 h with acetonitrile/acetone precursor of 1:1 exhibits the best catalytic activity and stability, as well as good resistance to methanol interference for oxygen reduction reaction (ORR), with half-wave potential being almost nearly to Pt/C, and a quasi-four-electron transfer process. This study would provide an economic, environmental feasible and scalable approach for fabricating novel heteroatom co-doped carbon materials for ORR applications.     

Increased interface effects of PtFe alloy/CeO2/C with PtFe selective loading on CeO2 for superior performance in direct methanol fuel cell

Here, a simple two-step solvothermal approach has been employed to synthesize PtFe alloy (or Pt)/CeO₂/C with PtFe (or Pt) selective loading on CeO₂ nanoparticles. In addition, the selective loading of PtFe alloy or Pt nanoparticles on the surface of CeO₂ is achieved under weak alkaline environment, which is mainly attributed to the opposite electrostatic force between H⁺ enriched on the surface of CeO₂ particles and OH⁻ covered with carbon supporters. As-prepared PtFe alloy (or Pt)/CeO₂/C catalysts with two-stage loading structures show more excellent electro-catalytic efficiency for methanol oxidation as well as duration compared with commercial Pt/C and PtCeO₂/C with random loading structure. Further, single-cell assembly based on Pt₃Fe/CeO₂/C as the anode catalyst exhibits a maximum power density of 31.1 mW cm⁻², which is 1.95 times that of an analogous cell based on the commercial Pt/C. These improved performances with considerable low Pt content (<0.3 mg cm⁻²) are mainly ascribed to the abundant three phase interfaces (PtCeO₂ carbon) induced by the selective and efficient dispersion of Pt nanoparticles on ceria.     

Phosphorus-doped hierarchical porous carbon as efficient metal-free electrocatalysts for oxygen reduction reaction

Recently, fuel cells and metal-air batteries have attracted extensive attentions. Researching and developing non-noble metal catalyst with high electrocatalytic activity and low cost is one of the important challenges for these energy storage and conversion devices. In this study, phosphorus doped hierarchical porous carbon (P-HPC) has been firstly synthesized via a hard template method. The prepared PHPC possesses a unique porous structure which consists of micropores, mesopores and macropores simultaneously. The electrocatalytic activity of the PHPC toward ORR in KOH solution has been studied and compared with the ordinary structured phosphorus doped carbon (PC) and the commercial Pt/C by means of rotating ring-disk electrode (RRDE) technique. The prepared PHPC exhibits an excellent electrocatalytic performance toward ORR in terms of the electrocatalytic activity, the reaction kinetics, the durability and the methanol tolerance. And the high electrocatalytic activity and durability of PHPC could be attributed to the special hierarchical porous structure. This research demonstrates that the rational design of the microstructures for catalyst plays significant roles in improving the catalytic activity for the ORR.     

Ruthenium catalyst supported on Ba modified ZrO2 for ammonia decomposition to COx-free hydrogen

The Ba modified ZrO₂ materials were prepared and loaded Ru nanoparticles for ammonia decomposition to CO_x-free hydrogen reaction. The catalytic activity of Ru supported on BaZrO₂ derived from sol-gel process (Ru/BaZrO₂) is found to be several times of those for Ru/ZrO₂ without any promoter and RuBa/ZrO₂ catalysts prepared by conventional immersion method at the identical conditions. It is found that the formation of BaZrO₃ phase in BaZrO₂ can enhance the electron-donating ability of the support and Ru nanoparticles dispersion. Therefore, mobile electrons would be transferred from BaZrO₃ to the surface Ru particles, facilitating the recombinative desorption of N over Ru particles, leading to the increase of activity for ammonia decomposition sufficiently. Additionally, the suitable size of spherical Ru particles with average size of 2.4 nm for the formation of active sites are also responsible factors for the higher activity of this catalyst. The catalytic performance of Ru/BaZrO₂ catalyst can also be further improved by introducing of K and Cs promoters, and the apparent activation energies over Ru/BaZrO₂ of 94.1 kJ/mol decrease to 70.7 kJ/mol and 64.2 kJ/mol for K and Cs promoted Ru/BaZrO₂, respectively.     

The preparation and performance of a novel spherical spider web-like structure RuNi / Ni foam catalyst for NaBH4 methanolysis

In this work, a spherical spider web-like structure RuNi/Ni foam catalyst was prepared for hydrogen evaluation from sodium borohydride (NaBH₄) by a combination of electroless plating and electroplating. Microstructure, surface morphology, surface area and elemental composition of the RuNi/Ni foam catalyst were analyzed by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM-EDS and X-ray Photoelectron Spectroscopy (XPS), Brunauere-Emmette-Teller method (BET, AS-1C-VP), respectively. The influences of RuNi with different molar ratios, NaOH concentration, NaBH₄ concentration, and solution temperature on the hydrogen production rate were investigated in this paper. The results showed that the RuNi metals were arrayed densely and uniformly on the surface of Ni foam. The average hydrogen production rate is 360 mL min ⁻¹ g⁻¹ in 20 wt % of NaBH₄, 1 wt% of NaOH at 30 °C in the presence of the RuNi/Ni foam catalysts. The calculated activation energy was 39.96 kJ mol⁻¹ for hydrogen production from sodium borohydride using the RuNi/Ni foam catalyst.     

Pt nanoparticles supported on a novel electrospun polyvinyl alcohol-CuOCo3O4/chitosan based on Sesbania sesban plant as an electrocatalyst for direct methanol fuel cells

Here, novel polyvinyl alcohol (PVA) nanofibers with incorporated CuO and Co₃O₄ nanoparticles (PVA-CuOCo₃O₄) were synthesized through a conventional single-nozzle electrospinning technique and characterized by atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX), fourier-transform infrared spectroscopy (FT-IR), elemental analysis, transmission electron microscopy (TEM), differential thermal analysis (DTA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Novel Pt/polyvinyl alcohol-CuOCo₃O₄/chitosan (Pt/PVA-CuOCo₃O₄/CH) catalyst was successfully prepared. EDX, TEM, and FT-IR spectroscopy techniques were used to characterize the prepared catalysts. The electrocatalytic activity of Pt/PVA-CuOCo₃O₄/CH catalyst was investigated for methanol electrooxidation through cyclic voltammetry, chronoamperometry, CO stripping voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental factors for methanol electrooxidation were studied on the prepared catalysts and the optimum conditions were determined. Pt/PVA-CuOCo₃O₄/CH catalyst had extraordinary electrocatalytic activity for methanol electrooxidation. It exhibited better stability, higher electrochemically active surface area, and better antipoisoning effect than Pt/PVA-CuOCo₃O₄ and Pt/PVA/CH catalysts indicating that Pt/PVA-CuOCo₃O₄/CH could be a promising catalyst for direct methanol fuel cell (DMFC) applications. A real DMFC was designed, assembled and tested with Pt/PVA-CuOCo₃O₄/CH as anodic catalyst.     

Ultra-thin phosphate glass exhibiting high proton conductivity at intermediate temperatures

Ultra-thin proton-conducting phosphate glass was fabricated by press-forming at high temperature. The glass was evaluated for its ohmic loss reduction when installed as an electrolyte in intermediate-temperature fuel cells. The 36HO_1/24NbO_5/22BaO4LaO_3/24GeO₂1BO_3/249PO_5/2 glass (36H-glass) was prepared by alkali-proton substitution. Herein, 3–4 mg of 36H-glass was placed onto a 50 μm-thick stainless steel or Pd support and then sandwiched by a glassy carbon plate, whereupon a 600 kg load was applied at temperatures varying as 333–391 °C. Ultra-thin 36H-glass with a thickness of 16 μm was successfully obtained without degradation of proton conductivity. A fuel cell incorporating the Pd-supported ultra-thin 36H-glass was successfully operated at 300 °C, and the ohmic loss of the fuel cell was reduced down to 2.7 Ω cm² from the previous reported value of several tens of Ω·cm².     

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.     

One-step synthesis of petals-like graphitic carbon nitride nanosheets with triazole defects for highly improved photocatalytic hydrogen production

Reaction atmospheres during graphitic carbon nitride preparation can have a significant influence on the chemical composition and structure of the material, subsequently improving the photocatalytic activity. However, it is still a challenge to introduce an atmosphere by one-step heat-treated method to synthesis graphitic carbon nitride without additive gases. Herein, we developed a new one-step method to gather a variety of gases for preparing petals-like graphitic carbon nitride nanosheets (CNC), such as CO(g), NH₃(g) and H₂O(g). NH₃(g) and H₂O(g) are respectively derived from melamine-cyanuric acid supermolecule during pyrolysis. The petals-like CNC with more triazole defects (Nc) significantly increases the separation efficiency and the mobility of photogenerated photo-induced electron-hole pairs. Compared with the g-C₃N₄ calcined under nitrogen atmosphere (CNN), CNC has smaller grain, higher porosity with larger surface area, and remarkably longer lifetime of charge carriers. As expected, the product CNC exhibited a hydrogen evolution rate of 1334 μmol g⁻¹ h⁻¹ under visible-light irradiation, which was 2.8 times higher activity than CNN, as well as higher than most of the reported bulk g-C₃N₄.     

Synthesis of mesoporous CuFe/silicates catalyst for methanol steam reforming

In this study, mesoporous CuFe/silicate catalysts were obtained from a simultaneously mixing the NaOH and metal-ion solution to sodium silicate solution and a hydrothermal treatment under alkaline condition without using any organic template. During hydrothermally reaction, the amorphous metal-silicate would reconstruct and formation of the mesostructured CuFe/silicate. At appropriate pH values, the silicate species can strongly bind with the Cu²⁺ ions to form the stable CuFe/silicate, and the [Cu²⁺] in the final filtrated solution is lower than the effluent standard in Taiwan (1.0 ppm). To find the appropriate synthetic parameters, the effects of the pH value, metal to silicate ratio, and the hydrothermal treatment time on the surface areas and mesostructure of the resulted CuFe/silicates were discussed in detail. In practice, the mesoporous CuFe/silicate catalyst with high surface area of 547 m²g^-1 demonstrated a high methanol conversion within 1 h up to >99% at 180 °C to be used as high-performance catalysts for steam reformer of methanol.