Mild hydrogen production from the hydrolysis of Al–Bi–Zn composite powder

The development of mild hydrogen-generating materials is of great significance to improve the working life of hydrogen–oxygen fuel cells. In this study, Al–Bi–Zn composite powders were designed by phase diagram calculation and then prepared via the gas atomization method. The results indicated that the conversion yield of Al–12Bi–7Zn (wt.%) powder reached 98% with stable hydrogen production within 280 min at 50 °C. When composite powder reacted with NaCl solution to produce hydrogen, the dormant period of the reaction process was significantly shortened, but the conversion rate was slightly reduced. Additionally, the evolution of powder morphology during the reaction was investigated. The results showed that the continuous cracking of the powder led to the continuous exposure of fresh Al to react.     

Hydrogen evolution reaction on in-plane platinum and palladium dichalcogenides via single-atom doping

Searching for the catalysts with excellent catalytic activity and high chemical stability is the key to achieve large-scale production of hydrogen (H₂) through hydrogen evolution reaction (HER). Two-dimensional (2D) platinum and palladium dichalcogenides with extraordinary electrical properties have emerged as the potential candidate for HER catalysts. Here, chemical stability, HER electrocatalytic activity, and the origin of improved HER performance of Pt/Pd-based dichalcogenides with single-atom doping (B, C, N, P, Au, Ag, Cu, Co, Fe, Ni, Zn) and vacancies are explored by first-principles calculations. The calculated defect formation energy reveals that most defective structures are thermodynamically stable. Hydrogen evolution performance on basal plane is obviously improved by single-atoms doping and vacancies. Particularly, Zn-doped and Te vacancy PtTe₂ have a ΔG_H value close to zero. Moreover, defect engineering displays a different performance on HER catalytic activity in sulfur group elements, in order of S < Te < Se in Pd-based chalcogenides, and S < Se < Te in Pt-based chalcogenides. The origin of improved hydrogen evolution performance is revealed by electronic structure and charge transfer. Our findings of the highly activating defective systems provide a theoretical basis for HER applications of platinum and palladium dichalcogenides.     

A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.     

Mixed-dimensional niobium disulfide-graphene foam heterostructures as an efficient catalyst for hydrogen production

Besides developing a large number of catalysts for hydrogen evolution reaction (HER) in alkaline electrolytes, its conversion efficiency remained low. Herein, we have developed mixed-dimensional heterostructures of niobium disulfide (NbS₂) with graphene foam grown on nickel foam (NbS₂-Gr-NF). The strong lateral fusion results in activating the catalytic sites of NbS₂, the three-dimensional substrate provides easy access of electrolyte to active sites and increased electrochemically active surface area, while enhanced conductivity provides faster transfer of electrons to and from active sites. Therefore, NbS₂-Gr-NF heterostructures resulted in an exceptionally high current density of 500 mA cm⁻² at a very low overpotential of 306 mV in 1 M KOH solution and even can achieve the current density values of 914 mAcm⁻² at 338 mV only at a slight increase in overpotential (32 mV). Moreover, a Tafel value of ~72 mV dec⁻¹ confirms that as-developed heterostructure provides fast reaction kinetics where the reaction is mainly controlled by the Volmer step. Achieving such high current density at a faster rate with high stability makes NbS₂-Gr-NF heterostructures a potential candidate for water-splitting, especially in alkaline electrolytes.     

Electrospinning as a tool in fabricating hydrated porous cobalt phosphate fibrous network as high rate OER electrocatalysts in alkaline and neutral media

Electrospinning (ES) is a most reliable method for synthesizing one dimensional (1D) fibrous material. Fibrous materials are having peculiar interest owing to their fascinating properties. For efficient hydrogen fuel generation, electrocatalytic water splitting is one of the finest way of producing hydrogen in a pure form. But it is encountered by the counter oxygen evolution reaction (OER) in more often. As of now, noble metal based catalysts are utilized in the commercial sector. Some of the disadvantages associated with the noble materials are restrict their usage commercially. To address this issue, herein, we have synthesized One dimensional (1D), hydrated porous cobalt phosphate fibrous network by an ES method and act as an electrocatalyst for OER in both alkaline and neutral media for the first time, which exhibits an overpotential of 245 and 457 mV respectively at a current density of 10 mAcm^?2 with astonishing stability.     

In situ growth of nickel phosphide nanoparticles on inner wall of graphitic carbon nitride tubes for efficient photocatalytic hydrogen evolution

A facile two-step approach is employed to prepare novel Ni₂P@CNT hybrid photocatalyst, which is assembled by nickel phosphide (Ni₂P) nanoparticles on the inner wall of graphitic carbon nitride tube (CNT). This unique microstructure endows Ni₂P@CNT with close interfacial interaction, promotes efficient separation of photoexcited charge carriers and provides enriched sites for photocatalytic reaction. Moreover, the hybrid system is found to exhibit more superior photocatalytic hydrogen evolution activity than pure CNT and Pt-decorated CNT (Pt@CNT). As a consequence, the work illustrates the essential role of experimental process on the final morphology and performance, which is expected to pave a new method to construct various kind of excellent photocatalyst.     

Electrochemical determination of niobium cathode as an efficient electrocatalyst for hydrogen generation in acidic media

Hydrogen gas (H₂) is notified as a renewable energy carrier. It is wanted to discover a low-cost electrocatalyst for the hydrogen evolution reaction (HER) to substitute the high-cost Pt in electrolysis cell. Niobium electrocatalyst nominated to substitute noble materials for electrocatalytic H₂ production and its electrochemical manner was estimated in H₂SO₄ acid of various concentrations utilizing a steady-state polarization and electrochemical impedance spectroscopy (EIS). The influences of acid concentration, cathodic potential and temperature on the H₂ creation were examined. The outcomes display that HER on Nb electrode proceeds by the Volmer-Heyrovsky mechanism. EIS tests, under open circuit and under cathodic polarization, were performed and the fitting has been done utilizing a suggested model for the electrode/electrolyte interface. Apparent activation energies (E_a) were estimated to be ca. 10.5 kJ mol^?1 for the HER on Nb. Thus, Nb is a good electrocatalyst for the cathodic H₂ manufacturing.     

NiMo/Cu-nanosheets/Ni-foam composite as a high performance electrocatalyst for hydrogen evolution over a wide pH range

We designed and fabricated non-precious and highly efficient electrocatalysts of nickelmolybdenum/copper-nanosheets/nickel-foam composites (NiMo/Cu-NS/NF) by step electrodepositions, combining with chemical oxidation method. The catalysts were charaterized by means of SEM, XRD and XPS spectra. Their electrocatalytic activities were assessed by hydrogen evolution reactions (HER) over a wide pH range, where acidic, neutral and alkaline electrolytes were used, respectively. Benefiting from the unique midlayer Cu nanosheets (NS) architecture and optimum Mo–Ni composition at the surface layer which led to high electronic conductivity and large electrochemically active surface area (ECSA), the NiMo/Cu-NS/NF-2 catalyst displayed superior electrocatalytic activities with low overpotentials of η₁₀ = 43, 86 and 89 mV in 0.5 M H₂SO₄, 1.0 M PBS and 1.0 M KOH electrolyte, respectively. Especially in the acidic condition, it exhibited the best electrocatalytic activity with smaller Tafel slope of 54 mV dec^?1 and higher exchange current density of 1.93 mA cm^?2.     

Surface controlled synthesis of Cu2FeSnS4 particles for enhanced hydrogen evolution reaction

Cu₂FeSnS₄ (CFTS) particles are synthesized using different surfactants such as thioglycolic acid (TGA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) via the solution process. The effect of surfactants on crystal structure, morphology, elemental composition, and electrocatalytic properties of CFTS particles are investigated. CFTS particles with a better crystalline phase are obtained in PVP (surfactant), while impurity phases are observed in TGA and PVA (surfactants). The morphology of CFTS is significantly changed when a different surfactant is used in the synthesis process. The mixture of aggregate and porous (1 μm) particles is observed when PVA is used as a surfactant to synthesize CFTS particles. At the same time, highly porous particles having nanosheets and nanoparticles at the surface are obtained in the case of PVP. In the TGA case, spherical particles with 1 μm size are observed. The electrocatalytic ability of all CFTS particles toward hydrogen evolution reactions (HER) is studied in 0.5 M H₂SO₄ electrolyte. The overpotential of PVP-based CFTS particles is the lowest as ƞ = 421 mV at 10 mA/cm² compared to the other two samples. CFTS particles synthesized using PVP exhibit enhanced electro-catalytic performance due to higher surface area.     

Magnetic field enhancement of electrochemical hydrogen evolution reaction probed by magneto-optics

External magnetic fields affect various electrochemical processes and can be used to enhance the efficiency of the electrochemical water splitting reaction. However, the driving forces behind this effect are poorly understood due to the analytical challenges of the available interface-sensitive techniques. Here, we present a set-up based on magneto- and electro-optical probing, which allows to juxtapose the magnetic properties of the electrode with the electrochemical current densities in situ at various applied potentials and magnetic fields. On the example of an archetypal hydrogen evolution catalyst, Pt (in a form of Co/Pt superlattice), we provide evidence that a magnetic field acts on the electrochemical double layer affecting the local concentration gradient of hydroxide ions, which simultaneously affects the magneto-optical and magnetocurrent response.