Synthesis conditions effect on the of photocatalytic properties of MnWO4 for hydrogen production by water splitting

This work aims to study the synthesis conditions effect on the photocatalytic properties of manganese tungstate (MnWO₄) for H₂ production by the water splitting reaction under visible light irradiation. This is achieved by relating the materials characterization and photocatalytic evaluation of MnWO₄ at different synthesis conditions. MnWO₄ was synthesized through a precipitation reaction between Mn²⁺ and (WO₄)^2- ionic species, while adding oleic acid (OA) as surfactant at two concentrations (0.1% and 1% V) and using three different stirring methods: magnetic stirring (AM), ultrasound (US) and high-shear stirring (UT). Characterization was carried out by TGA, XRD, BET surface area, UV–Vis spectroscopy and FESEM. XRD patterns confirm the wolframite structure of MnWO₄. BET surface area increased by using UT stirring. UV–Vis spectroscopy results revealed indirect transition Eg values of ≈2 eV, favorable for the MnWO₄ photoactivation under visible light irradiation. During the photocatalytic evaluation, sample 1%-UT produced the highest H₂ amount among all samples with a value of 72 μmolH₂g⁻¹, which was far higher compared to WO₃, which was taken as a reference photocatalyst.     

Evidence of nano-galvanic couple formation on in-situ formed nano-aluminum amalgam surfaces for passivation-bypassed water splitting

Reaction of Al metal with water is a well-known technique for large scale production of hydrogen. However, this method suffers from kinetic limitations due to formation of a passivation layer on Al, preventing optimal operations. Using high resolution Scanning Kelvin Probe Force Microscopy (SKPFM), we show the origin of formation of 'nano-galvanic couple' on in situ formed nano-aluminum amalgam surfaces in a water splitting system; passivation based limitations are completely bypassed in this approach. Furthermore, they offer an opportunity to beneficiate and recover mercury in contaminated water. The nano-galvanic corrosion due to substantial lateral variation in surface contact potential is responsible for the observed high throughput of hydrogen production (720 mL/min per 0.5 g Al salt). It may be noted that this process fares better than in situ prepared nano-Al based hydrogen production, wherein 600 mL/min of hydrogen is obtained for 0.5 g Al salt. Investigations using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) provide evidence for passivation-bypassed hydrolysis and favourable kinetics for in situ derived nano-AlHg hydrolytic agents (when compared to nano-Al). This study, to the best of our knowledge, reports the first direct proof of nano-galvanic couple formation on in-situ prepared nanoaluminum amalgam surface; paving a direct way to overcome the long standing passivation problem in Al hydrolysis. It is found that the hydrogen production rate and standard deviation (SD) of the contact potential of nanoaluminum amalgam are directly related to the rate of addition of the reducing agent, offering an opportunity for kinetic control for the in situ hydrolytic process.     

Heterogeneous Bimetallic Mo-NiPx/NiSy as a Highly Efficient Electrocatalyst for Robust Overall Water Splitting

Highly efficient electrocatalysts composed of earth-abundant elements are desired for water-splitting to produce clean and renewable chemical fuel. Herein, a heteroatomic-doped multi-phase Mo-doped nickel phosphide/nickel sulfide (Mo-NiP_x/NiS_y) nanowire electrocatalyst is designed by a successive phosphorization and sulfuration method for boosting overall water splitting (both oxygen and hydrogen evolution reactions (HER)) in alkaline solution. As expected, the Mo-NiP_x/NiS_y electrode possesses low overpotentials both at low and high current densities in HER, while the Mo-NiP_x/NiS_y heterostructure exhibits high active performance with ultra-low overpotentials of 137, 182, and 250 mV at the current density of 10, 100, and 400 mA cm⁻² in 1 m KOH solution, respectively, in oxygen evolution reaction. In particular, the as-prepared Mo-NiP_x/NiS_y electrodes exhibit remarkable full water splitting performance at both low and high current densities of 10, 100, and 400 mA cm⁻² with 1.42, 1.70, and 2.36 V, respectively, which is comparable to commercial electrolysis.     

Design of a Multilayered Oxygen-Evolution Electrode with High Catalytic Activity and Corrosion Resistance for Saline Water Splitting

The realization of seawater electrolysis requires high-performing anode materials that should possess good catalytic activity, stability, and specificity for the oxygen evolution reaction (OER) as well as high resistance toward chloride corrosion. Herein, the design of a multilayered oxygen-evolution electrode is reported to meet the multiple needs of anode material for saline water splitting. The multilayered electrode is synthesized through direct thermal boronization of commercially available NiFe alloy plate with boron powder, followed by electrochemical oxidation. And this electrode is composed of the surface oxidized NiFeBx alloy layer, the NiFeBx alloy interlayer, and the NiFe alloy substrate. The boron species are present in the form of metaborate in the outermost oxidized NiFeBx layer, and their existence is conductive to the generation and stabilization of the catalytic active phase γ-(Ni,Fe)OOH. The introduction of NiFeBx interlayer effectively prevents the excessive oxidative corrosion of the anode material in the electrolyte containing chloride ions.     

Cu2O nanowires based p-n homojunction photocathode for improved current density and hydrogen generation through solar-water splitting

Hydrogen generation through solar-water splitting is expected to address the global energy crisis by providing a source for a safer and sustainable alternative fuel. Herein, we report a facile synthesis of Cu₂O nanowires and show that the magnetic field could influence the nanowires’ distribution and alignment. Orientation of nanowires was observed to become more inclined towards the magnetic field lines as the values of full-width at half maximum decreased from 140° to 46.2° with the increase in the field strength. Crystallographic, morphological, optoelectronic, and photoelectrochemical properties of the constructed p-n homojunction were analyzed by using different characterization techniques. A high built-in potential of +0.93 V vs. RHE was observed for a 50 nm layer of n-Cu₂O over p-Cu₂O nanowires that resulted in a significantly high photocurrent density of −7.42 mA/cm². The stability in the photoelectrochemical medium was maintained for 14 h, generating 20 mmol/cm² of H₂.     

Ni2V2O7 dandelion microsphere for a high-performance electrocatalyst in water splitting

Water splitting is an effective way to produce hydrogen to solve the energy crisis problem, and inorganic metal compounds are widely used in electrocatalysis field due to efficient hydrogen evolution reaction (HER). Herein, we synthesize Ni₂V₂O₇ dandelion microsphere from nickel nitrate and vanadium pentoxide by “one-step hydrothermal” way, which exhibits large specific surface area of 102.74 m² g⁻¹. The as-prepared Ni₂V₂O₇ microsphere shows good electrocatalysis performances including OER overpotential of 358 mV and good stability, as well as HER overpotential of 195 mV. Furthermore, the Ni₂V₂O₇ microsphere electrode is assembled to Ni₂V₂O₇ microsphere//Ni₂V₂O₇ microsphere system, showing the water splitting voltage of 1.50 V at 10 mA cm⁻² by two-electrode method, which is much lower than those of commercial RuO₂//Pt/C system and most of spinel oxides electrocatalysts. Our work opens up a new and facile avenue for fabricating inorganic microsphere electrocatalyst in hydrogen production field.     

A highly active composite electrocatalyst Ni–Fe–P–Nb2O5/NF for overall water splitting

This work demonstrates a facile Nb₂O₅-decorated electrocatalyst to prepare cost-effective Ni–Fe–P–Nb₂O₅/NF and compared HER & OER performance in alkaline media. The prepared electrocatalyst presented an outstanding electrocatalytic performance towards hydrogen evolution reaction, which required a quite low overpotential of 39.05 mV at the current density of ?10 mA cm^?2 in 1 M KOH electrolyte. Moreover, the Ni–Fe–P–Nb₂O₅/NF catalyst also has excellent oxygen evolution efficiency, which needs only 322 mV to reach the current density of 50 mA cm^?2. Furthermore, its electrocatalytic performance towards overall water splitting worked as both cathode and anode achieved a quite low potential of 1.56 V (10 mA cm^?2).     

Carbon supported nickel phosphide as efficient electrocatalyst for hydrogen and oxygen evolution reactions

Hydrogen production through water splitting is an efficient and green technology for fulfilling future energy demands. Carbon nanotubes (CNT) supported Ni₂P has been synthesized through a simpler hydrothermal method. Ni₂P/CNT has been employed as efficient electrocatalysts for hydrogen and oxygen evolution reactions in acidic and alkaline media respectively. The electrocatalyst has exhibited low overpotential of 137 and 360 mV for hydrogen and oxygen evolution reactions respectively at 10 mA cm^?2. Lower Tafel slopes, improved electrochemical active surface area, enhanced stability have also been observed. Advantages of carbon support in terms of activity and stability have been described by comparing with unsupported electrocatalyst.     

Efficient overall water splitting over a Mo(IV)-doped Co3O4/NC electrocatalyst

To meet the demand of producing hydrogen at low cost, a molybdenum (Mo)-doped cobalt oxide (Co₃O₄) supported on nitrogen (N)-doped carbon (x%Mo–Co₃O₄/NC, where x% represents Mo/Co molar ratio) is developed as an efficient bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This defect engineering strategy is realized by a facile urea oxidation method in nitrogen atmosphere. Through X-ray diffraction (XRD) refinement and other detailed characterizations, molybdenum ion (Mo⁴⁺) is found to be doped into Co₃O₄ by substituting cobalt ion (Co²⁺) at tetrahedron site, while N is doped into carbon matrix simultaneously. 4%Mo–Co₃O₄/NC is the optimized sample to show the lowest overpotentials of 91 and 276 mV to deliver 10 mA cm^?2 for HER and OER in 1 M potassium hydroxide solution (KOH), respectively. The overall water splitting cell 4%Mo–Co₃O₄/NC||4%Mo–Co₃O₄/NC displays a voltage of 1.62 V to deliver 10 mA cm^?2 in 1 M KOH. The Mo⁴⁺ dopant modulates the electronic structure of active cobalt ion (Co³⁺) and boosts the water dissociation process during HER, while the increased amount of lattice oxygen and formation of pyridinic nitrogen due to Mo doping benefits the OER activity. Besides, the smaller grain size owing to Mo doping leads to higher electrochemically active surface area (ECSA) on 4%Mo–Co₃O₄/NC, resulting in its superior bifunctional catalytic activity.     

Accelerate the alkaline hydrogen evolution reaction of the heterostructural Ni2P@Ni(OH)2/NF by dispersing a trifle of Ru on the surface

Electrocatalytic water splitting for hydrogen production plays a vital role in the development of new energy field, but there is still a lack of low-content precious metal or cost-effective non-noble metal catalysts for the hydrogen evolution reaction (HER). Therefore, how to develop the catalysts with a smaller amount of precious metal to achieve higher performance is still a major challenge. Herein, we have fabricated Ru–Ni₂P@Ni(OH)₂/NF-2 heterostructure by phosphating Ni(OH)₂/NF and then anchoring Ru on the surface through wet chemical strategy. Benefiting from its optimal ΔG_H1 and synergistic effect, this Ru–Ni₂P@Ni(OH)₂/NF-2 catalyst shows superior electrocatalytic HER kinetics in alkaline electrolyte. A small overpotential of 31 mV is needed for this electrocatalyst to obtain the current densities of 10 mA cm^?2 with remarkable durability over 24 h. This work provides a new strategy for the preparation of effective HER electrocatalyst with a low precious metal content.