Recent advances in electrocatalysts for seawater splitting in hydrogen evolution reaction

Electrocatalytic water splitting is an important method to produce green and renewable hydrogen (H₂). One of the hindrances for wide applications of electrocatalysis in H₂ production is the lack of freshwater resources. Comparatively, seawater splitting has become an effective approach for large-scale H₂ production due to its abundant reserves. However, the increased complexity of seawater content emerged more problems in electrocatalytic seawater splitting. Recently, various strategies have been reported on improving the performance of electrocatalysts applied in seawater. Herein, this review firstly analyzed the mechanisms and challenges of electrocatalytic seawater splitting to evolve H₂, and summarized the recent progress on H₂ production in electrocatalytic seawater splitting. Furthermore, suggestions for future work have been provided for guidance.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

Combustion synthesis and electrochemical characterisation of Pt–Ru–Ni anode electrocatalyst for PEMFC

The present work studies the synthesis by the combustion method of an anode catalyst for protonic exchange membrane fuel cell (PEMFC) employing two different fuels, that is, urea and sucrose. The unsupported pure solid solution Pt_0.6Ru_0.3Ni_0.1 was selected from a calculated and empirical ternary phase diagram, which was previously studied. Theoretically, this particular composition exhibited single-phase features without the presence of secondary phases as RuO₃ and NiO, regarding the oxygen partial pressure conditions generated during the combustion synthesis. In the X-ray diffraction (XRD) analysis of the nanoparticles synthesized by using two different fuels, a single-phase Pt_0.6Ru_0.3Ni_0.1 alloy was detected. However, the X-ray photoelectron spectroscopy (XPS) studies showed that the nanoparticles prepared could present an onion-shell structure, in the case of the sample synthesized with sucrose as fuel, the external layers are partially constituted by Ni hydroxides, which can exhibit an active role in the hydrogen oxidation reaction. The electrochemical behaviour of this unsupported catalyst was performed by preparing MEAs, which were evaluated using a I–V polarisation curve test. The results obtained indicated that the nanoparticles prepared by sucrose have better performance, 260 mW/cm², than those prepared using urea, 170 mW/cm². These results are discussed in relation with the hydrogen oxidation mechanism. The results obtained reveal combustion synthesis as an appropriate method for preparing PEMFC electrocatalysts, due to its versatility, simplicity and fastness.     

Application of a deep eutectic solvent to prepare nanocrystalline Ni and Ni/TiO2 coatings as electrocatalysts for the hydrogen evolution reaction

The paper reports the electrochemical deposition of nanocrystalline nickel and composite nickel-titania films as effective electrocatalysts for the hydrogen evolution reaction. To produce the composite Ni/TiO₂ electrodeposits, a plating bath based on a deep eutectic solvent, a novel kind of ionic liquids, was used for the first time. The electrolyte contained ethaline (a eutectic mixture of choline chloride and ethylene glycol), 1 M NiCl₂⋅6H₂O and the addition of extra water (3, 6, 9 mol dm⁻³). Titania dispersed phase was introduced into the electrolyte as nanopowder Degussa P 25 (0–10 g dm⁻³). It was shown that the introduction of extra water to the plating bath allowed appreciably increasing the content of TiO₂ phase in the coating (from ca. 2 to 10 wt%). The effects of electrolysis conditions on the TiO₂ content in the coatings, surface morphology and microstructure were determined. The results of voltammetry measurements showed that the Ni and composite Ni/TiO₂ coatings electrodeposited from the plating electrolyte based on a deep eutectic solvent exhibit improved electrocatalytic properties towards the hydrogen evolution reaction as compared with deposits obtained from commonly used aqueous electrolytes. The mechanism of the hydrogen evolution reaction on the Ni and composite Ni/TiO₂ coatings is a combination of Volmer-Heyrovsky reactions. The introduction of TiO₂ particles into the nickel matrix results in the acceleration of the hydrogen evolution reaction. An improved catalytic activity of Ni/TiO₂ composites towards the hydrogen evolution reaction can be associated with the presence of titanium-containing redox couples on the surface.     

A combined physicochemical and electrocatalytic study of microwave synthesized tungsten mono-carbide nanoparticles on multiwalled carbon nanotubes as a co-catalyst for a proton-exchange membrane fuel cell

Tungsten mono-carbide (WC) nanoparticles supported on multiwalled carbon nanotube (MWCNT) was synthesized by a microwave-assisted solid-state carburization. The prepared samples were used as a co-catalyst to prepare Pt-WC/MWCNT catalyst for a proton-exchange membrane fuel cell. MWCNTs with and without oxidative pretreatments were characterized as the starting precursors. The influence of the carbide formation conditions on the physicochemical characteristics of the final product were extensively investigated. According to the results, surface pretreatment of the MWCNTs can improve the yield of carbide formation. Furthermore, carburization process can improve the catalyst utilization due to increasing the number of surface defects of the MWCNT supporting materials which can be interpreted as structural effect of the carburization process. It is believed that the superior performance of electrodes modified with tungsten carbide is mostly due to the structural effect of the carburization process and synergistic effect between the electrocatalytic activity of WC and Pt.     

Graphene-based electrocatalysts: Hydrogen evolution reactions and overall water splitting

Recently, carbon-based materials (e.g., graphene, carbon nanotubes, carbon quantum dots) have been used as electrocatalysts to catalyze the reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Among them, graphene has attracted attention as an electrocatalyst, and its electrocatalytic performances have been improved by doping with metals and non-metals, surface and defect engineering, and hybrid development. In this perspective, the present paper reviewed the recent advances (2018 onwards) on the progress of graphene-based electrocatalysts for HER and overall water splitting (OWS). It is emphasizing strategies for optimizing electrocatalytic properties followed by challenges and future outlook. This review will provide the essential ideas and strategies that can help design graphene-based electrocatalysts of high performance that can be implemented for sustainable energy application.     

Interface engineering of copper-cobalt based heterostructure as bifunctional electrocatalysts for overall water splitting

It is of great significance to develop highly active and cost-effective electrocatalysts for the oxygen evolution reaction and hydrogen evolution reaction in alkaline solution. Herein, we report an interface engineering strategy to fabricate 3D hierarchical CuCo₂O₄@CuCo₂S₄ heterostructure catalysts with efficient synergistic effects for water splitting. Owing to the special nano-architectures with abundant active interfaces, the as-prepared CuCo₂O₄@CuCo₂S₄ catalysts exhibit superior electrochemical activity and prominent electrochemical stability, with a small overpotential of 240 and 101 mV for oxygen and hydrogen evolution reactions to deliver a current density of 10 mA cm⁻², respectively. Remarkably, the CuCo₂O₄@CuCo₂S₄ materials directly applied as both anode and cathode electrode demonstrate excellent water splitting performance, achieving 10 mA cm⁻² at a low cell voltage of only 1.53 V, outperforming the integrated state-of-the-art RuO₂||Pt/C couple (1.56 V). Moreover, density functional theory calculations suggest that the excellent overall water splitting property of CuCo₂O₄@CuCo₂S₄ is attributed to a large amount of hierarchical hetero-interfaces, giving rise to effective adsorption and cleavage of H₂O molecules on the catalyst surface. This work represents a general strategy to exploit efficient and stable hybrid electrocatalysts for renewable energy applications by rational catalyst interface engineering.     

Enhanced Pt utilization in electrocatalysts by covering of colloidal silica nanoparticles

This work aims at enhancing Pt utilization in electrocatalysts by covering of preformed silica nanoparticles. Pt/C electrocatalysts were prepared by reductive deposition of Pt by citrate at moderate temperatures on silica nanoparticles with varying atomic silica to Pt ratios (1.7:1 and 3.3:1) to study the effects of silica to Pt ratio. Considerable voidages were created by inter-situated 10–20 nm silica nanoparticles between support carbon particulates to facilitate mass transfer of reactants and products. This particular method of catalyst preparation increases the Pt metal utilization, and generates a large amount of accessible voidage in the interpenetrating particle network of carbon and silica to support the facile transport of reactants and products. Electrochemical hydrogen adsorption/desorption has shown an increase in electrochemically active surface area by this approach. Methanol electro-oxidation was used as a test reaction to evaluate the catalytic activity. It was found that the Pt catalyst modified with silica at silica:Pt = 1.7:1 atomic ratio was more active than a catalyst prepared when silica to Pt ratio increased to 3.3:1.     

Synthesis and electrochemical characterization of stabilized nickel nanoparticles

Nickel stabilized nanoparticles produced by an organometallic approach (Chaudret's method) starting from the complex Ni(1,5-COD)₂ were used as electrode materials for hydrogen evolution in NaOH at two temperatures (298 and 323 K). The synthesis of the nickel nanoparticles was performed in the presence of two different stabilizers, 1,3-diaminopropane (DAP) and anthranilic acid (AA), by varying the molar ratios (1:1, 1:2 and 1:5 metal:ligand) in order to evaluate their influence on the shape, dispersion, size and electrocatalytic activity of the metallic particles. The presence of an appropriate amount of stabilizer is an effective alternative to the synthesis of small monodispersed metal nanoparticles with diameters around 5 and 8 nm for DAP and AA, respectively. The results are discussed in terms of morphology and the surface state of the nanoparticles. The importance of developing a well-controlled synthetic method which results in higher performances of the resulting nanoparticles is highlighted. Herein we found that the performance with respect to the HER of the Ni electrodes dispersed on a carbon black Vulcan substrate is active and comparable to that reported in the literature for the state-of-the-art electrocatalysts. Appreciable cathodic current densities of ∼240 mA cm⁻² were measured with highly dispersed nickel particles (Ni-5_DAP). This work demonstrates that the aforementioned method can be extended to the preparation of highly active stabilized metal particles without inhibiting the electron transfer for the HER reaction, and it could also be applied to the synthesis of bimetallic nanoparticles.     

Alkaline direct alcohol fuel cells

The faster kinetics of the alcohol oxidation and oxygen reduction reactions in alkaline direct alcohol fuel cells (ADAFCs), opening up the possibility of using less expensive metal catalysts, as silver, nickel and palladium, makes the alkaline direct alcohol fuel cell a potentially low cost technology compared to acid direct alcohol fuel cell technology, which employs platinum catalysts. A boost in the research regarding alkaline fuel cells, fuelled with hydrogen or alcohols, was due to the development of alkaline anion-exchange membranes, which allows the overcoming of the problem of the progressive carbonation of the alkaline electrolyte. This paper presents an overview of catalysts and membranes for ADAFCs, and of testing of ADAFCs, fuelled with methanol, ethanol and ethylene glycol, formed by these materials.