LED light-induced enhanced photocatalytic hydrogen evolution on Au@TiO2 core–shell modified by nitrogen doping and reduced graphene oxide

This study focused on the large band gap of TiO₂ for its use as a photocatalyst under light emitting diode (LED) light irradiation. The photocatalytic activities of core–shell structured Au@TiO₂ nanoparticles (NPs), nitrogen doped Au@TiO₂ NPs, and Au@TiO₂/rGO nanocomposites (NCs) were investigated under various light intensities and sacrificial reagents. All the materials showed better photocatalytic activity under white LED light irradiation than under blue LED light. The N-doped core–shell structured Au@TiO₂ NPs (Au@N–TiO₂) and Au@TiO₂/rGO NCs showed enhanced photocatalytic activity with an average H₂ evolution rate of 9205 μmol h^?1g^?1 and 9815 μmol h^?1g^?1, respectively. All these materials showed an increasing rate of hydrogen evolution with increasing light intensity and catalyst loading. In addition, methanol was more suitable as a sacrificial reagent than lactic acid. The rate of hydrogen evolution increased with increasing methanol concentration up to 25% in DI water and decreased at higher concentrations. Overall, Au@TiO₂ core–shell-based nanocomposites can be used as an improved photocatalyst in photocatalytic hydrogen production.     

S/Se dual-doping promotes the formation of active Ni/Fe oxyhydroxide for oxygen evolution reaction of (sea)water splitting

Surface reconstruction produces metal oxyhydroxide (1OOH) active sites, and promoting surface reconstruction is essential for the design of OER electrocatalysts. In this paper, we reported that a large amount of active NiFeOOH was generated in-situ on the surface of nickel-iron sulfide selenide, thus exposing more active sites and efficiently catalyzing OER. In 1 M KOH solution, NiFeOOH(S,Se) achieves an ultra-low overpotential of 195 mV at the current density of 10 mA cm^?2, and the Tafel slope is only 31.99 mV dec^?1, showing excellent catalytic performance. When the current density is 100  mA cm^?2, the over-potential of NiFeOOH(S,Se) in KOH + seawater solution is 239 mV, which is almost equivalent to 231 mV in KOH solution. The excellent OER stability of the NiFeOOH(S,Se) catalyst in alkaline electrolytes was confirmed, and the overpotential did not change significantly after 4 days of testing in KOH + seawater solution.     

Novel one- and two-dimensional InSbS3 semiconductors for photocatalytic water splitting: The role of edge electron states

Photocatalytic water splitting has become a promising technology to solve environmental pollution and energy shortage. Exploring stable and efficient photocatalysts are highly desired. Herein, we propose novel low-dimensional InSbS₃ semiconductors with good stability based on density functional theory. Such InSbS₃ structures could be obtained from their bulk crystal by suitable exfoliation methods. Our calculations indicate that two-dimensional (2D) and one-dimensional (1D) InSbS₃ nanostructures have moderate band gaps (2.54 and 1.97 eV, respectively) and suitable band edge alignments, which represents sufficient redox capacity for photocatalytic water splitting. 2D InSbS₃ monolayer possesses oxygen evolution reaction (OER) activity and 1D InSbS₃ single-nanochain possesses hydrogen evolution reaction (HER) activity under acidic conditions. Interestingly, two edge electron states can be introduced when the dimension of InSbS₃ is reduced from 2D to 1D and the new electron states can exist in arbitrary-width nanoribbons, which can effectively promote the process of HER. Moreover, InSbS₃ monolayer and single-nanochain also exhibit large solar-to-hydrogen efficiency, high carrier mobility, and excellent optical absorption properties, which can facilitate the process of photocatalytic reactions. Our findings can stimulate the synthesis and applications of low-dimensional InSbS₃ semiconductors for overall water splitting.     

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.     

A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

Pristine and cobalt doped copper sulfide microsphere particles for seawater splitting

In this work, copper sulfide particles are synthesized with different Co doping concentrations such as 0, 1 and 5% at 80 °C by optimizing synthesis times from 1 to 3 h. Copper sulfide particles possess two structural phases of covellite CuS and digenite Cu₉S₅. The increase in synthesis time from 1 to 3 h increases the Cu₉S₅ phase growth and changes the morphology from flower to microsphere. The CuS synthesized with 0, 1 and 5% Co dopant concentrations demonstrate flower consisting of agglomerated nanosheets, microsphere and flower like microsphere. The elemental investigation substantiates Co ions presence in CuS microspheres. The A_1g (LO) mode intensity is decreased with increase in Co dopant concentration confirming Co incorporation into CuS microsphere. The CuS synthesized with 0, 1, 5% Co dopants exhibit 322 mV, 305 mV and 289 mV to attain 100 mA/cm² in 1 M KOH seawater. The CuS synthesized with 5% Co dopant demonstrates higher double layer capacitance (C_dl) of 173.9 mFcm^?2 and lower charge transfer resistance (R_ct) of 6.07 Ω with 78.84% retention after 10 h continuous stability than that of the other pristine (118.3 mFcm^?2, 13.72 Ω) and 1% Co doped CuS microsphere (165.7 mFcm^?2, 8.55 Ω) indicating more surface active site and rapid charge carrier transport, respectively.     

Green synthesis of molybdenum-based nanoparticles and their applications in energy conversion and storage: A review

In the scope of the rapid technological advancements, nanoparticles (NPs) have gained prominence due to their excellent and tunable biological, and physicochemical properties. Nowadays, different methods are used for their synthesis. In particular, the green synthesis of metal precursors for the synthesis of NPs, represents a cost-effective, environmentally friendly, and hazardous chemical-free method for developing a large variety of NPs. By exploiting plant extracts, the production rate of NPs is relatively faster. Due to fossil reserves and high fuel consumption, renewable and clean energy materials are urgently needed to improve environmental sustainability. With outstanding electrochemical and physicochemical characteristics, molybdenum-based NPs (Mo-NPs) are gaining increasing attention in the fields of energy conversion and storage. Considering the significance of Mo-NPs synthesized from greener routes and their energy applications, it is necessary to review recent trends and developments in this field. This review summarizes important research studies and future research guidelines for the preparation of Mo-NPs through green routes and their applications to meet global energy and environmental demands. Moreover, future research directions are also highlighted to achieve sustainable greener precursors and Mo-NPs based energy storage devices.     

Core–Shell Photoanodes for Photoelectrochemical Water Oxidation

Photoelectrochemical (PEC) water splitting into hydrogen and oxygen is a promising solution for the conversion and storage of solar energy. Because sluggish water oxidation is the bottleneck of water splitting, the design and preparation of an efficient photoanode is intensively investigated. Currently, all known photoanode materials suffer from at least one of the following drawbacks: ① low carriers separation efficiency; ② sluggish surface water oxidation reaction; ③ poor long-term stability; ④ insufficient water adsorption and gas desorption. Core–shell configurations can endow a photoanode with improved activity and stability by coating an overlayer that plays energetic, catalytic, and/or protective roles. The construction strategy has an important effect on the activity of a core–shell photoanode. Nonetheless, the mechanism for the improvement of performance is still ambiguous and is worthy of a closer examination. In this review, the successes and challenges of core–shell photoanodes for water oxidation, focusing on synthesis strategies as well as functionalities (facilitating carrier separation, surface reaction promotion, corrosion prevention, and bubble detachment) are explored. Finally, the perspectives of this class of materials in terms of new opportunities and efforts are discussed.     

Ni activated Mo2C nanoparticles supported on stereotaxically-constructed graphene for efficient overall water splitting

Exploring cost-effective, high-efficiency and stable electrocatalysts for overall water splitting is greatly desirable and challenging for sustainable energy. Herein, a novel designed Ni activated molybdenum carbide nanoparticle loaded on stereotaxically-constructed graphene (SCG) using two steps facile strategy (hydrothermal and carbonization) as a bifunctional electrocatalyst for overall water splitting. The optimized Ni/Mo₂C(1:20)-SCG composites exhibit excellent performance with a low overpotential of 150 mV and 330 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively to obtain a current density of 10 mA cm^?2 in 1.0 M KOH solution. In addition, when the optimized Ni/Mo₂C(1:20)-SCG composite is used as a bifunctional electrode for overall water splitting, the electrochemical cell required a low cell voltage of 1.68 V at a current density of 10 mA cm^?2 and long-term stability of 24 h. More significantly, the synergetic effects between Ni-activated Mo₂C nanoparticles and SCG are regarded as a significant contributor to accelerate charge transfer and promote electrocatalytic performance in hybrid electrocatalysts. Our works introduce a novel approach to design advanced bifunctional electrodes for overall water splitting.     

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.