Photocatalytic hydrogen generation by splitting of water from electrospun hybrid nanostructures

MWCNT-TiO₂ hybrid nanostructures are prepared using sol–gel and electrospinning followed by post annealing of as-spun nanofibers at 450 °C per 1 h in air. These hybrid nanostructures composed of MWCNTs varied from 0 to 20% (w/w) and are characterized by SEM, TEM, XRD, and FT-IR analysis. MWCNT-TiO₂ hybrid structures are utilized in commercially available Methylene blue (MB) dye degradation and found that 2% of MWCNT exhibit superior kinetic constant 6.379 × 10⁻³ min⁻¹ extracted. In addition, we demonstrate that the doping of MWCTs within TiO₂ leads to a significant enhancement of the UV–vis light assisted photocatalytic activity is optimized in comparison with higher (5, 10 and 20%) compositions. UV–vis assisted photocatalytic hydrogen is evolved by photoelectrolytic splitting of water by using MWCNT-TiO₂ hybrid nanostructures as electrode.     

Enhanced hydrogen generation via overall water splitting using novel MoS2-BN nanoflowers assembled TiO2 ternary heterostructures

Envisaging headway in the applicability of sustainable H₂ energy, the novel report of the fabrication of MoS₂-BN/TiO₂ (MBT) heterogeneous nanostructures has been proposed via facile in-situ hydrothermal route with an aim to propound the superior substitute of noble metal based conventionally employed catalytic system to surmount their exorbitant cost. We inferred the ascendancy of MoS₂-BN nanoflowers over pristine MoS₂ counterpart in an establishment of TiO₂ based heterostructured catalysis. MBT heterostrucutres were extensively scrutinized with respect to their structural, optoelectronic and computational characteristics. En route to enhanced H₂ evolution, we have investigated the significance of interfacial junctions and exposed sites in the MBT heterostructures. In order to achieve broader pertinence in green H₂ fuel, the performance of MBT heterostrucutres was ascertained with subject to photochemical, electrochemical and photo-electrochemical (PEC) water splitting. Loaded concentration of MoS₂-BN was varied in MBT catalysts and 2.5 wt% MoS₂-BN/TiO₂ exhibited optimum photocatalytic response with an H₂ production rate of 2.6 mmol/g/h with 6.94% AQY and improved photo-current response of 0.99 mA/cm² towards PEC. Electrochemical investigations further intensified the caliber of MBT as HER catalyst ascribed to the higher cathodic current density of 49.23 mA/cm² at 1.22 V potential. The advancement in the catalytic efficiency of MBT heterostructures was evidenced by the synergetic relationship between MoS₂-BN and TiO₂ which stimulated the separation and transfer of photo-charged carriers, and lowered the overpotential values consequently surging the kinetics of H₂ evolution.     

Water photo splitting for green hydrogen energy by green nanoparticles

The demand of green energy will be the major issue in this 21 century. The researchers are trying to develop green energy using a variety of ways. Among various forms of green, safe and sustainable energy, hydrogen is considered as the best one due to its inexpensiveness and no pollution to the environment. Moreover, the abundance of sunlight and water resources are great assets for us to generate hydrogen fuel. The research has incased on water splitting after the development of nanotechnology but the various chemical routs of nanoparticles synthesis are toxic to the human and the environment. In recent years, many nanoparticles are synthesized by green methods utilizing plants and other microbes. Some papers are available on the applications of water splitting using these green nanoparticles. The future of this research is very bright and to increase the further research in this area, a review is written. The present article describes the state-of-the-art of water splitting using green nanoparticles. The attempts are made to describe the various methods of nanoparticles syntheses, their optimizations and applications in hydrogen generation. Besides, the efforts are also made to discuss the working mechanism and future challenges and perspectives.     

Photocatalytic hydrogen generation through water splitting on nano-crystalline LaFeO3 perovskite

Visible light active ABO₃ type photocatalyst with LaFeO₃ composition was synthesized by sol-gel method. The photocatalyst was characterized by different techniques such as X-ray diffraction, BET surface area analysis, particle size analysis, scanning electron microscopy, UV–visible diffuse reflectance spectroscopy (UV–Visible DRS), and photoluminescence spectroscopy. LaFeO₃ photocatalyst exhibited an optical band gap of 2.07 eV with the absorption spectrum predominantly in visible region of the spectrum. The BET surface area of photocatalyst LaFeO₃ was observed as 9.5 m²/g, with the crystallite size of 38.8 nm as calculated by the Debye-Scherer equation. The photocatalytic activity of LaFeO₃ was investigated for hydrogen generation through sacrificial donor assisted photocatalytic water splitting reaction by varying conditions in feasible parametric changes using visible light source, ethanol as a sacrificial donor and Pt solution of H₂PtCl₆ as a co-catalyst. The rate of photocatalytic hydrogen evolution was observed to be 3315 μmol g⁻¹ h⁻¹ under optimized conditions and using 1 mg dose of photocatalyst with reaction time of 4 h and illumination of 400 W.     

Combustion-derived BaNiO3 nanoparticles as a potential bifunctional electrocatalyst for overall water splitting

Electrochemical water electrolyser though an assuring solution for clean hydrogen production, the sluggish kinetics and high cost of existing precious metal electrocatalyst remains a barrier to its effective utilization. Herein, solution combustion route derived perovskite type barium nickelate (BaNiO₃) nanoparticles were developed and studied for their bifunctional electrocatalytic properties towards overall water splitting. The unannealed BaNiO₃ nanoparticles exhibited the highest OER and HER activity with overpotentials 253 mV and 427 mV respectively to attain 10 mAcm⁻² in 1.0 M KOH. Using unannealed BaNiO₃ as a bifunctional electrocatalyst in a two-electrode alkaline electrolyser, the cell was able to achieve the benchmark current density at a low cell voltage of 1.82 V. Impressively the setup's electrocatalytic performance improved 4.9% after continuous overall water splitting for 24 h at 30 mAcm⁻². Therefore, BaNiO₃ nanoparticles can be a low-cost and efficient alternative for noble metal electrocatalysts for clean H₂ production.     

Fabrication of CuO/MoO3 p-n heterojunction for enhanced dyes degradation and hydrogen production from water splitting

The development of excellent photocatalytic material is highly required for energy and environmental applications. In this study, visible light responsive p-n heterojunction photocatalysts based on CuO/MoO₃ with varying ratios of CuO were prepared by the facile hydrothermal method. The crystalline structure, surface morphology, chemical compositions and optical properties of the synthesized photocatalysts were studied using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), photoluminescence (PL) techniques and UV–Vi's absorption spectroscopy. The results showed that the 5%CuO/MoO₃ nanocomposite displayed enhanced photocatalytic performance for the production of hydrogen (98.5 μmol h^?1g^?1) and degradation of dyes rhodamine B (RhB) and alizarine yellow (AY) than all other samples. Furthermore, 5% CuO/MoO₃ composite exhibited excellent stability after five consecutive cycles for both RhB and AY dyes. Overall, the improved photocatalytic performance of 5%CuO/MoO₃ composite was due to increased adsorption of visible light, good surface morphology, enhanced charge separation/transfer which inhibited recombination of electrons and holes. This study could encourage the synthesis of novel and effective p-n heterojunction photocatalysts for practical applications.     

Insight into the mechanism of hydrogen permeation inhibition by cerium during electroplating: Enhanced kinetics of hydrogen desorption

In our previous work, we found that hydrogen permeation can be noticeably reduced during Ni–Cu electroplating by the addition of Ce salt to the plating solution. The mechanism of hydrogen permeation inhibition via Ce salt was further studied in the present work. Through the Iver–Pickering–Zamenzadeh (IPZ) model fitting of the kinetic of hydrogen evolution reaction, we found that the trace Ce salt that precipitated during electroplating could improve Tafel reaction kinetic parameters and reduce the strength of the Ni–H and Cu–H bonds due to its abundant d/f electrons and enough d/f orbitals. Meanwhile, Ce can provide electrons for the Heyrovsky reaction. These effects promoted surface electron migration and thus led to the desorption of adsorbed hydrogen atoms (H_ads) and the decreased diffusion of H_ads into the Ni–Cu coatings. The accuracy of the IPZ model fitting results was verified by hydrogen evolution rate experiments during the electroplating process. Hence, Ce salt can effectively inhibit hydrogen permeation and reduce the dehydrogenation annealing time, thereby showing great potential for energy saving and emission reduction in the electroplating industry.     

Facile hydrothermal synthesis of rare earth phosphate for boosting hydrogen evolution reaction

The water electrolysis process has attracted great attention due to the production of high energy density pure hydrogen. However, the involved cell reactions in this process such as hydrogen and oxygen evolution reactions are kinetically sluggish and demands high input energy to accelerate the rate of these reactions. Therefore, the development and application of efficient electrocatalyst is essential for hydrogen evolution reaction (HER) as well as oxygen evolution reaction (OER). In the present work, we have successfully synthesized two rare earth phosphates through the hydrothermal route and used as a catalysts towards HER in an acidic medium. The rare earth phosphate PrPO₄ exhibits better catalytic activity than YPO₄ catalyst. The overpotential of PrPO₄, YPO₄ and standard Pt/C were found as 147, 484.3 and 58 mV vs. reversible hydrogen electrode, respectively, to reach current density 10 mA·cm^?2 and corresponding Tafel slopes were found as 107.58, 118.73 and 80.89 mV decade^?1, respectively in 0.5 M H₂SO₄. The catalytic activity of PrPO₄ (472.83 mA·cm^?2) overcome standard Pt/C (179.60 mA·cm^?2) at high overpotential 450 mV vs. reversible hydrogen electrode. The prepared PrPO₄ shows efficient electrocatalytic activity towards HER in acidic medium because it possess high BET surface area, large ECSA value and small charge transfer resistance than YPO₄.     

Integrating Co3O4 nanoparticles with MnO2 nanosheets as bifunctional electrocatalysts for water splitting

Developing high-efficiency and low-cost electrocatalyst is significant for the application of water splitting technology. Herein, Co₃O₄ nanoparticles and MnO₂ nanosheets are separately synthesized and subsequently assembled into a unique 0/2-dimensional heterostructure via van der Waals interactions. The consequent composites expose abundant accessible active sites and expedite the reaction kinetics, which can be testified by the superiorities in Tafel slope, exchange current density and double-layer capacitance, only requiring overpotentials of 355 and 129 mV for oxygen and hydrogen evolution reactions in 1.0 M KOH at 10 mA cm^?2, respectively. Moreover, a cell voltage of 1.660 V can drive the electrolyzer at 10 mA cm^?2. Benefitted from robust integration, the original aggregation and restacking of individual materials have been overcome, thereby leading to superior elelctrocatalysis durability. This facile and universal strategy may inspire the researchers on the design and construction of advanced functional composites.     

CoO/NF nanowires promote hydrogen and oxygen production for overall water splitting in alkaline media

The exploration of catalysts with high activity and low cost for water splitting is still necessary. Herein, a nanowire-like morphology CoO/NF electrode is synthesized using facile hydrothermal reaction and calcination treatment. The urea can regulate its morphology during the synthetic process of CoO/NF. Electrochemical studies reveal that the as-obtained CoO/NF exhibits excellent electrocatalytic performance with overpotential of 307 mV at current density of 10 mA cm⁻² and Tafel slope of 72 mV dec⁻¹ for oxygen evolution reaction, and CoO/NF delivers current density of 10 mA cm⁻² at overpotential of 224 mV for hydrogen evolution reaction. The results of the oxygen evolution reaction stability show that the overpotential of CoO/NF electrode is only increased by 4 mV at current density of 10 mA cm⁻². The two-electrode water splitting with CoO/NF electrodes as both anode and cathode needs a cell potential of 1.76 V to reach 10 mA cm⁻². Therefore, this simple method to prepare CoO/NF electrode can enhance the properties of electrocatalysts, which makes CoO/NF a promising material to replace noble metal-based catalysts.     

ZnO thin films,surface embedded with biologically derived Ag/Au nanoparticles,for efficient photoelectrochemical splitting of water

ZnO thin films, showing nano-ridges at the surface and the top layer embedded with metal (Ag/Au) nanoparticles (MNP), were obtained by sol-gel synthesis, using zinc acetate dihydrate [(CH₃.COO)₂Zn.2H₂O] as precursor. The method involved prior synthesis of Ag and Au nanoparticles via biological reduction of AgNO₃ and HAuCl₄, respectively, using algae Spirulina platensis. The XRD analysis indicated dominant evolution of wurtzite ZnO phase. Low-angle shift in peaks, seen with nanoparticles embedded films, indicated partial diffusion of metals into ZnO lattice. Band gap energy was least affected and lied in the expected range. AFM and SEM analysis revealed the surface topography and morphology, while EDX analysis confirmed the elemental stoichiometry and existence of Ag/Au nanoparticles in samples. Significant gain in photoelectrochemical current using MNP embedded films is largely accountable to the improvement in electrical conductance and the role played by metal nanoparticles in charge-carrier separation, collection and transport.     

Pristine and Se-/In-doped TlAsS2 enhance the solar energy-driven water splitting for hydrogen generation

The enhanced photocatalytic performance of Se-/In-doped TlAsS₂ to generate hydrogen from water splitting is investigated based on the first-principle density functional theory calculation with meta-GGA + TPSS. Three structures, namely, pristine TlAsS₂ and substitutions of S with Se and Tl with In, are considered. Their geometrical lattices are fully optimized and their electronic and optical properties are calculated to evaluate the photocatalytic efficiency for hydrogen generation. Results show that the three structures can be used for solar energy photocatalysis to generate hydrogen from water splitting. Moreover, the Se- and In-doped atoms can strengthen the absorption coefficient within the visible light range. Therefore, these structures are promising catalysts for generating hydrogen from water splitting through solar energy photocatalysis.     

Pulsed current water splitting electrochemical cycle for hydrogen production

A pulsed current 3 D MnO₂ electrode water splitting electrochemical cycle is being proposed for hydrogen production. In 3D MnO₂ electrochemical cycle, the reactions take place at the solid/liquid and solid/gas two phase boundaries. Also, this electrochemical cycle should be able to generate hydrogen and oxygen gas separately at different periods of time. Here, we applied an interrupted pulsed current to reduce the overpotential caused by diffusion layers in conventional direct current electrolysis. The pulsed current, which disturbs the formation of the ion diffusion layer in the vicinity of the electrodes, is observed to be effective above 50 Hz. The best electrolysis performance was recorded at a current density of 0.2 A cm^?2, and the observed cell voltage was 1.69 V at 25 °C for a pulse frequency of 500 Hz, which is less than the corresponding conventional alkaline electrolysis.     

Synthesis and high photocatalytic hydrogen production of SrTiO3 nanoparticles from water splitting under UV irradiation

Cubic SrTiO₃ powders were synthesized by three methods: the polymerized complex (PC) method, the solid state reaction, and the milling assistant method. The samples obtained were characterized by X-ray diffraction (XRD), UV–vis spectroscopy (UV–vis), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The mean diameters of the as-synthesized SrTiO₃ particles were 30 nm by the polymerized complex method, 140 nm by the solid state reaction, and 30 nm by the milling assistant method. The photocatalytic activity of hydrogen evolution from water splitting over SrTiO₃ powders by the polymerized complex method is higher than that by the solid state reaction and the milling assistant method. Particle size, uniformity of components, and particle aggregation extent affect the photocatalytic activity of SrTiO₃ for hydrogen evolution. The best rate of photocatalytic hydrogen evolution over SrTiO₃ by the polymerized complex method under UV illumination is as high as 3.2 mmol h⁻¹ g⁻¹.     

Recent development in electrocatalysts for hydrogen production through water electrolysis

Hydrogen is a carbon-free alternative energy source for use in future energy frameworks with the advantages of environment-friendliness and high energy density. Among the numerous hydrogen production techniques, sustainable and high purity of hydrogen can be achieved by water electrolysis. Therefore, developing electrocatalysts for water electrolysis is an emerging field with great importance to the scientific community. On one hand, precious metals are typically used to study the two-half cell reactions, i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, precious metals (i.e., Pt, Au, Ru, Ag, etc.) as electrocatalysts are expensive and with low availability, which inhibits their practical application. Non-precious metal-based electrocatalysts on the other hand are abundant with low-cost and eco-friendliness and exhibit high electrical conductivity and electrocatalytic performance equivalent to those for noble metals. Thus, these electrocatalysts can replace precious materials in the water electrolysis process. However, considerable research effort must be devoted to the development of these cost-effective and efficient non-precious electrocatalysts. In this review article, we provide key fundamental knowledge of water electrolysis, progress, and challenges of the development of most-studied electrocatalysts in the most desirable electrolytic solutions: alkaline water electrolysis (AWE), solid-oxide electrolysis (SOE), and proton exchange membrane electrolysis (PEME). Lastly, we discuss remaining grand challenges, prospect, and future work with key recommendations that must be done prior to the full commercialization of water electrolysis systems.     

Rare earth metals co-doped ZnO/CNTs composite as high performance photocatalyst for hydrogen production from water_triethanolmine mixture

This study investigated the zinc oxide (ZnO) based heterojunction photocatalysts for improved hydrogen production from water splitting. A sol-gel route was adopted to produce terbium (Tb) and samarium (Sm) co-doped ZnO/CNTs composites where CNTs worked as a support material. The built-in redox couples of lanthanides in co-doped TS-ZnO/CNTs composite showed higher hydrogen evolution activity than Sm doped (Sm-ZnO/CNTs) and Tb doped (Tb–ZnO/CNTs) photocatalysts. When triethanolamine was utilized as a sacrificial agent, the TS-ZnO/CNTs photocatalyst result in a remarkable hydrogen evolution rate of 2683 molh^?1g^?1 under visible light illumination. The optimum photocatalyst also showed high stability over five successive hydrogen evolution cycles. The better hydrogen evolution rate with TS-ZnO/CNTs was referred to its fine particle size, high reactive surface area, small optical band gap, suppressed reunification of charge carriers and built-in redox couples. The photocatalytic mechanism, involved in water splitting with TS-ZnO/CNTs photocatalyst, is also deduced in this study. This study can stimulate the attempts towards construction of lanthanides based co-doped semiconductor photocatalysts for efficient hydrogen evolution.     

Effect of carbon coating on Cu electrodes for hydrogen production by water splitting

In recent years, fossil fuel depletion has been increasing, which leads to environmental issues. Hydrogen energy is considered a promising renewable energy to replace fossil fuels because it is a sustainable, clean, and green energy source. Among hydrogen production methods, water splitting has the highest reliability and is used the most often. Platinum is normally used as water splitting catalyst and an electrode. However, there has been much effort to replace it as such owing to its high cost. Copper (Cu) is not used as water splitting catalyst or an electrode, despite its high current density, because of its corrosive properties. In this study, carbon was coated onto a Cu substrate and a hydrogen production experiment was carried out with 0.1 M Na₂SO₄ and 0.1 M H₂SO₄ electrolytes. As a result, the carbon coating decreased oxidation rate of the Cu electrode and effected stability in short-term hydrogen evolution experiment. This indicates the possibility of carbon-Cu electrode with other catalytic materials.     

CoP@NC electrocatalyst promotes hydrogen and oxygen productions for overall water splitting in alkaline media

Design and synthesis of high-performance bi-functional electrocatalysts can play a crucial role for electrolytic water splitting. Herein, we develop a simple phosphating process to construct cobalt phosphide@nitrogen-doped carbon (CoP@NC) using metal organic frame (MOF) as a precursor and a template. In alkaline solution, CoP@NC-350 exhibits exceptional hydrogen and oxygen evolution reaction performances with over potentials of 75 mV and 268 mV at 10 mA cm^?2, respectively. For a symmetric CoP@NC-350 two-electrode water splitting setup, the potential can be low as 1.69 V to obtain 10 mA cm^?2. Therefore, low-temperature phosphating treatment can be a simple and promising method to produce electrocatalysts for water splitting.     

PBA derived FeCoP nanoparticles decorated on NCNFs as efficient electrocatalyst for water splitting

Transition metal phosphides have been known as promising electrocatalysts for hydrogen evolution and oxygen evolution reactions (HER and OER) due to their high catalytic activity. In this work, the FeCoP nanoparticles decorated on N-doped electrospun carbon nanofibers (FeCoP@NCNFs) was successfully synthesized through depositing Fe, Co-based Prussian blue analogue Co₃[Fe(CN)₆]₂·10H₂O (FeCo-PBA) onto the electrospun PVP/PAN nanofibers via layer-by-layer approach, followed by carbonization and phosphorization treatments. Benefiting from the high electrical conductivity, abundant catalytic active sites and the synergistic effect between FeCoP nanoparticles and N-doped carbon nanofibers network, the obtained FeCoP@NCNFs displays good bifunctional electrocatalytic activity. In 1 M KOH, the FeCoP@NCNFs achieves 10 mA cm^?2 at an overpotential of 290, 226 mV for OER and HER, respectively. Moreover, it demands overpotential of 196 mV to achieve 10 mA cm^?2 for HER in 0.5 M H₂SO₄. The FeCoP@NCNFs is used as both anode and cathode for overall water splitting, it requires a low voltage of 1.65 V to achieve a current density of 10 mA cm^?2 and maintains outstanding stability over 10 h. Herein, a strategy for preparing bifunctional electrocatalysts of compositing transition metal phosphides with carbon nanofibers is proposed, and the application of metal-organic framework in electrocatalytic field is further extended.