Search Results (109)

Despite significant progress in photoelectrochemical (PEC) water splitting, high fabrication costs and limited efficiency of photoanodes hinder practical applications. Bismuth vanadate (BiVO₄), with its low cost, non-toxicity, and suitable band structure, is a promising photoanode material but suffers from poor charge transport, sluggish surface kinetics, and photocorrosion. In this study, porous monoclinic BiVO₄ films are fabricated via a simplified successive ionic layer adsorption and reaction (SILAR) method, followed by borate treatment and PEC deposition of NiFeO_x. The resulting B/BiVO₄/NiFeO_x photoanode exhibits a significantly enhanced photocurrent density of 2.45 mA cm⁻² at 1.23 V vs. RHE—5.3 times higher than pristine BiVO₄. It also achieves an ABPE of 0.77% and a charge transfer efficiency of 79.5%. These results demonstrate that dual surface modification via borate and NiFeO_x is a cost-effective strategy to improve BiVO₄-based PEC water splitting performance. This work provides a promising pathway for the scalable development of efficient and economically viable photoanodes for solar hydrogen production. Full article

Constructing a heterojunction is considered one of the most effective strategies for enhancing photocatalytic activity. Herein, we employ Ta₃N₅ and tubular graphitic carbon nitride (TCN) to construct a Ta₃N₅/TCN van der Waals heterojunction via electrostatic self-assembly for enhanced photocatalytic H₂ production. SEM and TEM results show that Ta₃N₅ particles (~300 nm in size) are successfully anchored onto the surface of TCN. The light absorption capability of the Ta₃N₅/TCN heterojunction is between those of Ta₃N₅ and TCN. The strong interaction between Ta₃N₅ and TCN with different energy structures (Fermi levels) by van der Waals force renders the formation of an interfacial electric field to drive the separation and transfer of photogenerated charge carriers in the Ta₃N₅/TCN heterojunction, as evidenced by the photoluminescence (PL) and photoelectrochemical (PEC) characterization results. Consequently, the optimal Ta₃N₅/TCN heterojunction exhibits a remarkable H₂ production rate of 12.73 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 3.3 and 16.8 times those of TCN and Ta₃N₅, respectively. Meanwhile, the cyclic experiment demonstrates excellent stability of the Ta₃N₅/TCN heterojunction upon photocatalytic reaction. Notably, the photocatalytic performance of 15-TaN/TCN outperforms the most previously reported CN-based and Ta₃N₅-based heterojunctions for H₂ production. This work provides a new avenue for the rational design of CN-based van der Waals heterojunction photocatalysts with enhanced photocatalytic activity. Full article

Developing high-efficiency photoelectrodes plays an important role in the photoelectrocatalytic generation of hydrogen peroxide (H₂O₂) in the photoelectrochemical (PEC) water splitting field. In this work, an innovative strategy was proposed, the synergistic photocatalytic production of H₂O₂ using a bidirectional photoanode–photocathode coupling system under visible-light irradiation. Fe₂O₃-Ti, as the photoanode, which was built by way of Fe₂O₃ loaded on Ti-mesh using the hydrothermal-calcination method, was investigated in terms of the suitability of its properties for PEC H₂O₂ production after optimization of the bias voltage, the type of electrolyte solution, and the concentration of the electrolyte. Afterwards, a H-type double-electrode coupling system with an Fe₂O₃-Ti photoanode and a WO₃@Co₂SnO₄ photocathode was established for the bidirectional synergistic production of H₂O₂ under visible-light irradiation. The yield of H₂O₂ reached 919.56 μmol·L⁻¹·h⁻¹ in 2 h over −0.7 V with 1 mol·L⁻¹ of KHCO₃ as the anolyte and 0.1 mol·L⁻¹ Na₂SO₄ as the catholyte (pH = 3). It was inferred that H₂O₂ production on the WO₃@Co₂SnO₄ photocathode was in line with the 2e^- oxygen reduction reaction (ORR) principle, and on the Fe₂O₃-Ti photoanode was in line with the 2e^- water oxidation reaction (WOR) rule, or it was indirectly promoted by the electrolyte solution KHCO₃. This work provides an innovative idea and a reference for anode–cathode double coupling systems for the bidirectional production of H₂O₂. Full article

Hydrogen production via water splitting is a crucial strategy for addressing the global energy crisis and promoting sustainable energy solutions. This review systematically examines water-splitting mechanisms, with a focus on photocatalytic and electrochemical methods. It provides in-depth discussions on charge transfer, reaction kinetics, and key processes such as the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Various electrode synthesis techniques, including hydrothermal methods, chemical vapor deposition (CVD), pulsed laser deposition (PLD), and radio frequency sputtering (RF), are reviewed for their advantages and limitations. The role of carbon-based materials such as graphene, biochar, and graphitic carbon nitride (g-C₃N₄) in photocatalytic and photoelectrochemical (PEC) water splitting is also highlighted. Their exceptional conductivity, tunable band structures, and surface functionalities contribute to efficient charge separation and enhanced light absorption. Further, advancements in heterojunctions, doped systems, and hybrid composites are explored for their ability to improve photocatalytic and PEC performance by minimizing charge recombination, optimizing electronic structures, and increasing active sites for hydrogen and oxygen evolution reactions. Key challenges, including material stability, cost, scalability, and solar spectrum utilization, are critically analyzed, along with emerging strategies such as novel synthesis approaches and sustainable material development. By integrating water splitting mechanisms, electrode synthesis techniques, and advancements in carbon-based materials, this review provides a comprehensive perspective on sustainable hydrogen production, bridging previously isolated research domains. Full article

The relentless consumption of fossil fuels and soaring CO₂ emissions have plunged the world into an energy and environmental crisis. As society grapples with these challenges, the demand for clean, renewable, and sustainable energy solutions has never been more urgent. However, even though many efforts have been made in this field, there is still room for improvement concerning efficiency, material stability, and catalytic enhancement regarding kinetics and selectivity of photoelectrochemical (PEC) processes. Herein, we provide the experimental proof for the enhancement of the photocurrent efficiency by the critical focus on semiconductor–electrolyte interface (SEI) properties. By tailoring electrolyte composition, researchers can unlock significant improvements in catalytic efficiency and stability, paving the way for advanced PEC technologies. In this study, we investigate the influence of electrolyte composition on SEI properties and its impact on PEC performance. By employing electrolytes enriched with carbonates, borates, sulphates, and alkali cations, we demonstrate their profound role in optimising photoelectrochemical CO₂ reduction reaction (CO₂RR) efficiency. Central to this work is Cu₂O—an affordable, highly promising photocatalyst. While its potential is undeniable, Cu₂O’s inherent instability and diverse reduction products, ranging from CH₃OH to CO, HCOOH, CH₃COOH, and CH₃CH₂OH, have hindered its widespread adoption in PEC CO₂ reduction (CO₂RR). Our approach leverages a straightforward yet powerful electrodeposition method, enabling a deeper exploration of SEI dynamics during photocatalysis. Key parameters, such as carbonate concentration, local pH, alkali cation presence, anionic geometry, CO₂ solubility, and electrolyte conductivity, are systematically investigated. The findings reveal the formation of a unique “rigid layer” at the photocatalyst surface, driven by specific cation–anion interactions. This rigid layer plays a pivotal role in boosting PEC performance, offering a new perspective on optimising, among other PEC processes, CO₂RR catalytic efficiency. This profound study bridges a critical knowledge gap, shedding light on the dual influence of cations and anions on SEI properties and PEC CO₂RR. By unravelling these intricate interactions, we provide a roadmap for designing next-generation PEC systems. These insights pave the way for sustainable energy advancements, inspiring innovative strategies to tackle one of the most pressing challenges of our time. Full article

Considering the poor conductivity of Fe₂O₃ and the weak oxygen evolution reaction associated with it, surface hole accumulation leads to electron hole pair recombination, which inhibits the photoelectrochemical (PEC) performance of the Fe₂O₃ photoanode. Therefore, the key to improving the PEC water oxidation performance of the Fe₂O₃ photoanode is to take measures to improve the conductivity of Fe₂O₃ and accelerate the reaction kinetics of surface oxidation. In this work, the PEC performances of Fe₂O₃ photoanodes are synergistically improved by combining loaded an FeOOH cocatalyst and oxygen vacancy doping. Firstly, amorphous FeOOH layers are successfully prepared on Fe₂O₃ nanostructures through simple photoassisted electrodepositon. Then oxygen vacancies are introduced into FeOOH-Fe₂O₃ through plasma vacuum treatment, which reduces the content of Fe-O (O_L) and Fe-OH (-OH), jointly promoting the generation of oxygen vacancies. Oxygen vacancy can increase the concentration of most carriers in Fe₂O₃ and form photo-induced charge traps, promoting the separation of electron holes and enhancing the conductivity of Fe₂O₃. The other parts of -OH act as oxygen evolution catalysts to reduce the reaction obstacle of water oxidation and promote the transfer of holes to the electrode/electrolyte interface. The performance of FeOOH-Fe₂O₃ after plasma vacuum treatment has been greatly improved, and the photocurrent density is about 1.9 times higher than that of the Fe₂O₃ photoanode. The improvement in the water oxidation performance of PEC is considered to be the synergistic effect of the cocatalyst and oxygen vacancy. All outstanding PEC response characteristics show that the modification of the cocatalyst and oxygen vacancy doping represent a favorable strategy for synergistically improving Fe₂O₃ photoanode performance. Full article

The modular photoelectrochemical (PEC) reactor accommodating eight photoelectrodes with a total active area of up to 46 cm² has been designed and manufactured using the fused deposition modeling method. The device was equipped with an electrolyte flow system, a relay module for the photoelectrode connection, and a feedback-loop module for switching between counter electrodes. The performance and durability of the system were tested within three case study experiments. The water splitting process was successfully combined with an in situ hydrogen storage in the form of metal hydride phases (confirmed by powder X-ray diffraction) using Fe₂O₃- or WO₃-based photoanodes and LaNi₅-based cathodes. The PEC water oxidation at the anodes was realized either in a strongly alkaline electrolyte (pH > 13.5) or in acidified synthetic seawater (pH < 2) for Fe₂O₃ and WO₃ electrodes, respectively. In the latter case, the photoresponse of the anodes decreased the cell charging voltage by 1.7 V at the current density of 60 mA∙g⁻¹. When the seawater was used as an anolyte, the oxygen evolution reaction was accompanied by the chlorine evolution reaction. The manufactured PEC-metal hydride reactor revealed mechanical and chemical stability during a prolonged operation over 300 h and in the broad range of pH values. Full article

In this work, three carboxymethyl starches (CMS) were obtained by the two-step reaction process of carboxymethylation with different degrees of substitution (0.16, 0.33, and 0.36). From these samples, (bio)polyelectrolyte complexes ((bio)PECs) were obtained with chitosan (Chit) by the mixing of individual solutions of polymers (0.25 wt.%) at different volume ratios. The effect of the biopolymer and ionized groups of z ratios, pH, and degree of substitution of CMS in the formation of PEC were evaluated by turbidimetry and dynamic light scattering. The results showed that increasing the amount of CMS samples (ratio of z) led to an increase in the efficiency of the formation of (bio)PEC using CMS with a high DS value. Using the turbidimetry method for the chitosan and CMS mixtures, it was observed that the formation of (bio)PEC is divided into four transition zones delimited by pH transition points, and the stoichiometric complexation (z = 1) is achieved at a pH that displayed morphological changes “pH_morph”, which is a single point for Chit:CMS 1, and for Chit:CMS 2 and Chit:CMS 3, this is a range of 4.9–6.4 and 4.3–6.4, respectively. Analysis of the structural properties of the structures of (bio)PECs by dynamic light scattering was characterized by monomodal distribution, and the main observed effect was associated with an increase in the value of D_avg with an increase in the ratio of Chit:CMS. Full article

Cobalt ferrite (CoFe₂O₄) combined with multi-walled carbon nanotubes (MWCNTs) is an outstanding material regarding photoelectrochemical water oxidation (PEC-WO) because of its excellent catalytic properties and stability. On the other hand, surface imperfections in CoFe₂O₄ can cause band bending and surface Fermi level pinning, significantly reducing its PEC conversion efficiency. Heterostructure engineering is essential for achieving increased light-gathering capacity and charge separation efficiency for PEC-WO. In this study, a quaternary heterostructure of CoFe₂O₄/MWCNT-doped Metal–Organic Framework-100 (Iron), MIL-100(Fe)/Titanium Oxide (TiO₂) was synthesized by using a combination of hydrothermal, solvothermal, and “dip and dry” techniques. Characterization results confirmed the formation of a structural network of MIL-100(Fe) on TiO₂ surfaces, enhanced by the incorporation of MWCNTs during the hydrothermal reaction. Under 1 sun irradiation, the resultant quaternary heterostructure displayed a photocurrent density (J_ph) of 3.70 mA cm⁻² under free bias voltage, which is around 3.08 times more than that of pristine TiO₂ photoanodes (J_ph = 1.20 mA cm⁻²). This investigation highlights the advantages of the MIL-100(Fe) network in improving the solar PEC-WO performance of TiO₂ photoanodes. Full article

In the realm of photoelectrocatalytic (PEC) water splitting, the BiVO₄/WO₃ photoanode exhibits high electron–hole pair separation and transport capacity, rendering it a promising avenue for development. However, the charge transport and reaction kinetics at the heterojunction interface are suboptimal. This study uses the hydrothermal–electrodeposition–dip coating–calcination method to prepare a microcrystalline WO₃ photoanode thin film as the substrate material and combines it with nanocrystalline BiVO₄ to form a micro–nano-structured heterojunction photoanode to enhance the intrinsic and surface/interface charge transport properties of the photoanode. Under the condition of 1.23 V vs. RHE, the photoelectric current density reaches 1.09 mA cm⁻², which is twice that of WO₃. Furthermore, by using a simple impregnation–mineralization method to load the amorphous FeOOH catalyst, a noncrystalline–crystalline composite structure is formed to increase the number of active sites on the surface and reduce the overpotential of water oxidation, lowering the onset potential from 0.8 V to 0.6 V (vs. RHE). The photoelectric current density is further increased to 2.04 mA cm⁻² (at 1.23 V vs. RHE). The micro–nano-structure and noncrystalline–crystalline composite structure proposed in this study will provide valuable insights for the design and synthesis of high-efficiency photoelectrocatalysts. Full article

ZnIn₂S₄ nanosheets are a promising photoanode for driving photoelectrochemical (PEC) hydrogen fuel production; nevertheless, poor charge separation and sluggish surface reaction kinetics hinder its PEC performance to an extreme degree. Herein, a facile element doping strategy (i.e., P element) was developed to obtain the desired photoanode. As a result, the ZnIn₂S₄-P (ZIS-P₅) photoanode exhibits a remarkable photocurrent density of 1.66 mA cm⁻² at 1.23 V versus a reversible hydrogen electrode (V_RHE) and a much lower onset potential of 0.12 V vs. RHE for water oxidation. Careful electrochemical analysis confirms that the P doping and sulfur vacancies (Sv) not only facilitate the hole transfer, but also boost surface reaction kinetics. Finally, the “killing two birds with one stone” goal can be achieved. Moreover, the optimized photoanode also presents high PEC performance for urea oxidation, obtaining a photocurrent density of 4.13 mA cm⁻² at 1.23 V vs. RHE. This work provides an eco-friendly, simple and effective method to realize highly efficient solar-to-hydrogen conversion. Full article

A Z-scheme heterojunction photo(electro)catalyst was fabricated by coupling sulfonic acid-modified graphitic carbon nitride (SA-g-CN) with bismuth oxyiodide (BiOI). The SA-g-CN component was prepared via wet-impregnation, while BiOI was synthesized through a hydrothermal method. Comprehensive characterization elucidated the structural and morphological properties of the resulting composite. The SA-g-CN/BiOI exhibited exceptional performance in both photocatalytic degradation of tartrazine (TTZ) and photoelectrochemical oxygen evolution reaction (OER). Notably, 98.26% TTZ removal was achieved within 60 min of irradiation, while an OER onset potential of 0.94 V (vs. Ag/AgCl) and a high photocurrent density of 6.04 mA were recorded under AM 1.5G illumination. Band energy calculations based on Mott–Schottky measurements confirmed the formation of a Z-scheme heterojunction, which facilitated efficient charge separation and transfer, thereby enhancing catalytic activity. These findings establish the SA-g-CN/BiOI composite as a promising candidate for sustainable energy generation and environmental remediation applications. Full article

The study utilized a simple and cost-effective approach to improve the photoelectrochemical (PEC) water-splitting performance of various materials, including reduced graphene oxide (rGO), tin oxide nanostructures (SnO₂), and rGO/SnO₂ composites. The composites examined were rS15, containing 15 mg of rGO and 45 mg of SnO₂, and rS5, with 5 mg of rGO and 50 mg of SnO₂, tested in a sodium hydroxide (NaOH) electrolyte. Notably, the rS5 electrode showed a significant increase in PEC efficiency in 0.1 M NaOH, achieving a peak photocurrent density of 13.24 mA cm⁻² under illumination, which was seven times higher than that of pristine rGO nanostructures. This enhancement was attributed to the synergistic effects of the heterostructure, which reduced resistance and minimized charge recombination, thereby maximizing the catalytic activity across the various electrochemical applications. Furthermore, the rS5 anode demonstrated improved Tafel parameters, indicating faster reaction kinetics and lower overpotential for efficient current generation. These results highlight the potential for optimizing nanostructures to significantly enhance PEC performance, paving the way for advancements in sustainable water-splitting technologies. Full article

Petroleum-based food packaging causes environmental problems such as waste accumulation and microplastic generation. In this work, biobased films from stable polyelectrolyte complex suspensions (PECs) of xylan and chitosan (70 Xyl/30 Ch wt% mass ratio), at different concentrations of citric acid (CA) (0, 2.5, 5, 7.5 wt%), were prepared and characterized. Films were treated at two temperatures (135 °C, 155 °C) and times (30 min, 60 min) to promote covalent crosslinking. Esterification and amidation reactions were confirmed by Fourier Transform Infrared Spectroscopy and Confocal Raman Microscopy. Water resistance and dry and wet stress–strain results were markedly increased by thermal treatment, mainly at 155 °C. The presence of 5 wt% CA tended to increase dry and wet stress–strain values further, up to 88 MPa—10% (155 °C for 60 min), and 5.6 MPa—40% (155 °C for 30 min), respectively. The UV-blocking performance of the films was improved by all treatments, as was thermal stability (up to T_onset: 230 °C). Contact angle values were between 73 and 84°, indicating partly wettable surfaces. Thus, thermal treatment at low CA concentrations represents a good alternative for improving the performance of Xyl/Ch films. Full article

Hydrogen generation via photoelectrochemical (PEC) overall water splitting is an attractive means of renewable energy production so developing and designing the cost-effective and high-activity bifunctional PEC catalysts both for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) has been focused on. Based on first-principles calculations, we propose a feasible strategy to enhance either HER or OER performance in the monoclinic exposed BiVO₄ (110) facet by the introduction of oxygen vacancies (O_vacs). Our results show that oxygen vacancies induce charge rearrangements, which enhances charge transfer between active sites and adatoms. Furthermore, the incorporation of oxygen vacancies reduces the work function of the system, which makes charge transfer from the inner to the surface more easily; thus, the charges possess stronger redox capacity. As a result, the O_vac reduces both the hydrogen adsorption-free energy (ΔG_H*) for the HER and the overpotential for the OER, facilitating the PEC activity of overall water splitting. The findings provide not only a method to develop bifunctional PEC catalysts based on BiVO₄ but also insight into the mechanism of enhanced catalytic performance. Full article