Separation Efficiency Of Charge Carriers Research Articles

Interconnected Periodic Macroporous NaNbO3 for High-Efficiency Solar-Driven Photocatalytic Hydrogen Evolution.

Highly ordered periodic macroporous structures have been extensively utilized to significantly enhance the photocatalytic activity. However, constructing 3D interconnected ordered porous ternary nanostructures with highly crystalline frameworks remains a formidable challenge. Here, we introduce the design and fabrication of 3D interconnected periodic macroporous NaNbO3 (PM NaNbO3) to effectively increase the density of surface-active sites and optimize the photogenerated carrier-transfer efficiency. By incorporating Pt as a cocatalyst, PM NaNbO3 exhibits an exceptional photocatalytic hydrogen generation rate of 10.04 mmol h-1 g-1, which is approximately six and five times higher than those of calcined NaNbO3 (C-NaNbO3) and hydrothermal NaNbO3 (H-NaNbO3), respectively. This outstanding performance can be attributed to the synergistic effects arising from its well-interconnected pore architecture, large surface area, enhanced light absorption capability, and improved charge carrier separation and transport efficiency. The findings presented in this study demonstrate an innovative approach toward designing hierarchically periodic macroporous materials for solar-driven hydrogen production.

Enhanced Photocatalytic Hydrogen Evolution of In2S3 by Decorating In2O3 with Rich Oxygen Vacancies.

The hydrogen (H2) evolution rates of photocatalysts suffer from weak oxidation and reduction ability and low photogenerated charge carrier separation efficiency. Herein, by combining band-gap structure optimization and vacancy modulation through a one-step hydrothermal method, In2O3 containing oxygen vacancy (Ov/In2O3) is simply introduced into In2S3 to promote photocatalytic hydrogen evolution. Specifically, the change in the sulfur source ratio can induce the coexistence of Ov/In2O3 and In2S3 in a high-temperature hydrothermal process. Under light irradiation, In2S3@Ov/In2O3-0.1 nanosheets hold a remarkable average H2 evolution rate up to 4.04 mmol g-1 h-1, which is 32.14, 11.91, and 2.25-fold better than those of pristine In2S3, In2S3@Ov/In2O3-0.02, and In2S3@Ov/In2O3-0.25 nanosheets, respectively. The ultraviolet-visible (UV-vis) diffuse reflectance and photoluminescence (PL) spectra reveal that the formation of Ov/In2O3 in In2S3 optimizes the band-gap structure and accelerates the migration of the photogenerated charge carrier of In2S3@Ov/In2O3-x nanosheets, respectively. Both the enhancement of oxidation and reduction ability and photogenerated charge carrier separation ability are responsible for the remarkable improvement in photocatalytic H2 evolution performance. This work provides a new strategy to prepare a composite of metal sulfide and metal oxide through a one-step hydrothermal method.

Photocatalytic Synthesis of Ammonia from Hollow Coral-Like Graphitic Carbon Nitride/FeOCl Loaded with Fe-1T MoS2 Nanosheets as Cocatalysts.

Photocatalytic ammonia synthesis (PAS) represents an emerging environmentally friendly approach to ammonia production. In this work, we employed Fe doping to modify the cocatalyst 1T MoS2, enhancing the active N2 sites on Fe-1T MoS2 by inducing defects on the surface of 1T MoS2. Afterward, Fe-1T MoS2 was loaded onto a hollow coral-like graphitic carbon nitride (CCN)/FeOCl composite. Under simulated sunlight, the efficiency of 5% Fe-1T MoS2@CCN/FeOCl (Fe-MCN/FeOCl) reached 367.62 μmol g-1 h-1, surpassing 1T MoS2@CCN(MCN) by 3.2 times, CCN by 16.9 times, and g-C3N4 by 32.5 times, where 5% means the doping amount of Fe in 1T MoS2. The good performance of Fe MCN/FeOCl should be attributed to the Fe doping in Fe-MCN/FeOCl which not only increases the separation efficiency of active sites and charge carriers, but also reduces the sample impedance significantly through the heterojunction formed between CCN and FeOCl. This work also presents a method for creating more efficient and stable photocatalysts for ammonia synthesis.

A new Ni-based cocatalyst nickel thiocarbonate enhancing graphitic carbon nitride photocatalytic hydrogen production by constructing a built-in electric field

Despite the excellent photocatalytic activity under visible light, graphitic carbon nitride (g-C3N4) exhibits a high overpotential for hydrogen evolution. To address this issue, cocatalysts have been utilized to modify g-C3N4. However, the use of high-performance cocatalysts typically involves noble metals such as platinum and palladium, which are cost-prohibitive for practical applications. Therefore, the development of efficient and cost-effective cocatalysts is crucial for advancing photocatalysis. In this study, we synthesized a new Ni-based cocatalyst, nickel thiocarbonate (NiCS3), to enhance the photocatalytic hydrogen evolution reaction (HER) on g-C3N4. The NiCS3/g-C3N4 composite demonstrated a significantly increased hydrogen evolution rate of 951 μmol·h−1·g−1 under visible light, representing more than a 105-fold improvement compared to pure g-C3N4. Theoretical calculations suggested that the enhanced performance in photocatalytic hydrogen production can be attributed to the generation of a built-in electric field within the composite, facilitating efficient charge carrier separation and migration. Additionally, the C site in NiCS3 provides a favorable Gibbs free energy of adsorbed H* (ΔGH∗). This work underscores the potential of NiCS3 as a viable alternative to precious metals in photocatalytic hydrogen production using g-C3N4.

Advancing photocatalytic activity through a green route: Bismuth ferrite@molybdenum trioxide heterostructure for sustainable water treatment

Photocatalysis has become increasingly pervasive in the chemical industry, profoundly impacting operational costs. However, an ideal photocatalyst must possess characteristics such as excellent reactivity, high selectivity, prolonged stability, low toxicity, and cost-effectiveness. Moreover, it should facilitate the efficient separation of photo-generated charge carriers, thereby minimizing recombination rates. In pursuit of advancing photocatalytic activity for sustainable water treatment, this investigation focused on synthesizing a groundbreaking photocatalyst, the Bismuth Ferrite@Molybdenum trioxide heterostructure, using an eco-friendly green chemistry technique with pomegranate extract. This approach aligns with the goal of environmental sustainability and represents a novel contribution to the field. Employing a comprehensive approach, advanced characterization techniques such as XRD, SEM, FT-IR, and UV–Vis were applied to analyze the material's structural, morphological, and optical properties. According to the characterization results, the heterostructure demonstrates superior photocatalytic efficiency, heightened crystallinity, and reduced recombination rates during dye degradation for water treatment compared to both individual photocatalysts. Notably, the composite catalyst exhibits a synergistic impact, outperforming individual BiFeO3 and MoO3 photocatalysts. SEM observations confirm the successful integration of rod-like MoO3 and cylindrical BiFeO3 morphologies, highlighting the strategic combination achieved through the green chemistry route. Furthermore, UV–Vis spectroscopy reveals key optical parameters, emphasizing a narrow bandgap energy of 2.74 eV with a high refractive index of 2.43 eV. The exceptional efficacy of the heterostructure in degrading dyes within the visible spectrum, surpassing expectations within a 4-hour timeframe, highlights its efficiency and precision. Remarkably, achieved degradation rates for Rhodamine B dye (98 %), Methyl Blue (96 %), and Methyl Orange dye (95 %) highlights the promising role of proposed photocatalytic system in effectively addressing water pollutant challenges.

Ultrathin 2D Alloyed Cu−Ga−Zn−S Curved Nanobelts for Boosting Visible‐Light Photocatalytic Hydrogen Evolution

Abstract2D semiconductor nanomaterials have received significant attention as photocatalysts for solar‐to‐hydrogen conversion due to their robust light absorption capacity, large specific surface area, and superior electron transport characteristics. Nevertheless, it is challenging to develop 2D quaternary copper‐based sulfides (QCSs) with functional integration of conducive structural features for photocatalysis from multiple elements and intricate control conditions. Herein, ultrathin 2D alloyed Cu−Ga−Zn−S (CGZS) curved nanobelts (NBs) are fabricated by using a facile one‐pot colloidal method. Subsequently, the derived Cu31S16‐CGZS Janus heterostructures are designed by increasing Cu concentrations. The formation mechanism of 2D curved alloys and Janus heterostructures is systematically investigated. Without cocatalysts, curved alloyed CGZS NBs demonstrated superior photocatalytic activities of 1264.2 µmol g−1 h−1 compared to Janus heterostructured Cu31S16−CGZS (463.1 µmol g−1 h−1) under visible light (> 400 nm). Experimental and theoretical results unveiled that the improved photocatalytic activities of curved CGZS NBs can be attributed to enhanced charge–carrier separation efficiency resulting from high crystallinity and ultrathin 2D structure, abundant active sites from curved structure, high‐active (0001) crystal facet with the lowest reaction Gibbs energy, work function, and metal‐like properties. This work offers new insights into functional integration into ultrathin 2D QCSs with enhanced visible‐light photocatalytic performance.

Full-Space Electric Field in Mo-Decorated Zn2In2S5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production.

Integration of photocatalytic hydrogen (H2) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H2 fuel and high-value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated Zn2In2S5 (Mo-Zn2In2S5) photocatalyst. Specifically, this full-space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn-S] regions to [In-S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of Zn2In2S5. Notably, the optimized Mo1.5-Zn2In2S5 catalyst achieves exceptional H2 and benzaldehyde production rates of 34.35 and 45.31mmol gcat -1 h-1, respectively, outperforming pristine ZnIn2S4 by 3.83- and 4.15-fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.

Construction of carbon and nitride double vacancy defects on ultrathin porous g-C3N4 nanosheets assisted by freeze-drying for enhanced photocatalysis

Graphitic carbon nitride based photocatalysts have been found extensive application in the degradation of antibiotics and organic pollutants. However, the insufficient of surface active sites and the low efficiency of photogenerated charge carriers separation hinder the development. Herein, ultrathin porous polymer carbon nitride nanosheets (PCNS-F) with carbon and nitride double vacancy defects were successfully fabricated. The facile freeze-drying step, following solvent-thermal treatment and preceding the thermal etching process, stands as a critical step for triggering vacancy generation and adjusting the carbon/nitride ratio. The optimized PCNS-F photocatalyst exhibits an ultrathin structure featuring a substantial abundance of defects in a porous state, resulting in exceptional structural characteristics (183.3 m² g-1, 0.84 cm³ g-1). Surface defect sites increase, and the efficient separation and transfer of photo-generated charge carriers are promoted with the introduction of a suitable vacancy density. PCNS-F demonstrated outstanding photocatalytic degradation performances for tetracycline (81.7 %) and methylene blue (97.7 %) under visible light irradiation for 2 h, which are 10 and 7.2 times higher than those of bulk g-C3N4. The active species of ∙O2- was confirmed to play a major role in the photodegradation process. This work provides a mild approach for engineering carbon and nitride double vacancy defects on g-C3N4 nanosheets, accompanied by tuning carbon/nitride ratio, to effectively eliminate pollutants and cleanse the environment.’

Regulation of Charge Transfer Pathway in Ag-ZnIn2S4 Nanowires for Visible Photodynamic Therapy on Candida Albicans Infections.

Photodynamic therapy (PDT) is receiving extensive attention as an antimicrobial strategy that does not cause drug resistance by reactive oxygen species (ROS). Herein, hierarchical Ag-ZnIn2S4 (Ag-ZIS) core-shell nanowires are synthesized by in situ Metal-Organic Framework derived method for efficient PDT of Candida albicans (C. albicans). The core-shell structure enables spatial synergy strategy to regulate the charge transfer pathway under visible light excitation, in which the Ag nanowires are like the highway for the photogenerated electrons. The enhanced charge carrier separation efficiency greatly increased the chances for the generation of ROS. As expected, the optimized Ag-ZIS nanowires exhibit excellent performance for inactivation of C. albicans under visible light irradiation (λ ≥ 420 nm, 15 min), and the effective sterilization concentration is as high as 107CFU mL-1. Moreover, in vivo infection experiments suggested that the PDT effect of Ag-ZIS nanowires on the mouse wound healing is better than that of the clinical Ketoconazole drug. The PDT antifungal mechanism of Ag-ZIS nanowires is also investigated, and superoxide anion is found to be the predominant active species to causes C. albicans damage. This work provides a new perspective for designing novel interface structures to regulate charge transfer to achieve efficient PDT antifungal therapy.

Photocatalytic application towards the degradation of ciprofloxacin and algae by Z-scheme 2D/3D heterojunction of Bi12O17Cl2/UiO-66-NH2

With the continuous emergence of antibiotics in natural water bodies, the crisis of water environment is becoming increasingly serious. To efficiently remove antibiotics, a novel 2D/3D Z-scheme heterojunction of Bi12O17Cl2/UiO-66-NH2 was constructed by in situ growth technology. The formation of Z-scheme heterojunction between Bi12O17Cl2 and UiO-66-NH2 not only significantly improves the transfer rate and separation efficiency of charge carriers, but also greatly prolongs the lifetime of electrons and improves their light absorption ability. Free radical capture experiments and ESR spectra display that ⋅O2− and ⋅OH radicals dominate the degradation process of ciprofloxacin. The synthesized Z-scheme heterojunction shows a high degradation rate of 83.5 % for antibiotic ciprofloxacin within 60 min, much higher than those of Bi12O17Cl2, UiO-66-NH2 monomers and many other reported photocatalysts. The heterojunction Bi12O17Cl2/UiO-66-NH2 also exhibits excellent degrading performance towards antibiotics in three actual water bodies (tap water, lake water and the effluent of domestic sewage treatment plant). Meanwhile, the as-prepared photocatalyst can effectively degrade Microcystis aeruginosa and algal toxin Microcystin-LR in surface water bodies contaminated by algae and antibiotics. The QSAR analysis indicates that the toxicities of both ciprofloxacin and its intermediates are greatly reduced. The degradation pathways of ciprofloxacin were analyzed via Density Functional Theory calculations and QSAR analysis. This study provides an excellent synthesis method of Z-scheme heterojunction for the purification of surface water bodies contaminated by algae and antibiotics via photocatalytic technology.

Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration

AbstractPhotocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD‐COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 μmol g−1 h−1 in O2 and air) than TBC‐COF with hcb topology through the O2‐O2⋅−‐H2O2, O2‐O2⋅−‐O21‐H2O2, and H2O‐H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2⋅− generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O21, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high‐performance photocatalysts for H2O2 production by topological structure modulation.

Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration.

Photocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD-COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 μmol g-1 h-1 in O2 and air) than TBC-COF with hcb topology through the O2-O2⋅--H2O2, O2-O2⋅--O2 1-H2O2, and H2O-H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2⋅- generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O2 1, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high-performance photocatalysts for H2O2 production by topological structure modulation.

Unraveling Interfacial Photoinduced Charge Transfer and Localization in CsPbBr3 Nanocrystals/Naphthalenediimide.

Halide perovskites have attracted much attention for energy conversion. However, efficient charge carrier generation, separation, and mobility remain the most important issues limiting the higher efficiency of solar cells. An efficient interfacial charge transfer process associated with exciton dynamics between all-inorganic CsPbBr3 nanocrystals and organic electron acceptors has been suggested. We observed a strong PL quenching of 78% in thin films when silane-functionalized naphthalenediimides (SNDI), used as electron-acceptors, are anchored on CsPbBr3 nanocrystals. Optical and structural characterizations confirm the charge transfer process without QDs degradation. The issue of whether these transferred charges are indeed available for utilization in solar cells remains uncertain. Our results reveal that the CsPbBr3 nanocrystals capped with these electron-acceptor SNDI molecules show a drastic increase in the electrical resistance and the absence of a photoconductivity effect. The results suggest charge transfer followed by strong localization of the charge carriers, preventing their extraction toward the electrodes of solar cell devices. We hope that this crucial aspect to attract attention and unveil a potential mechanism for charge delocalization, which could, in turn, lead to a groundbreaking enhancement in solar cell efficiency.

Ag nanocubes-decorated ammonium hydroxide-treated carbon nitride to improve photocatalytic H2O2 production and fuel cell performance

A novel photocatalyst is designed by surface modification and cocatalyst loading of graphitic carbon nitride (g-C3N4) with ammonium hydroxide and silver nanocubes (AgNCs), respectively. The synergistic effect of the modification in the intralayer of g-C3N4 and surface plasmon resonance (SPR) bands of AgNCs significantly enhances the migration and separation efficiency of photo-induced charge carriers. A nickel mesh coated with photocatalyst and the carbon paper loaded with pristine g–C3N4–mixed iron phthalocyanine (FeIIPc) used as the photoanode and cathode, respectively, are constructed for the self-powered photoelectrochemical cell, which exhibits the maximum power density of 0.74 mW cm−2. The AHCN/AgNCs-based cell reveals approximately a 3.1-times enhancement in maximum power density compared with the pristine g–C3N4–based cell. In addition, the photocatalytically generated H2O2 (chemical energy) can be stored in water, and then used as fuel by the connection of two electrodes in the dark. After the fuel cell is operated for 12 h, the specific capacitance retention rate still maintains as high as 57.2 %, which is the greatest retention rate in comparison with the previously reported H2O2 fuel cell systems. Our work offers a feasible opinion on how to improve the visible light utilization of semiconductors by tuning the intralayer properties and loading plasmonic metal.

Photo-induced in-situ synthesis of Cu2O@C nanocomposite for efficient photocatalytic evolution of hydrogen

Cuprous oxide (Cu2O) is an ideal visible light catalyst owing to its narrow band gap, environmental benignity and abundant storage; however, the fast recombination of photogenerated charge carriers and poor stability of Cu2O has impeded its application in photocatalysis. Herein, we demonstrate that Cu2O@C nanocomposite can spontaneously evolve from a methanol aqueous solution containing cupric ions under the induction of irradiation. Compared with the traditional carbon coating method, the Cu2O@C nanocomposite obtained by the photo-induced in-situ synthesis can reserve superior original characteristics of the semiconductor under mild reaction conditions, promote the charge transfer and enhance the separation efficiency of charge carriers; in addition, the carbon shells can also effectively prevent Cu2O from photo-corrosion. As a result, the Cu2O@C nanocomposite exhibits excellent photocatalytic activity in the hydrogen evolution in comparison with the Cu2O particles; the H2 evolution rate over the Cu2O@C nanocomposite reaches 1.28 mmol/(g·h) under visible light, compared with the value of 0.065 mmol/(g·h) over Cu2O. Moreover, the Cu2O@C nanocomposite displays good cycle stability, viz., without any deactivation in the catalytic activity after five cycles.

Selective activation of dioxygen to singlet oxygen over La-Si co-doped TiO2 microspheres for photocatalytic degradation of formaldehyde

Volatile Organic Compounds (VOCs) are highly harmful to human beings and other organisms, and thus the elimination of VOCs is extremely urgent. Here, La-Si co-doped TiO2 microsphere photocatalysts, which were prepared by a hydrothermal method, exhibited high photocatalytic activity in the decomposition of formaldehyde compared with TiO2. The improved activity can be attributed to the promoted separation efficiency and density of the charge carriers, as verified by the electrochemical results in combination with density functional theory calculations. In addition, the Si dopant changed the microstructure and surface acidity, while the addition of La promoted the separation efficiency of charge carriers. More interestingly, it was found that singlet oxygen was the key species in the activation of molecular dioxygen, and it played a pivotal role in the photocatalytic decomposition of formaldehyde. This work provides a novel strategy for the selective activation of dioxygen for use in the decomposition of formaldehyde.

A facile route for decoration of hematite photoanodes by transition metal hydroxide co‐catalysts

AbstractEarth‐abundant α‐Fe2O3 (hematite) is a convincing photoanode for photoelectrochemical (PEC) water splitting; however, its intrinsic properties of inferior charge transfer and sluggish water oxidation kinetics limit its performance. Here, we report a straightforward decoration method for transition metal hydroxides to accelerate the oxygen evolution reaction (OER) of hematite photoanodes grown by electric field‐assisted liquid phase deposition (EA‐LPD). The investigations revealed that Co(OH)2 acts as a superior co‐catalyst compared with hydroxides of Mn, Fe, Co, Ni, and Zn. EA‐LPD‐grown hematite photoanode loaded with cobalt hydroxide exhibited an excellent PEC performance. A photocurrent density of 0.93 mA.cm−2 at 1.23 V versus reversible hydrogen electrode was achieved for the modified hematite, ∼3 times more than that of pristine hematite, and a cathodic shift of 100 mV for the onset potential was observed. The proposed simple and cost‐effective co‐catalyst loading strategy provides a high degree of freedom in the design of co‐catalysts with a complex chemical composition comprising transition metal oxyhydroxides and hydroxides on different photoanodes for more efficient charge carrier separation for the PEC applications.

Enhanced oxygen evolution of a new copper-based metal-organic framework through the construction of a heterogeneous structure with bismuth oxyiodide

Herein, a newly developed MOF, Cu-based on 2-amino terephthalic acid (CuATPA) is successfully prepared and utilized as a photoanode material. To achieve high-efficiency electron/hole separation and rapid catalytic kinetics, a heterojunction architecture is designed by combining CuATPA with BiOI. Scanning electron microscopy images reveal the formation of CuATPA nanoplates within the structures of BiOI nanoflakes. Electrochemical characterization demonstrates the excellent photoelectrocatalytic performance of the CuATPA-BiOI nanocomposite. Linear sweep voltammetry reveals a reduced overpotential value for the CuATPA-BiOI nanocomposite, indicating enhanced catalytic activity. Moreover, the CuATPA-BiOI photoanode displays a photo-voltage of 0.43 V compared to 0.23 and 0.24 V for the CuATPA and BiOI photoanodes, respectively, indicating a deeper band bending. The improved photoelectrochemical performance of the nanocomposite is attributed to efficient separation and transfer of photo-generated charge carriers, as evidenced by higher charge density extracted from the Mott-Schottky plot and smaller semicircle radius in the Nyquist plot.

Accelerating Surface Reaction Kinetics and Enhancing Bulk as well as Surface Charge Carrier Dynamics in Al/ Al2O3‐Coated BiVO4 Photoanode

AbstractPhotoelectrochemical (PEC) hydrogen evolution from water splitting of semiconductor photoanodes is intricately linked to their light‐absorbing capacity, surface reaction kinetics, bulk charge carrier separation efficiency, and surface charge carrier injection efficiency. Harnessing the surface plasmon resonance effect of metals emerges as a promising approach to enhance PEC performance of semiconductor photoanodes. This work presents the first application of non‐noble metal Al nanoparticles to sensitize a BiVO4 nanoporous film (NPF) photoanode. This process significantly expedites the surface kinetics of water oxidation, and improves both bulk charge carrier separation and surface carrier injection efficiencies of BiVO4 NPF photoanode. Additionally, the surface‐formed Al2O3 film effectively preserves the stability of photoanode, leading to a substantial improvement in PEC hydrogen evolution of BiVO4 NPF photoanode in a three‐electrode PEC cell with sulfite scavenger. The constructed BiVO4/Al NPF heterojunction photoanode exhibits a hydrogen evolution rate of 73.9 µmol cm⁻2 h⁻¹ at 1.23 V versus reversible hydrogen electrode, 1.68 times of BiVO4 photoanode. Additionally, BiVO4/Al NPF photoanode exhibits excellent stability under long‐time light irradiation of 8 h. This study provides valuable insights into the design of nonnoble‐metal‐based plasmonic photoanodes for efficient hydrogen generation through PEC cell from the perspectives of surface reaction kinetics, charge carrier injection, and separation.

Preparation of BiOBrxCl1‐x solid solution photocatalyst with oxygen vacancies for degradation of methyl orange under simulated sunlight

AbstractBiOBrxCl1‐x solid solution with oxygen vacancies was synthesized using a simple one‐step hydrothermal method. The sample was characterized using comprehensive characterization techniques, and the results showed that the solid solution material was successfully prepared. Adjusting the relative proportion of halogens in BiOBrxCl1‐x solid solution has a significant impact on the morphology, optical properties, and photocatalytic activity of the sample, and oxygen vacancies are introduced into the material. The presence of oxygen vacancies improves the separation efficiency of charge carriers and facilitates the activation of oxygen molecules into superoxide radicals. Among them, BiOBr0.2Cl0.8 showed flower‐like microspheres morphology and exhibited the best photocatalytic activity. After 30 min of dark adsorption and 1 h of simulated sunlight exposure, the removal rate of methyl orange (MO) was 92.5%, which was 2.38 times higher than that of pure BiOBr (38.9%) and 2.09 times higher than that of pure BiOCl (44.3%), respectively.