光照下红磷材料稳定性的提高方法

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Developing efficient catalysts to enhance photoreduction carbon dioxide (CO2) into hydrocarbon fuels is a great challenge. As metallic material, molybdenum dioxide (MoO2) has very high conductivity and charge density, which make it a promising candidate as photocatalyst. However, its photocatalytic activity is limited by the serious charge recombination. How to effectively make full use of the metallic MoO2 for photocatalytic CO2 reduction is still a critical issue. The potential effective way to solve this problem is to introduce appropriate auxiliary catalysts to construct electron-rich interfaces. In this study, red phosphorus (P) is dispersed on MoO2 nanoparticles to construct electron-rich interfaces which can serve as the active site for photocatalytic CO2 reduction. The results show that the reduction of CO2 by pure MoO2 only produces carbon monoxide (CO) and methane (CH4). However, with the aid of red P, the P-MoO2 photocatalyst can produce ethylene (C2H4) with the yield of 5.43 μmol h-1 g-1, and the CO and CH4 yields are also significantly improved. Experimental results and density functional theory (DFT) calculations indicate that photogenerated carriers can migrate from MoO2 to the interface, and the reduction of CO2 occurs at the interface. This study provides a significant insight for the design of efficient photocatalysts by using metallic photocatalysts.

The development of efficient photocatalyst materials is crucial for solar hydrogen production through photocatalytic water splitting. Recently, earth‐abundant elemental red phosphorus (RP) materials with broader light absorption ability and appropriate band structure characteristics have been considered as promising metal‐free photocatalysts. Herein, this review seeks to provide a comprehensive overview of the progress achieved so far in the utilization of RP‐based photocatalysts for solar driven hydrogen production applications. It starts off with a summary of the discovery, crystal and electronic structures of various RP allotropes, including amorphous, type Ⅱ, Hittorf's and fibrous phosphorus materials. Subsequently, the synthesis strategies of RP and RP‐based materials utilized in photocatalysis were discussed. Furthermore, the elemental RP, and the modification of RP with cocatalyst and other semiconductors were examined to ascertain its potential in efficient photocatalytic hydrogen production. Finally, an overview and outlook on the challenges and future avenues in designing and constructing advanced visible‐light‐driven RP‐based photocatalysts were also proposed.

Photocatalytic hydrogen evolution (PHE) from water splitting is a promising technology for clean and renewable energy production. Elemental crystalline red phosphorus (CRP) is purposefully designed and developed for PHE reaction. However, the photocatalytic activity of CRP is limited by its intrinsic P vacancy (VP) defects, which lead to detrimental charge trapping at deep states and hence its severe recombination. To address this issue, a boron (B) incorporated CRP (B‐CRP) photocatalyst is tailored, synthesized via a simple and mild boric acid‐assisted hydrothermal strategy. The incorporation of B effectively fills the VP defects, reducing deep trap states (DTS) and introducing beneficial shallow trap states (STS) within the band structure of CRP. This defect engineering approach leads to enhanced photocatalytic activity, with B‐CRP achieving a PHE rate of 1392 µmol g−1 h−1, significantly outperforming most reported elemental photocatalysts in the literature. Density functional theory (DFT) simulations and ultrafast spectroscopy support the constructive role of B‐dopant‐induced STS in prolonging active charge carrier lifetimes, promoting more efficient photocatalytic reactions. The findings not only demonstrate the effectiveness of B‐CRP as a photocatalyst but also highlight the usefulness of dopant‐induced STS in advancing PHE technologies.

The clinical application of photodynamic therapy (PDT) faces limitations due to the poor tumor‐targeting efficiency and systemic toxicity of conventional photosensitizers. To overcome these challenges, a biomimetic nanoplatform (C3N4‐RP@RBCm) is developed by covalently coupling graphitic carbon nitride (C3N4) with red phosphorus nanoparticles, followed by encapsulation with erythrocyte membranes. This design utilizes CD47‐mediated immune evasion and achieves tumor‐specific accumulation through enhanced permeability and retention (EPR) effects. C3N4‐RP@RBCm demonstrates outstanding antitumor activity. Specifically, a 24‐h exposure to 20 µg mL−1 of C3N4‐RP@RBCm is sufficient to saturate HeLa cells. Upon 660 nm laser irradiation, controlled reactive oxygen species (ROS) are generated, resulting in apoptosis in 89% of HeLa cells, thereby efficiently enhancing anti‐tumor effects. In tumor‐bearing mice, laser‐activated C3N4‐RP@RBCm induces apoptosis in tumor cells and more effectively inhibits tumor xenografts. Moreover, at a concentration of 100 µg mL−1, the percentage of live cells remains above 99%, and the treatment induces less than 1.2% hemolysis in human erythrocytes, indicating excellent biocompatibility. Consequently, C3N4‐RP@RBCm causes minimal histopathological injuries in heart, liver, spleen, lung, and kidney tissues. Thus, this photosensitizer demonstrates significant potential for clinical application.

Crystalline red phosphorus(CRP), known for its promising photocatalytic properties, faces challenges in photocatalytic hydrogen evolution(PHE) due to undesired inherent charge deep trapping and recombination effects induced by defects. This study overcomes these limitations through an innovative strategy in integrating ruthenium single atoms(Ru1) within CRP to simultaneously repair the intrinsic undesired vacancy defects and serve as the uniformly distributed anchoring sites for a controllable growth into ruthenium nanoparticles(RuNP). Hence, a highly functionalized CRP with Ru1 and RuNP(Ru1-NP/CRP) with concerted effects in regulating electronic structures and promoting interfacial charge transfer has been achieved. Advanced characterizations unveil the pioneering dual role of pre-anchored Ru1 in transforming CRP photocatalysis. The regulations of vacancy defects on the surface of CRP minimize the detrimental deep charge trapping, resulting in the prolonged lifetime of charges. With the well-distributed in-situ growth of RuNP on Ru1 sites, the constructed robust "bridge" that connects CRP and RuNP facilitates constructive interfacial charge transfer. Ultimately, the synergistic effect induced by the pre-anchored Ru1 endows Ru1-NP/CRP with an exceptional PHE rate of 3175μmolh-1g-1, positioning it as one of the most efficient elemental-based photocatalysts. This breakthrough underscores the crucial role of pre-anchoring metal single atoms at defect sites of catalysts in enhancing hydrogen production.

Abstract Co3O4/red phosphorus (Co3O4/RP) photocatalysts were synthesized via facile hydrothermal and mechanically grinding approach. The catalysts were characterized via XRD, TEM, XPS, N2 sorption, photoelectro chemical measurements and UV–vis DRS. The results showed that the Co3O4 nanocrystals were assembled on the surface of the RP. The loading of Co3O4 on RP was beneficial to enhance the light absorption compared with pure RP. Under visible light, 94.5% of malachite green (MG) can be photodegraded within 20 min over 10% Co3O4/RP composite, while only 17.3% and 59.9% of MG can be photodegraded over pure Co3O4 and RP. The reaction rate constant k obtained over 10% Co3O4/RP heterojunction (0.1464 min−1) is approximately 3.2 times that of pure RP (0.0457 min−1), and 15.3 times that of bare Co3O4 (0.0096 min−1). The cycle experiments showed that the catalyst had high photocatalytic stability. Co3O4 nanocrystals inhibit the photoelectron-hole pair recombination of red phosphorus semiconductor, and exhibit improved visible light absorption. Consequently, the catalytic performance of Co3O4/RP has been enhanced under visible light.

Visible-light-sensitive crystalline red phosphorus (P) nanorod composited with SrTiO3 (STO) particles have been successfully assembled via a solid-state reaction routine, wherein STO nanoparticles were immobilized on the surface of P nanorods. The obtained crystalline P/STO heterostructured composites with an intimate interfacial contact facilitate efficient charge separation and transfer of photogenerated electron–hole pairs, and the P nanorods with a large exposed surface exhibit strong Vis-light absorption. Therefore, by adjusting different molar ratio and calcination temperature, the P2.0/STO-700 °C composites presented the best photocatalytic activities of RhB degradation and hydrogen evolution (169.95 µmolh−1 g−1) and possessed high stability during three cycling experiments. The reaction rate constant (kapp) of the optimum P2.0/STO-700 °C composites is about 215 times and 11.3 times as high as that of pristine STO and P, respectively. In this paper, the crystalline, morphologies and optical properties of the as-prepared photocatalysts were sufficiently studied via various characterization techniques. Meanwhile, a reasonable charge transfer mechanism on P/STO composites was brought up and a trapping experiment was analysized in detail. This research provides some perspectives for the future development of P-based photocatalytic materials.

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The practical applications of fibrous red phosphorus (FRP), an emerging quasi-one-dimensional material, might be hindered by its environmental instability. Although other phosphorus allotropes such as white phosphorus, violet phosphorus, and black phosphorus are reported unstable under ambient conditions, the chemical stability of FRP remains unexplored. Herein, we investigate the degradation chemistry of FRP by combining experimental study and density functional theory calculations. The results reveal that both oxygen and water can react with FRP, while light illumination may accelerate these reactions. Furthermore, the degradation behavior of FRP shows a pseudo-first-order reaction in oxygenated water, while it follows a pseudo-zero-order reaction in deoxygenated water. Such different reaction kinetics originates from the preferable dissociative adsorption behaviors of O2 molecular and H2O molecular on a FRP surface or at a FRP edge. A covalent modification approach using an aryl diazonium salt was adopted to passivate the surface of FRP flakes and significantly enhance their stability in air.

Abstract Novel heterojunction compounds between Fe-based metal organic framework (MIL-101(Fe)) and non-metallic red phosphorus (RP) were firstly and successfully fabricated by a facile low-temperature solvothermal process. The experimental results show that RP (15 wt%)/MIL-101(Fe) composite exhibits excellent photocatalytic efficiency for tetracycline (TC) degradation (90.1% in 80 min) with the following reaction conditions: initial pH at 5, TC concentrations of 50 mg/L, catalyst dosage of 0.50 g/L and full spectrum irradiation. Besides, the as-prepared RP (15 wt%)/MIL-101(Fe) shows a good stability after multiple usage cycles. High specific surface areas, improvement of light absorption intensity and suppression of charge recombination should be responsible for the high photocatalytic performance. Moreover, a possible photocatalytic mechanism was proposed based on the trapping experiments and electron spin resonance analysis. As expected, the as-prepared RP/MIL-101(Fe) composite could be used as an excellent photocatalyst for the removal of many hazard pollutants in the wastewater.

Abstract Highly available and active photocatalysts and cocatalysts play key roles in the of efficient and stable visible-light-driven photocatalytic systems. In this work, a nickel phosphide (Ni2P)/red phosphorus (RP) heterojunction composite was fabricated for the first time by an in situ hydrothermal method using nanosized RP and nickel chloride as the starting materials. The results indicated that the heterojunction exhibits a two-dimensional (2D) nanostructure with a good contact interface and stability. The surface edges of pure RP are the active sites during the photocatalytic reaction. The introduction of Ni2P could improve the light-harvetsing ability of RP and facilitate charge separation, leading to an enhanced photocurrent intensity and excellent photocatalytic performance for H2 evolution. The H2 production rate of the 3% Ni2P/RP sample was 2183 μmol·g−1·h−1 under visible light irradiation, which was higher than that of Pt/RP, indicating that Ni2P could be used as an efficient noble-metal-free cocatalyst. In addition, a possible mechanism for H2 production was proposed for Ni2P/RP composite. Further work should be conducted in the exploration of P-based transition metal cocatalysts and RP-based photocatalysts.

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Abstract Elemental red phosphorus (RP) has an ultra-low activity of splitting water for H2 and O2 evolution. In this study, RP was decorated by trace amount of WO3 to greatly enhance the photocarriers separation and photocatalytic activity for overall water splitting under visible light. The 2.5% WO3/RP composite achieved the highest activity to produce H2 and O2, and the activity was 7.0 times that of pure RP under visible light (λ ≥ 420 nm). The significantly increased photocarriers separation of WO3/RP was ensured by transient photocurrent, electrochemical impendence, photoluminescence, and time-resolved photoluminescence characterizations. More importantly, WO3/RP maintained high stability when it was persistently used for 20 cycles. Based on the reactive oxygen species (•O2- and •OH) detected during the photocatalytic process, an S-scheme mechanism was proposed for WO3/RP composite to efficiently separate the photocarriers. This work provides a notion for improving the overall water splitting activity of RP via an S-scheme photocarriers separation mode.

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Coupling solar-powered CO2 conversion with pollutant removal via Z-scheme heterojunctions offers a promising strategy to simultaneously address energy and environmental challenges. However, achieving efficient charge separation and optimizing active sites for both reduction and oxidation reactions are still significant challenges. Herein, a Z-scheme heterojunction photocatalyst with spatially separated dual active sites (hydroxyl-functionalized red phosphorus (HRP) and amino-functionalized graphitic carbon nitride (ACN)) was developed to enable the concurrent photoreduction of CO2 and photooxidation of tetracycline (TC). The optimized heterojunction, incorporating 1.25 wt% HRP, achieved a 4.96-fold increase in CO yield and 1.09-fold improvement in TC degradation compared with a red phosphorus/graphitic carbon nitride (RP/CN) system without surface functionalization. Density functional theory calculations and experimental analyses confirmed a Z-scheme charge transfer mechanism wherein hydroxyl groups facilitated hole-mediated TC oxidation and amino groups promoted electron-driven CO2 reduction. The 1.25HRP/ACN photocatalyst demonstrated an electron transfer efficiency of 87.8 %, significantly surpassing the 64.9 % observed for 1.25RP/CN, highlighting the synergistic benefits of dual-site engineering. This study provides detailed insights into dual-functionalized Z-scheme heterojunctions with spatially separated redox-active sites, advancing the design of integrated systems for solar fuel generation and environmental remediation.

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Abstract The photocatalytic production of H2 by low-cost semiconductors is a promising approach to store solar energy. Photocatalysts with heterojunctions convert visible light into H2 faster because of more efficient charge separation. The morphology, the structure, and the crystallinity are additional factors to consider when developing a photocatalyst. Here, highly-crystalline CdS nanorod (NR) were synthesized by a facile one-pot process. Under visible light, pure CdS NR produced H2 2.1 times faster than conventional CdS nanoparticles (NP). CdS NR were then combined with the semiconductor red phosphorus (RPh). A CdS NR-based heterojunction photocatalyst with RPh5% had an excellent photocatalytic H2 evolution rate of 11.72 mmol g−1 h−1, which was 3.6 times higher than pure CdS NR. The apparent quantum efficiency of RPh5%/CdS NR was 19.57%. Furthermore, RPh5%/CdS NR exhibited a superior photogenerated charge separation efficiency and was stable with little photocorrosion compared to CdS NP showing the high potential of this heterojunction photocatalyst.

Photocatalysis is a green technique that can convert solar energy to chemical energy, especially in H2 production from water splitting. In this study, ZnO and red phosphorus (ZnO/RP) heterostructures were fabricated through a facile calcination method for the first time, which showed the considerable photocatalytic activity of H2 evolution. The photocatalytic activities of heterostructures with different ratios of RP have been investigated in detail. Compared to bare ZnO, ZnO/RP heterostructures exhibit a 20.8-fold enhancement for H2 production and furthermore overcome the photocorrosion issue of ZnO. The improved photocatalytic activities highly depend on the synergistic effect of the high migration efficiency of photo-induced electron–hole pairs with the inhibited charge carrier recombination on the surface. The presented strategy can also be applied to other semiconductors for various optoelectronics applications.

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The rapid progress of elemental phosphorus families raises a pressing question: which of the allotropes is the most environmentally stable? Clear experimental evidence remains lacking. To this end, the stability discrepancies and underlying degradation chemistry of black phosphorus (BP), violet phosphorus (VP), and fibrous red phosphorus (FP), -the three most extensively studied among phosphorus families are systematically investigated, by monitoring the spectroscopic and microscopic evolution combined with first-principles calculations. The ambient degradation behavior of three elemental phosphorus flakes follows pseudo-first-order reaction kinetics. The corresponding monoexponential fitting yields rate constants kBP, kVP, and kFP of 0.11, 0.18, and 0.23 day-1, respectively, quantitatively revealing that the environmental stability decreases in the order BP > VP > FP. Such stability discrepancy can also be qualitatively explained by the dissociative chemisorption energy of oxygen atoms based on first-principles calculations. This work sheds new light on stability discrepancies and underlying degradation chemistry, paving the way for effective stabilization techniques.

Abstract Red phosphorus (P) anodes possesses the highest theoretical capacities for both potassium-ion and sodium-ion batteries (PIBs/SIBs). An optimal strategy to play out its electrochemical performance is to confine nanoscale red P within a porous carbon structure. Nevertheless, the practical application of these P/carbon nanocomposites is challenged by their high air-sensitivity and poor cyclability associated with inevitable P deposition onto the external surface of carbon matrices, especially with high P content in the P/carbon composite. Herein, a dual-protection red P material was designed and fabricated by simple surface coating of a polypyrrole (PPy) layer onto a red P-activated carbon (P@AC) composite. The conducting PPy coating plays a multifunctional role including, promoting the structural stability by isolating the direct contact of active material from the electrolyte, improving electrical conductivity, and enhancing the air oxidation resistance by the PPy barrier layer. The PPy-coated P@AC with a relatively high P content of ~52 wt% demonstrates excellent air stability while exhibiting high reversible capacities (~800 mAh g−1 at 0.05 A g−1 for SIBs; ~400 mAh g−1 at 0.02 A g−1 for PIBs) and long cycle life. This study sheds light on the rational design of advanced P-based anodes for alkali metal-ion batteries.

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Abstract Here, we report a nano-sized red phosphorous/biomass-derived porous carbon (P@BDPC) which is employed as anode materials for lithium ion batteries (LIBs) via a facile vaporization−condensation−conversion strategy (VCC) with tobacco stem as the carbon precursor. The biomass-derived porous carbon not only acts as the host of red phosphorus to enhance the electrical conductivity, but also minimizes the volume expansion (≈400%) during cycling. The obtained P@BDPC composite with a high red phosphorus content (62.1 wt%) delivers a high specific capacity of 1689 mA h g−1 at 500 mA g−1 with an initial Coulombic efficiency (ICE) of 91.7% and superior rate capability of 599 mA h g−1 at 30 A g−1. Furthermore, a high reversible capacity of 918 mA h g−1 can be retained over 600 cycles at 5 A g−1, indicating a remarkable cycle stability. More importantly, the introduction of agriculture waste-tobacco stem contributes to building low-cost, high-performance anode materials.

Red phosphorus (RP) is a promising anode material for use in lithium-ion batteries (LIBs) due to its high theoretical specific capacity (2596 mA h g-1). However, the practical use of RP-based anodes has been challenged by the material's low intrinsic electrical conductivity and poor structural stability during lithiation. Here, we describe a phosphorus-doped porous carbon (P-PC) and disclose how the dopant improves the Li storage performance of RP that was incorporated into the P-PC (designated as RP@P-PC). P-doping porous carbon was achieved using an in situ method wherein the heteroatom was added as the porous carbon was being formed. The phosphorus dopant effectively improves the interfacial properties of the carbon matrix as subsequent RP infusion results in high loadings, small particle sizes, and uniform distribution. In half-cells, an RP@P-PC composite was found to exhibit outstanding performance in terms of the ability to store and utilize Li. The device delivered a high specific capacitance and rate capability (1848 and 1111 mA h g-1 at 0.1 and 10.0 A g-1, respectively) as well as excellent cycling stability (1022 mA h g-1 after 800 cycles at 2.0 A g-1). Exceptional performance metrics were also measured when the RP@P-PC was used as an anode material in full cells that contained lithium iron phosphate as the cathode material. The methodology described can be extended to the preparation of other P-doped carbon materials that are employed in contemporary energy storage applications.

Phosphorus is considered an ideal anode material for lithium ion storage by virtue of its high theoretical capacity and moderate lithiation potential. However, issues such as large volume expansion of phosphorus leading to an electrical loss of contact and instability of the solid electrolyte interface hinder its practical performance. Improvement strategies that can effectively suppress volume expansion and provide stable electrical contacts are urgently needed. Herein, by introduction of a carbon nanotube cross-linked microstructure into the polyimide coating layer, a high-modulus coating layer is effectively constructed to suppress volume expansion and provide a stable and fast conductive network. The prepared dual-cross-linked phosphorus-carbon composites exhibit excellent cycling stability and high-rate performance. After cycling 500 cycles at a current density of 1 A g-1, it can still provide a specific capacity of 1467.68 mAh g-1, with a capacity retention rate of 87.28%. And even at a high current of 10 A g-1, it can still provide a high specific capacity of 1450.72 mAh g-1.

Phosphorus‐doped carbons provide a balance between the electrochemical stability of graphitic lattices and the high energy density of phosphorus materials when used in lithium and sodium‐ion batteries. Herein, a comprehensive ex situ 31P, 7Li, and 23Na solid‐state nuclear magnetic resonance analysis of the intercalation mechanism of novel, stable, dual‐phase phosphorus‐doped, and phosphorus‐encapsulated turbostratic graphite microspheres is presented. Results indicate that lithium intercalation occurs through the formation of Li3P from white phosphorus trapped within the graphitic layers, with the involvement of lithiated phosphorus atoms within the graphitic lattice. A dual‐lithiated carbon doped‐phosphorus environment is tentatively proposed at low voltages. Sodiation occurs through a similar mechanism; however, no evidence of a dual‐sodiated doped‐phosphorus environment is observed. Upon removal of ions, carbon‐encapsulated phosphorus with a local structure similar to red phosphorus forms, which subsequently allows effective reversible ion storage.

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Red phosphorus (RP) has attracted great attention as a potential candidate for anode materials of high-energy density sodium-ion batteries (NIBs) due to its high theoretical capacity, appropriate working voltage, and natural abundance. However, the low electrical conductance and huge volumetric variation during the sodiation-desodiation process, causing poor rate performance and cyclability, have limited the practical application of RP in NIBs. Herein, we report a rational strategy to resolve these issues by encapsulating nanoscaled RP into conductive and networked carbon nanocages (denoted as RP@CNCs) using a combination of a phosphorus-amine based method and evacuation-filling process. The large interior cavities volume of CNCs and controllable solution-based method enable the ultrahigh RP loading amount (85.3 wt %) in the RP@CNC composite. Benefiting from the synergic effects of the interior cavities and conductive network, which afford high structure stability and rapid electron transport, the RP@CNC composite presents a high systematic capacity of 1363 mA h g-1 at a current density of 100 mA g-1 after 150 cycles, favorable high-rate capability, and splendid long-cycling performance with capacity retention over 80% after 1300 cycles at 5000 mA g-1. This prototypical design promises an efficient solution to maximize RP loading as well as to boost the electrochemical performance of RP-based anodes.

Abstract In this study, we reported a novel type-I heterojunction between red phosphorus and graphitic carbon nitride under vacuum condition, which is a novel synthesis process. For preparing the red phosphorus composites, the vacuum condition is appropriate to prevent it from self-ignition. The prepared materials were analyzed with different analytic techniques for the confirmation of their heterojunctions and structure formation. The introduction of red phosphorus into graphitic carbon nitride, reduce the structural defects and increase the charge separation ability. After medication, the synthesized composite shows an enhanced photocatalytic activity against acute toxicity category-III non-color (MTSM, Metsulfuron methyl) and color (RhB), organic pollutants. The photocatalytic degradation mechanism (Mott-Schottky and VB-XPS) study reveal that red phosphorus /graphitic carbon nitride possess type-I heterojunction with enhanced catalytic behavior, due to the effective transformation of photo-generated electrons from CB of GCN to CB of RP with the help of heterojunctions and due to unmoved photo holes on VBs. Synthesized composites also maintained their performance after reused them in three cyclic form.

The hydrothermally treated red phosphorus (HRP) was dispersed on the intercalated bentonite (EB) supporter to prepare the EB/HRP photocatalyst for improved photocatalytic performance. The as-synthesized samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscope, scanning electron microscope, and Brunauer-Emmett-Teller analysis. Rhodamine B was selected as the model pollutant to evaluate the photodegradation property of EB/HRP. Results showed that the photodegradation efficiency of the EB/HRP photocatalyst composite increased with increased EB mass fraction, and decreased after reaching the highest value. When the mass fraction of EB was 9%, the EB9/HRP photocatalyst composite exhibited the strongest adsorption performance and photodegradation activity. Its degradation rate constant k was 0.0641 min, which was two times that of HRP. In addition, after five cycles of photodegradation experiments, EB9/HRP still had high photocatalytic activity (96.8%). Therefore, the EB9/HRP catalyst composite had good photocatalytic activity and stability, which can be an efficient and stable photocatalyst for the degradation of pollutants.

The construction of wide bandgap semiconductors with heterojunctions is an effective strategy to improve the photocatalytic activity of narrow-bandgap semiconductors, such as red phosphorus (RP). The novel step-scheme (S-scheme) heterojunction can separate photocarriers effectively while retaining the high reduction-oxidation capacity of the catalyst. Herein, a SnO2/hydrothermally treated RP (SnO2/HRP) S-scheme heterojunction was constructed and was found to display superior performance in the photocatalytic degradation of pollutants and the disinfection of bacteria. The 5%SnO2/HRP (mass ration of SnO2 with 5 wt%) composite had the strongest photocatalytic activity. It could degrade 97.5% of Rhodamine B (RhB) after 12 min of light exposure. The photodegradation rate constant of this composite reached 2.96 × 10-1 min-1, which was 4.4 and 59.2 times higher than that of pure HRP and SnO2, respectively. Furthermore, this S-scheme heterojunction composite exhibited a higher efficient photocatalytic antibacterial rate (99.4%) for Escherichia coli (E. coli) under visible-light irradiation, than pure HRP (66.4%) and SnO2 (72.9%). Further mechanistic investigations illustrated that the intimate contact between HRP and SnO2 in the S-scheme system heterojunction could effectively boost carrier transfer and improve the photocatalytic activity of the semiconductor. This investigation provided an efficient recyclable S-scheme heterojunction composite for the photocatalytic degradation of pollutants and bacteria.

The semiconductor photocatalyst is crucial for dealing with the current environmental and energy crises. However, the large-scale applications of the reported semiconductor materials are hampered by the recombination of electrons and holes, low kinetic properties, and slow reaction rates. Herein, a three-dimensional structured kaolin/hydrothermally treated red phosphorus (K/HRP) composite photocatalyst was synthesized. The composition ratio was optimized, and the K7/HRP composites (contained 7%) exhibited the highest photocatalytic activity. The rhodamine B photodegradation rate constant and the hydrogen production rate were 0.25 min-1 and 252 μmol h-1 g-1, which were higher than those of HRP by 12.4 and 7.2 times, respectively. The enhancement of the HRP photocatalytic activity was attributed to the presence of K, which inhibited the overgrowth and the agglomeration of HRP and shortened the carrier migration distance. The electrostatic interaction between the K and the HRP effectively promoted the separation of photogenerated charge carriers. In addition, the three-dimensional structure of the K and the HRP construct enhanced the light absorption and provided a pollution-free and large-area transport interface for carriers. This work has paramount guiding importance in the preparation of high-efficiency, cheap, and recyclable nanocomposite photocatalyst materials.

Abstract Ultrathin red phosphorus nanosheets (N-RP) have been first attempt synthesized through thermal decomposition reaction. N-RP exhibits a higher surface area compared to that of hydrothermal treatment red phosphorus (HT-RP). The crystal violet (CV) dye solution photodegradation ratio of N-RP is 94.5% in 40 min, higher than that with HT-RP only 38.0% under visible light irradiation.

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Herein, zeolitic imidazole framework (ZIF)-8/red phosphorus photocatalysts were prepared via a solvothermal method for simultaneous organic dye degradation and hydrogen (H2) generation. The 5 wt% ZIF-8/RP photocatalyst achieved the highest H2 generation rate of 822.5 μmol h-1 g-1 and 92% rhodamine dye degradation under natural sunlight irradiation. This approach offers an effective strategy to replace costly and toxic traditional electron donors with organic dye pollutants for H2 generation.

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Developing active photocatalysts using wide-spectrum light is crucial to promote the application of photocatalytic water splitting. Elemental red phosphorus (RP) has attracted much attention as a p...

Red phosphorus as a novel visible-light-responsive and metal-free photocatalyst has attracted extensive attention in the area of energy conversion and environmental remediation. Herein, nano-sized red phosphorus photocatalyst was synthesized via a hydrothermal and ultrasonic method and used for reduction of Cr (VI) for the first time. The as-prepared photocatalysts were characterized by XRD, UV-Vis-DRS, XPS, SEM, TEM and photoelectrochemical measurements. Compared to bulk red phosphorus, nano-sized red phosphorus exhibit a significantly enhanced photocatalytic activity for reduction of Cr (VI) due to the greatly reduced charge transfer resistance and enhanced adsorption capability of Cr (VI).

Abstract A novel 2D MoS2/RP heterojunction photocatalyst with intimate interfacial contact was successfully fabricated for the first time. The photocatalytic activity of this nanocomposite was evaluated by the removal of the Cr(VI)-RhB coexistence system under visible light irradiation, to 72.7% for Cr(VI) and 97.5% for RhB simultaneously in 80 min. Photoelectrochemical analyses revealed that the MoS2/RP composite show an outstanding charge separation ability compared to the pristine RP, resulting in the enhanced photocatalytic activity. In particular, it can be considered as an efficient and meaningful nanocomposite building method, moreover, provides guidance to further design of photocatalyst toward various applications.

Elemental P is considered a compelling option for constructing a simple, cost‐effective, and full‐spectrum responsive catalytic system for hydrogen production, while its full potential for overall water‐splitting reactions remains underexplored. This study introduces a novel cobalt single‐atom‐assisted photocatalytic system for efficient hydrogen production via water splitting. Utilizing an in situ surface phase transformation, amorphous red phosphorus (a‐RP) is converted into crystalline black phosphorus (c‐BP), forming a Z‐scheme heterojunction with cobalt single atoms (Co1) uniformly dispersed across the heterojunction surface. Advanced characterization techniques confirm the intimate contact and strong electronic interactions between Co1, c‐BP, and a‐RP, significantly enhancing photocatalytic performance. This system achieves a high hydrogen production rate of ≈2497 µmol g−1 h−1 from pure water splitting under visible light irradiation and a remarkable solar‐to‐hydrogen (STH) efficiency of 0.86%, outperforming most reported photocatalytic systems. This study highlights the potential of single‐atom catalysts in enhancing the performance of photocatalysts. It provides a new perspective on designing efficient and stable elemental‐based photocatalytic systems for sustainable hydrogen production.

Antibiotic contamination, especially from persistent compounds like tetracycline (TC), has emerged as a serious environmental concern due to its resistance to conventional treatment processes. In this study, crystalline red phosphorus nanoribbons (cRP NRs) were integrated with iron-based metal–organic frameworks (MOF) (MIL-101 and MIL-101-B) via a solvothermal method to construct composite photocatalysts for enhanced TC degradation. The optimized cRP NRs/MIL-101 composite (mass ratio 1:1) exhibited the highest photocatalytic efficiency, achieving 80% TC removal under visible-light irradiation—significantly outperforming both pristine cRP and MIL-101. Structural and optical characterizations confirmed the formation of a Z-scheme heterojunction between cRP NRs and MIL-101, which effectively promoted charge separation, broadened light absorption, and enhanced the generation of reactive oxygen species. Radical scavenging experiments and band structure analysis revealed that ·O2− and h+ played dominant roles in the degradation pathway. The composite also demonstrated good stability and recyclability over multiple cycles. This work provides a rational strategy for designing MOF-based heterostructured photocatalysts for efficient antibiotic removal from wastewater.

Photocatalytic water disinfection has emerged as a promising approach for water purification. However, exploring efficient and rapid visible light driven materials for photocatalytic bacterial inactivation is still a challenging problem. Herein, red phosphorus/titanium oxide (TiO2@RP) nanofibers were developed for effective water disinfection by a vacuum ampoule strategy. The complete E. coli and S. aureus (7-log CFU mL-1) could be rapidly killed within 25 min and 30 min over the optimized TiO2@RP heterostructure under the white LED irradiation. The efficient photocatalytic antibacterial activity should be mainly ascribed to the synergetic enhancement in light absorption by RP decoration and charge migration and separation by the interface between TiO2 and RP. And then more unpaired photo-carriers would be transferred to the surface to facilitate the generation of photo-holes, •O2- radicals, and H2O2 species, which could destroy the bacterial cells efficiently.

Abstract Pathogens pose a serious challenge to environmental sanitation and a threat to public health. The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs, which further threatens public health. To address this issue, the use of non-chemical antibacterial means has become a new trend for environmental disinfection. In this study, we developed red phosphorus nanoparticles (RPNPs), a safe and degradable photosensitive material with good photocatalytic and photothermal properties. The red phosphorus nanoparticles were prepared using a template method and ultrasonication. Under the irradiation of simulated sunlight for 20 min, the RPNPs exhibited an efficiency of 99.98 % in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities. Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks. Both the RPNPs and their degradation products were nontoxic to fibroblast cells. Therefore, such RPNPs are expected to be used as a new type of low-cost, efficient, degradable, biocompatible, and eco-friendly photosensitive material for environmental disinfection.

No abstract available

Red phosphorus (RP) is an emerging visible‐light‐responsive photocatalyst, yet the rapid charge recombination has limited photocatalytic hydrogen production activity. In this work, a Z‐scheme heterostructure with RP nanolayer coated on high‐index (116) faceted anatase TiO2 nanoparticles (TiO2@RP) is designed and fabricated via chemical vapor deposition. Compared with pristine TiO2 and RP, the optimized TiO2@RP Z‐scheme heterostructure exhibits a significantly boosted photocatalytic activity for pure water splitting, with hydrogen evolution rate reaching 12.9 µmol·h−1, under simulated solar light irradiation. The strong interfacial interaction and staggered band alignment between (116) faceted TiO2 and RP result in the formation of built‐in electric field, which can drive the directional charge migration from the conduction band (CB) of TiO2 to the valance band (VB) of RP under light irradiation, with photoelectrons and holes of high redox ability maintained at the CB of RP and the VB of TiO2, respectively. This well‐designed heterostructure greatly promotes photogenerated charge separation and migration via a direct Z‐scheme charge transfer pathway.

Solar-driven photocatalytic hydrogen production utilizing S-scheme heterojunctions holds great potential due to their capacity for spatial carrier separation and maintaining a high redox potential. In this work, an S-scheme heterojunction consisting of oxygen vacancy (VO)-enriched BiVO4@Type II red phosphorus (BiVO4@RP) was synthesized by a facile ball-milling approach, resulting in Type II RP nanosheets enwrapping the surface of decahedral BiVO4. The introduction of VO in BiVO4 induces defect electronic states that serve as effective trapping sites for photogenerated electrons at the heterojunction interface. Consequently, the synergistic effect of VO in BiVO4 and intimate interfacial contact between BiVO4 and RP facilitate the migration of photo-electrons through an S-scheme transfer route, thereby enhancing the hydrogen production activity from pure water splitting. Remarkably, the optimized BiVO4@RP composite achieves a hydrogen evolution rate of 518.5 µmol·h-1·g-1 under simulated solar light irradiation. This study may provide valuable insights into the design of defect-modulated S-scheme heterojunction photocatalysts for efficient artificial photosynthesis.