Separation Efficiency Of Charge Carriers Research Articles

Exploring Geometric Chirality in Nanocrystals for Boosting Solar-to-Hydrogen Conversion.

Advancing catalyst design is pivotal for the enhancement of photocatalytic processes in renewable energy conversion. The incorporation of structural chirality into conventional inorganic solar hydrogen nanocatalysts promises a significant transformation in catalysis, a feature absent in this field. Here we unveil the unexplored potential of geometric chirality by creating a chiral composite that integrates geometric chiral Au nanoparticles (NPs) with two-dimensional C3N4 nanosheets, significantly boosting photocatalytic H2 evolution beyond the achiral counterparts. The superior performance is driven by the geometric chirality of Au NPs, which facilitates efficient charge carrier separation through the favorable C3N4-chiral Au NP interface and chiral induced spin polarization, and exploits high-activity facets within the concave surfaces of chiral Au NPs. The resulting synergistic effect leads to a remarkable increase in photocatalytic H2 evolution, with an apparent quantum yield of 44.64% at 400 nm. Furthermore, we explore the selective polarized photo-induced carrier separation behavior, revealing a distinct chiral-dependent photocatalytic HER performance. Our work advances the design and utilization of chiral inorganic nanostructures for superior performance in energy conversion processes.

Self-coupling of electron acceptor units in conjugated microporous polymers strengthening local donor-acceptor interaction for improving photocatalytic activity

The partial self-coupling of donor or acceptor unit during donor-acceptor (D-A) type CMPs synthesis is often overlooked for the effect on photocatalytic activity. Herein, we developed three D-A type CMPs, named SATE-CMP-n (n=1–3), which were constructed from triazine (TEPT) unit (A) and three salen units (D). With the rigidity of salen units increasing (the rigidity: salen-1 <salen-2 <salen-3), the self-coupling proportion of TEPT decreases. The experiments and DFT calculations reveal that salen-1 has the stronger electron-donating ability compared to salen-2 and salen-3, and that the self-coupling of TEPT units also enhances the electron-accepting ability. Therefore, SATE-CMP-1 exhibits the strongest D-A interaction and the highest separation and transfer efficiency of charge carriers, and has been used a photocatalyst for S−S and S−N coupling reactions. This work proves that the self-coupling of monomers in the construction of CMPs is not overlooked for adjusting the photocatalytic activity of catalyst.

Rationally modulating thiophene‐ and porphyrin‐based donor‐acceptor type covalent organic framework for effective photocatalytic organic reactions

In order to specifically demonstrate the improvement of photocatalytic activity attributed to the donor‐acceptor (D‐A) structure rather than other contributing factors, two highly comparable COFs incorporating porphyrin and thiophene species are synthesized in this work. The first COF, named BTDA‐Por, is composed of porphyrin (Por) as the donor unit and 2,2′‐bithiophene (BTDA) as the acceptor moiety. The second COF, referred to as TT‐Por, is constructed using Por and thieno[3,2‐b]thiophene (TT) units while lacking a D‐A structure. These synthesized COFs serve as effective models for investigating the role of D‐A structures in improving photocatalytic activity. Photoelectronic property studies and density function theory calculations indicate that the D‐A configuration can significantly enhance the efficiency of charge carrier generation, separation, and migration. Consequently, the D‐A type BTDA‐Por exhibits superior performance in photochemical reactions such as oxidative homocoupling of aromatic amine and reversible complexation‐mediated radical polymerization when compared to the non‐D‐A type TT‐Por.

In situ Ion Pumping Anodization to Confine Single‐Atom Fe onto TiO2 Nanotubes for Enhanced Noble‐Metal‐Free Photocatalytic Hydrogen Generation

AbstractAchieving a high dispersity of deposited transition metal is crucial in the anodization preparation of noble‐metal‐free composites for photocatalytic hydrogen generation. Herein, for the first time, an in situ ion pumping anodization method is proposed to confine single‐atom Fe within the spatially ordered structure of anodized TiO2 nanotubes (TNT), assisted by ferric sodium salt of ethylenediaminetetraacetic acid (EDTA) as an “ion pump” to deliver Fe3+ toward anodes. Both experimental and theoretical calculations confirm that highly dispersed single‐atom Fe can interact with single‐electron‐trapped oxygen vacancies (SETOV), effectively reducing the oxygen vacancy concentration in TiO2 nanotubes. This reduction promotes efficient charge carrier separation through the Fe(III)/Fe(II) pathway and enhances hydrogen desorption, ultimately boosting the photocatalytic hydrogen evolution performance.

MoO3 with the Synergistic Effect of Sulfur Doping and Oxygen Vacancies: The Influence of S Doping on the Structure, Morphology, and Optoelectronic Properties.

Molybdenum trioxide (MoO3) is an attractive semiconductor. Thus, bandgap engineering toward photoelectronic applications is appealing yet not well studied. Here, we report the incorporation of sulfur atoms into MoO3, using sulfur powder as a source of sulfur, via a self-developed hydrothermal synthesis approach. The formation of Mo-S bonds in the MoO3 material with the synergistic effect of sulfur doping and oxygen vacancies (designated as S-MoO3-x) is confirmed using Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The bandgap is tuned from 2.68 eV to 2.57 eV upon sulfur doping, as confirmed by UV-VIS DRS spectra. Some MoS2 phase is identified with sulfur doping by referring to the photoluminescence (PL) spectra and electrochemical impedance spectroscopy (EIS), allowing significantly improved charge carrier separation and electron transfer efficiency. Therefore, the as-prepared S-MoO3-x delivers a sensitive photocurrent response and splendid cycling stability. This study on the synergistic effect of sulfur doping and oxygen vacancies provides key insights into the impact of doping strategies on MoO3 performance, paving new pathways for its optimization and development in relevant fields.

Staggered band alignment of n-Er2O3/p-Si heterostructure for the fabrication of a high-performance broadband photodetector

The low responsivity of conventional Silicon photodiodes in ultraviolet and near-infrared regimes restricts their utility as broadband photodetectors (BBPDs). Despite ongoing investigations into various p-n heterostructures for Silicon-based BBPDs, challenges such as high dark current (Idark), low collection efficiency, low detectivity, and compatibility issues with large-scale Silicon-based devices persist. In this context, we have fabricated relatively unexplored n-Er2O3/p-Si heterojunction-based BBPDs. Polycrystalline Er2O3 thin films (∼110 nm) were deposited on p-Si 〈100〉 substrates by radio frequency magnetron sputtering. Although this process induces a microstrain of approximately 0.022 and a dislocation density of about 0.00303/nm2, the presence of optically active defects is minimal, indicated by a low Urbach energy (∼0.35 eV). X-ray photoelectron spectroscopy (XPS) analysis confirms staggered band alignment at the heterointerface, facilitating efficient charge carrier separation and transport. Consequently, the In/p-Si/n-Er2O3/In device demonstrated significant BBPD properties– low Idark ∼0.15 μA (at +5 V), photo-to-dark current ratio (PDCR) ∼6.5 (at +5 V, 700 nm) with a maximum photoresponsivity ∼22.3 A W−1, and impressive detectivity (∼1013 Jones) even in UV-C region where traditional silicon-based photodetectors respond feebly. The device also demonstrates transient photo-response across an ultrawide spectrum (254 nm–1200 nm) with a fast rise time/fall time ∼79 ms/∼86 ms (at −5 V for 600 nm illumination). This work establishes a straightforward and reliable method for proper material engineering, surface texturing, staggered heterojunction formation, and high-performance BBPD fabrication with prominent broad-spectrum responsivity, sizeable detectivity, and fast response. The integration of these BBPDs with Silicon opens possibilities for their use in electronic devices containing optical switches for communications and broadband image sensors, enhancing their utility in various applications.

Fabrication of ternary Bi2S3/BiVO4/g-C3N4 composite material for enhanced photocatalytic degradation of antibiotics

Antibiotic contaminants are known to pose a serious threat to the human health and environment, thus a great deal of effort has been made to develop destruction technologies for antibiotic treatment in the water environment. Photocatalytic oxidation technology is regarded as one of the most promising strategies for decomposing antibiotics from water. In this work, ternary Bi2S3/BiVO4/g-C3N4 composite material is dexterously designed and synthesized to obtain the enhanced photocatalytic performance for tetracycline (TC) degradation via a facile strategy. Therein, the optimal Bi2S3/BiVO4/g-C3N4 material showed the excellent degradation efficiency under visible light irradiation in comparison to the nude g-C3N4 and BiVO4/g-C3N4 photocatalysts, and it can continuously degrade the TC pollutant in 90 min and achieve a degradation percentage of 80.7 %. The designed materials can not only intensify photo-absorption efficiency of g-C3N4 material, but also improve its separation and transfer efficiency of photo-generated charge carriers, which is attributed to the incorporation of BiVO4 and Bi2S3 materials. The active species trapping experiments verified that the superoxide radicals (•O2−) is the main active species, and holes (h+) also played an important role in the Bi2S3/BiVO4/g-C3N4 system. Furthermore, the photoelectrochemical measurement (PEC) clearly demonstrated that the incorporation of BiVO4 and Bi2S3 materials could accelerate the separation and transfer of photo-generated electron and hole pairs. As expected, our present work could spark new inspirations to further develop the efficient photocatalysts for solar energy conversion.

Surface-Grafted Single-Atomic Pt-Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor-Inducing Interfacial Electron Transfer.

Based on the electron-withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post-modification amide reaction was firstly used to graft it onto the surface of NH2-MIL-125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post-modification with additional bipyridine to investigate the effect of Pt-Nx coordination numbers on reaction activity. The as-synthesized NML-PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g-1 h-1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2-MIL-125 and NML-PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h-1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF-Molecule catalysts with efficient charge carrier separation and precise regulation of single-atom coordination sphere.

Surface‐Grafted Single‐Atomic Pt−Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor‐Inducing Interfacial Electron Transfer

AbstractBased on the electron‐withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post‐modification amide reaction was firstly used to graft it onto the surface of NH2‐MIL‐125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post‐modification with additional bipyridine to investigate the effect of Pt−Nx coordination numbers on reaction activity. The as‐synthesized NML‐PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g−1 h−1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2‐MIL‐125 and NML‐PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h−1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF‐Molecule catalysts with efficient charge carrier separation and precise regulation of single‐atom coordination sphere.

Cadmium doping induced type-II to Z-scheme switching in CdSe/BiVO4 heterojunction for enhancing photocatalytic hydrogen production

Heterojunction type in composite photocatalysts determines their charge carrier transfer path, which is critical to the redox capacity of their charge carriers and needs careful modulation for their designed photocatalytic reactions. In this work, a transit from the type-II (BVO/CdSe) to Z-scheme (CdSe/BVO) in CdSe/BiVO4 heterojunction happened by changing the deposition sequence of CdSe and BiVO4 layers to introduce Cd-doping into the BiVO4 layer, which fundamentally changed their charge carrier separation and transfer behaviors as demonstrated by both experimental and calculation results. So, the charge carrier separation efficiency in CdSe got largely enhanced, more photogenerated electrons with high reduction potential were allowed to participate in the photocatalytic H2 production, and photogenerated hole accumulation in CdSe reduced. As a result, the CdSe/BVO photoelectrode demonstrated the best photocatalytic hydrogen production rate (2.59 μmol cm−2 h−1), which is about 136.3 and 5.9 times higher than that of BVO/CdSe and pure CdSe, and the stability under visible light irradiation is also greatly improved.

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 (&gt; 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.

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.

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.

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.