Separation Efficiency Of Charge Carriers Research Articles

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

Abstract 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, 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.

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.

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.

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.

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.

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.

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 formed 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, precise control 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

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 formed 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, precise control 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.

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.