Interstitial decoration of Ag linking 3D Cu2O octahedron and 2D CaWO4 for augmented visible light active photocatalytic degradation of rifampicin and genotoxicity studies.

A morphological oriented highly active Cu2O-Ag-CaWO4 (CAC) nano-heterojunction was fabricated for the visible light driven degradation of rifampicin (RFP). Octahedron shaped Cu2O being a base material, where the Tagetes shaped CaWO4 and Ag were embedded on it. The shape-controlled morphology of Cu2O and CaWO4 as well as Ag decoration influence high degree of adsorption of RFP and interfacial charge transfer between the nano-heterojunction. Further, the larger specific surface area (129.531 m2/g) and narrow band gap energy (2.57 eV) of CAC nano-heterojunction than the controls support the statement. Positively, CAC nano-heterojunction following Z-scheme-type charge transport mechanism attained 96% of RFP degradation within 100 min. O2•- and •OH are the primarily involved reactive oxidation species (ROS) during the photocatalytic reactions, determined by scavenger study and ESR analysis. The stability and reusability of the CAC nano-heterojunction was assessed through performing cyclic experiment of RFP degradation and it holds 96.8% of degradation even after 6th cycle. The stability of CAC nano-heterojunction after photodegradation was further confirmed based on crystalline pattern (XRD analysis) and compositional states (XPS analysis). Intermediates formed during RFP degradation and its toxicity was discovered by using GC-MS/MS and ECOSAR analysis respectively. The end-product toxicity against bacterial system and genotoxicity of CAC nano-heterojunction against Allium cepa were evaluated and the results were seemed to have no negative causes for the aquatic lives.

Controllable Synthesis, Photocatalytic Property, and Mechanism of a Novel POM-Based Direct Z-Scheme Nano-Heterojunction α-Fe2O3/P2Mo18.

In order to improve photocatalytic activity and maximize solar energy use, a new composite material Fe2O3/P2Mo18 was prepared by combining polyoxometalates (P2Mo18) with Fe2O3 nanosheets. FT-IR, XRD, XPS, SEM, TEM, UV-vis, EIS, and PL were used to characterize the composite material, and nano-Fe2O3 of different sizes and morphologies with a controllable absorption range was prepared by adjusting the reaction time, and, when combined with P2Mo18, a composite photocatalyst with efficient visible light response and photocatalytic activity was constructed. The EIS, Bode, and PL spectra analysis results show that the Fe2O3/P2Mo18 composite material has outstanding interfacial charge transfer efficiency and potential photocatalytic application possibilities. Model reactions of methylene blue (MB) and Cr (VI) photodegradation were used to evaluate the redox activity of Fe2O3/P2Mo18 composites under simulated visible light. The photocatalytic degradation rate was as high as 98.98% for MB and 96.86% for Cr (VI) when the composite ratio was Fe2O3/P2Mo18-5%. This research opens up a new avenue for the development of high-performance photocatalysts.

Regulating the interface defect of TiO2/Ag2O nanoheterojunction and its effect on photogenerated carrier dynamics.

In this paper, the defects of TiO2/Ag2O nanoheterojunctions are regulated to evaluate the effect of the interface defects on carrier trapping and recombination dynamics by time-resolved photoluminescence spectroscopy (TRPL) and time-resolved terahertz (THZ) spectroscopy. TRPL spectra reveal that interface defects can act as a recombination center and have an accelerative effect on the recombination process of photogenerated carriers under ultraviolet light. Moreover, THZ spectroscopy results demonstrate that interface defects can effectively trap electrons and expedite the Auger recombination. Furthermore, the influence of interface defects on the photocarrier dynamics of TiO2/Ag2O nanoheterojunctions was comprehensively analyzed, providing a valuable experimental reference for the regulation and application of interface defect-fabricated nanoheterojunctions.

Au-SnO2-CdS ternary nanoheterojunction composite for enhanced visible light-induced photodegradation of imidacloprid.

Herein, we have developed a novel synthetic strategy for the fabrication of Au-SnO2-CdS ternary nano-heterojunction catalyst and its utility towards LED light derived photocatalytic degradation of imidacloprid has been evaluated. The synthesized ternary nanocomposite was characterized using sophisticated analytical techniques to evaluate the catalyst's morphological, structural and surface chemical properties. The photocatalytic activity of the ternary catalyst towards the degradation of imidacloprid was evaluated under LED irradiation. Approximately 95% of the degradation efficiency was achieved with a pseudo-first-order reaction rate of 15.6 × 10-3 min-1. The degradation efficiency of Au-SnO2-CdS nano-catalyst was found to be ~1.2, 1.4 and 2.1 times to that of the pristine Au, CdS and SnO2 nanomaterials under similar experimental conditions. The effect of variation of parameters like contact time, initial pollutant concentration and pH on degradation efficiency has also been investigated. Moreover, the identification of various degradation products and reactive intermediates were made with high-performance liquid chromatography and electron spin resonance techniques.

Modification engineering of TiO2-based nanoheterojunction photocatalysts.

Titanium dioxide (TiO2)-based photocatalysts have gained increasing attention for their versatile applications in organic degradation, hydrogen production, air purification, and CO2 reduction. Various TiO2-based heterojunction structures, including type I, type II, Schottky junction, Z-scheme, and S-scheme, have been extensively studied. The current research frontier is centered on the engineering modifications of TiO2-based nanoheterojunction photocatalysts, such as defect engineering, morphological engineering, crystal phase/facet engineering, and multijunction engineering. These modifications enhance carrier transport, separation, and light absorption, thereby improving the photocatalytic performance. Remarkably, this aspect has been less addressed in existing reviews. This review aims to fill this gap by focusing on the engineering modifications of TiO2-based nanoheterojunction photocatalysts. We delve into specific topics like oxygen vacancies, n-p homojunctions, and double defects. The review also systematically discusses the applications of multidimensional heterojunctions and examines carrier transport pathways in heterophase/facet junctions and their interactions with heterojunctions. A comprehensive summary of multijunction systems, including multi-Schottky junctions, semiconductor-based heterojunction-attached Schottky junctions, and multisemiconductor-based heterojunctions, is presented. Lastly, we outline future perspectives in this promising research field. This paper will assist researchers in constructing more efficient TiO2-based nanoheterojunction photocatalysts.

Selenium-Doped Nanoheterojunctions for Highly Efficient Cancer Radiosensitization.

Exploring efficient and low-toxicity radiosensitizers to break through the bottleneck of radiation tolerance, immunosuppression and poor prognosis remains one of the critical developmental challenges in radiotherapy. Nanoheterojunctions, due to their unique physicochemical properties, have demonstrated excellent radiosensitization effects in radiation energy deposition and in lifting tumor radiotherapy inhibition. Herein, they doped selenium (Se) into prussian blue (PB) to construct a nano-heterojunction (Se@PB), which could promote the increase of Fe2+/Fe3+ ratio and conversion of Se to a high valence state with Se introduction. The Fe2+-Se-Fe3+ electron transfer chain accelerates the rate of electron transfer on the surface of the nanoparticles, which in turn endows it with efficient X-ray energy transfer and electron transport capability, and enhances radiotherapy physical sensitivity. Furthermore, Se@PB induces glutathione (GSH) depletion and Fe2+ accumulation through pro-Fenton reaction, thereby disturbs the redox balance in tumor cells and enhances biochemical sensitivity of radiotherapy. As an excellent radiosensitizer, Se@PB effectively enhances X-ray induced mitochondrial dysfunction and DNA damage, thereby promotes cell apoptosis and synergistic cervical cancer radiotherapy. This study elucidates the radiosensitization mechanism of Se-doped nanoheterojunction from the perspective of the electron transfer chain and biochemistry reaction, which provides an efficient and low-toxic strategy in radiotherapy.

Construction of p-n-p nano heterojunction through coupling La2O3, (BiO)2CO3 and Ag3PO4 for effective photocatalytic degradation of doxycycline: Insights into mechanism, pathway and intermediate toxicity evaluation.

The present work is centred around the development of La2O3/(BiO)2CO3/Ag3PO4 (LBA), a p-n-p nano-heterojunction to photodegrade doxycycline under visible light irradiation. Here, ultrasonication assisted co-precipitation method was employed to synthesize the photocatalyst. The photocatalyst was characterized using different analysis such as SEM, TEM, elemental mapping, XRD, XPS, FTIR, Raman, BET, DRS, PL and EIS which confirmed the successful fabrication of LBA and their excellent ability to refrain the e-/h+ recombination owing to the construction of the heterojunction. LBA was found to degrade DOX by 91.75 % with the high mineralization of 87.23%. The impact of the reaction parameters influencing the photodegradation process including the concentration of the NCs and DOX, pH and the influence of the commonly present anions were studied. The stability and reusability of the LBA was assessed through subjecting it to four cycles of photodegradation of DOX. In addition, the recovered LBA was characterized through XPS and XRD analysis to confirm the particles stability and reusability. The active participation of the photogenerated charges and the reactive oxygen species were identified through the scavenging assay and ESR analysis. Further, GC-MS/MS analysis was performed to put forward a plausible photodegradation pathway. The toxicity of the end products as well as the intermediates was predicted through ECOSAR software.

Self-sacrifice-template epitaxial growth of hierarchical MnO2@NiCo2O4 heterojunction electrode for high-performance asymmetric supercapacitor.

Constructing three-dimensional (3D) hierarchical bimetallic pseudocapacitive materials with abundant opening channel and heterojunction structures is rather promising but still challenging for high-performance supercapacitors. Herein, a self-sacrifice-template epitaxial growth strategy was proposed for the first time to construct 3D hierarchical bimetallic pseudocapacitive material. By using this strategy, NiCo2O4 nanowires (NiCo2O4NW) arrayed randomly to form a porous shell via in-situ epitaxial growth fully enclosing a MnO2 tube core, forming multiple transport channels and nano-heterojunctions between MnO2 and NiCo2O4NW, which facilitates electron transfer, i.e. exhibiting high electronic conductivity than any single component. As a result of the self-sacrifice-template epitaxial growth method, special hollow tectorum-like 3D hierarchical structure with considerable inter-nanowire space and hollow interior space enables easy access of electrolyte to NiCo2O4NW surface and MnO2 core, thereby resulting in highly exposed redox active sites of MnO2 core and NiCo2O4NW shell for energy storage. Comprehensive evaluations confirmed MnO2@NiCo2O4NW was a supercapacitor electrode candidate, delivering a superior energy density of 106.37 Wh kg-1. Such performance can be ascribed to the synergistic coupling effect of 3D hierarchical tube and nano-heterojunction structures. The proposed self-sacrifice-template epitaxial growth strategy provides important guidance for designing high-performance energy storage materials.

Facile fabrication of novel Fe3O4-SnO2-gC3N4 ternary nanocomposites and their photocatalytic properties towards the degradation of carbofuran.

Herein, Fe3O4-SnO2 nanoheterojunction has been synthesized and successfully encapsulated in gC3N4 matrix using a novel hydrothermal technique. The synthesized material was characterized using sophisticated analytical methods like XRD, TEM, BET, UV-Vis, VSM and XPS to evaluate structural, morphological, optical, magnetic and surface chemical properties. The hybrid nanostructure Fe3O4-SnO2-gC3N4 has been utilized for the LED light-induced photocatalytic degradation of carbofuran. The catalyst exhibited notable photocatalytic performance under visible light with an efficiency of ~89% and pseudo first order rate constant of 0.015 min-1. The result of change in variables like catalyst dose, pollutant concentration, pH and contact time on the photodegradation efficiency and degradation kinetics was studied. The incorporation of Fe3O4 improved the magnetic separation of the catalyst after several cycles of operation, thereby improving the practical utility of the catalyst system to tackle organic pollutants.

Molybdenum Oxide/Tungsten Oxide Nano-heterojunction with Improved Surface-Enhanced Raman Scattering Performance.

By virtue of their high uniformity and stability, metal oxide-based surface-enhanced Raman spectroscopy (SERS) substrates have attracted enormous attention for molecular trace detection. However, strategies for further enhancing the SERS sensitivity are still desired. Herein, MoOx/WOx nano-heterojunctions are constructed by mixing MoOx and WOx together (MoOx/WOx hybrid) with diverse weight ratios. Using a 532 nm laser as the excitation source and R6G as the Raman reporter, it is shown that the Raman signal intensity (for the peak @ 1360 cm-1) obtained on the optimal MoOx/WOx hybrid (MoOx/WOx = 1:1/3) is twice that observed on a pure MoOx or WOx substrate. Moreover, a limit of detection of 10-8 M and an enhancement factor of 108 are achieved. In the SERS enhancement mechanism investigation, it is revealed that MoOx and WOx form a staggered band structure. During the SERS measurement, electron-hole pairs are generated in the nano-heterojunction using the incident laser. They are then separated by the built-in potential with the electrons moving toward WOx. The accumulated electrons on WOx are further transferred to the R6G molecules through the coupling of orbitals. Consequently, the molecular polarizability is amplified, and SERS performance is enhanced. The abovementioned explanation is supported by the evidence that the contribution of the chemical enhancement mechanism in the optimal MoOx/WOx hybrid substrate is about 2.5 times or 5.9 times that in the pure WOx or MoOx substrate.

Three-Layer PdO/CuWO4/CuO System for Hydrogen Gas Sensing with Reduced Humidity Interference.

The growing hydrogen industry is stimulating an ongoing search for new materials not only for hydrogen production or storage but also for hydrogen sensing. These materials have to be sensitive to hydrogen, but additionally, their synthesis should be compatible with the microcircuit industry to enable seamless integration into various devices. In addition, the interference of air humidity remains an issue for hydrogen sensing materials. We approach these challenges using conventional reactive sputter deposition. Using three consequential processes, we synthesized multilayer structures. A basic two-layer system composed of a base layer of cupric oxide (CuO) overlayered with a nanostructured copper tungstate (CuWO4) exhibits higher sensitivity than individual materials. This is explained by the formation of microscopic heterojunctions. The addition of a third layer of palladium oxide (PdO) in forms of thin film and particles resulted in a reduction in humidity interference. As a result, a sensing three-layer system working at 150 °C with an equalized response in dry/humid air was developed.

Exfoliated Molybdenum Disulfide-Wrapped CdS Nanoparticles as a Nano-Heterojunction for Photo-Electrochemical Water Splitting.

We developed a heterojunction photocathode, MoS2@CdS, based on the wrapping of CdS nanoparticles by the MoS2 nanocrystals. The liquid-phase exfoliation method was adopted for preparing few-layer MoS2 nanocrystals of a layer thickness of ∼7.9 nm, whereas CdS nanoparticles of an average diameter of ∼17 nm were synthesized by the one-step hydrothermal process. The synthesized nanocrystals and nanoparticles were characterized by AFM, FESEM, HRTEM, STEM, XRD, GIXRD, UV-vis absorption, fluorescence emission, and Raman spectroscopy. The difference between two modes in the Raman spectrum of MoS2 indicates the formation of few-layer MoS2. The photoelectrochemical performance of the heterojunction photocathode was excellent. The MoS2@CdS heterostructure photocathode increased the photocurrent density (JPh) under 100 mW/cm2 illumination. We obtained the maximum applied biased photoconversion efficiency (ABPE) of ∼1.2% of the MoS2@CdS heterojunction photocathode in optimum device configuration. The production of H2 was measured as ∼72 µmol/h for the MoS2@CdS heterostructure with a cyclic stability of up to 7500 s.

A novel Au-SnO2-rGO ternary nanoheterojunction catalyst for UV-LED induced photocatalytic degradation of clothianidin: Identification of reactive intermediates, degradation pathway and in-depth mechanistic insight.

Herein, we have developed Au-SnO2-rGO ternary nanoheterojunction catalyst for photocatalytic degradation of clothianidin under UV-LED irradiation. Au nanoparticles (Au NPs) were decorated with quantum sized SnO2 nanoparticles (SnO2 NPs) and embedded in the reduced graphene oxide (rGO) matrix. The synthesized photocatalyst was characterized using common instrumentation techniques to evaluate the morphological, structural and surface chemical properties of the catalyst. The photocatalytic property of the as-synthesized nanocomposite was investigated by studying the degradation of clothianidin under UV-LED irradiation. Approximately 97% of the degradation was achieved in 120 min with pseudo first-order reaction rate of 0.0309 min-1. The effect of various parameters like contact time, catalyst dose, initial concentration, pH, irradiation source and interfering ions on the degradation performance has also been investigated. Identification of various intermediates in the degradation process was done with high performance liquid chromatography- mass spectral (LC/HRMS) technique. The reactive intermediates responsible for the degradation have also been identified with electron spin resonance (ESR) technique and complete mechanism of the degradation process has been proposed with the help of photo luminescence (PL) quenching studies.

Wide spectral degradation of Norfloxacin by Ag@BiPO4/BiOBr/BiFeO3 nano-assembly: Elucidating the photocatalytic mechanism under different light sources.

Metallic Ag deposited BiPO4/BiOBr/BiFeO3 ternary nano-hetero-structures were rationally designed and synthesized by a simple precipitation-wet impregnation-photo deposition method. The plasmonic junction possesses an excellent wide spectrum photo-response and makes best use of BiPO4 which is otherwise a poor photocatalyst. Ag@BiPO4/BiOBr/BiFeO3 showed superior photocatalytic activity for degradation of norfloxacin (NFN) under visible, ultra-violet, near-infra-red and natural solar light. Especially catalyst APBF-3 (0.3 wt% Ag@BiPO4/BiOBr/BiFeO3) shows 98.1% degradation of NFN (20 mg/L) in 90 min under visible light and 99.1% in less than 45 min under UV exposure. Free radical scavenging experiments and electron spin resonance (ESR) results has been used for explanation of charge transfer, photocatalytic mechanism and role of radicals for binary, ternary and Ag deposited ternary junctions for UV and visible exposure. Metallic Ag in addition to its surface plasmon resonance helps in protection of high conduction band and valence band in the three semiconductors. A dual Z-scheme mechanism has been predicted by comparing with possibilities of double charge and vectorial charge transfer.

A Co2 P/WC Nano-Heterojunction Covered with N-Doped Carbon as Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction.

The hydrogen evolution reaction (HER) produces clean hydrogen through an electrochemical process. However, new nonprecious-metal electrocatalysts for the HER are required to reduce the consumption of energy. Herein, we report a new Co2 P/WC nano-heterojunction that consists of Co2 P and WC composite phases coated with a few-layer N-doped graphitic carbon shells (Co2 P/WC@NC). The composite was prepared by a one-step annealing of the polyoxometalate Na9 (NH4 )5 [{(B-α-PW9 O34 )Co3 (OH)(H2 O)2 (Ale)}2 Co]⋅35 H2 O (Co7 P6 W18 ) and dicyandiamide (DCA). The preparation method consisted of the simultaneous phosphorization of Co and carbonization of W in a confined space to isolate a Co2 P/WC nano-heterojunction phase for the first time. Co2 P/WC@NC facilitated the generation of hydrogen in the electrolysis process, which had an overpotential of only 91 mV at a current density of 10 mA cm-2 in the acid solution; an excellent HER performance (2 H+ +2 e- →H2 ) and Tafel slope (40 mV dec-1 ) as well as durability over a period of 50 h were achieved. Theoretical calculations showed that the Co2 P, WC, and Npyridinic C dopants in the material synergistically promoted the HER activity rather than the individual constituents. Furthermore, Co2 P/WC@NC nano-heterojunctions showed good HER performance in the whole pH range of electrolytes and considerable durability in acidic media containing transition metal ions, which may attract more attention for the exploration and optimization of nano-heterojunction catalysts for the HER.

The decisive effect of interface states on the photocatalytic activity of the silver(I) oxide/titanium dioxide heterojunction.

A one-step hydrothermal method was adopted to synthesize the Ag2O/TiO2 nanoheterojunction. Its photocatalytic activity was evaluated by degrading methylene blue (MB) aqueous solution under UV and visible light. The MB degradation results showed that the Ag2O/TiO2 nanoheterojunction enhances the photocatalytic activity under UV irradiation rather than visible light. X-ray photoelectron spectroscopy (XPS) was performed to detect the electronic structure at the interface of Ag2O and TiO2. The XPS results confirmed that the electronic band structure of the nanoheterojunction was determined by the interface states between the Ag2O and TiO2 interface. Thus, the photocatalytic enhancement mechanism can be ascribed to the creation of an additional potential barrier in the conduction band between Ag2O and TiO2, which facilitates the transport of holes from TiO2 to Ag2O but inhibits the flow of electrons in the reverse direction unless sufficient potential energy is provided to overcome the additional barrier. Our results have provided a new insight on the role of interface states between the p-n nanojunction in the photocatalytic activity.

Porphyrin-Based Nanostructures for Photocatalytic Applications.

Well-defined organic nanostructures with controllable size and morphology are increasingly exploited in optoelectronic devices. As promising building blocks, porphyrins have demonstrated great potentials in visible-light photocatalytic applications, because of their electrical, optical and catalytic properties. From this perspective, we have summarized the recent significant advances on the design and photocatalytic applications of porphyrin-based nanostructures. The rational strategies, such as texture or crystal modification and interfacial heterostructuring, are described. The applications of the porphyrin-based nanostructures in photocatalytic pollutant degradation and hydrogen evolution are presented. Finally, the ongoing challenges and opportunities for the future development of porphyrin nanostructures in high-quality nanodevices are also proposed.

Facile Synthesis of n-type (AgIn)(x)Zn(2(1-x))S2/p-type Ag2S Nanocomposite for Visible Light Photocatalytic Reduction To Detoxify Hexavalent Chromium.

n-type (AgIn)(x)Zn(2(1-x))S2/p-type Ag2S nanocomposites with 10%, 20%, and 30% Ag2S loading were successfully synthesized via the simple solvothermal and sol gel methods. The as-prepared nanocomposites were characterized, and their visible light photocatalytic reductions were tested for detoxification of hexavalent chromium (Cr(VI)). The results showed only 20 mg of the as-prepared nanocomposites could reduce 100 mL of 20 ppm potassium dichromate by almost 100% in less than 90 min without adding any hole scavenger agents and pH adjustment (pH = 7). The good photocatalytic reduction was related to the narrower bandgap of (AgIn)(x)Zn(2(1-x))S2 solid solution because of the hybridized orbitals of Ag, In, Zn, and S and low recombination rate of photogenerated electron and hole pairs due to the effectiveness of p-type Ag2S and n-type (AgIn)(x)Zn(2(1-x))S2 nanoheterojunctions. This work not only gives a contribution to the creation of visible light photocatalysis for wide-bandgap semiconductors, but also extends our technological viewpoints in designing highly efficient metal sulfide photocatalyst. To the best of our knowledge, this work is the first finding of a high photocatalytic reduction of hexavalent chromium under visible light illumination by simultaneously using both concepts of p-n nanoheterojunction and solid solution in our photocatalyst design. In this present work, these concepts were used to replace the use of hole scavenger agents, which were commonly used by many other works to retard the recombination rate of photoinduced electron and hole pairs for photodegradation of hexavalent chromium.