Unveiling the photocatalytic marvels: Recent advances in solar heterojunctions for environmental remediation and energy harvesting.

In the quest for effective solutions to address Environ. Pollut. and meet the escalating energy demands, heterojunction photocatalysts have emerged as a captivating and versatile technology. These photocatalysts have garnered significant interest due to their wide-ranging applications, including wastewater treatment, air purification, CO2 capture, and hydrogen generation via water splitting. This technique harnesses the power of semiconductors, which are activated under light illumination, providing the necessary energy for catalytic reactions. With visible light constituting a substantial portion (46%) of the solar spectrum, the development of visible-light-driven semiconductors has become imperative. Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light. In this comprehensive review, we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media, as well as the remarkable progress made in renewable energy production. Moreover, we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems. Finally, we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain. By unraveling the potential of heterojunction photocatalysts, this review contributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.

Efficient photodegradation of perfluoroalkyl substances under visible light by hexagonal ZnIn2S4 nanosheets.

Perfluoroalkyl substances (PFASs) are typical persistent organic pollutants, and their removal is urgently required but challenging. Photocatalysis has shown potential in PFASs degradation due to the redox capabilities of photoinduced charge carriers in photocatalysts. Herein, hexagonal ZnIn2S4 (ZIS) nanosheets were synthesized by a one-pot oil bath method and were well characterized by a series of techniques. In the degradation of sodium p-perfluorous nonenoxybenzenesulfonate (OBS), one kind of representative PFASs, the as-synthesized ZIS showed activity superior to P25 TiO2 under both simulated sunlight and visible-light irradiation. The good photocatalytic performance was attributed to the enhanced light absorption and facilitated charge separation. The pH conditions were found crucial in the photocatalytic process by influencing the OBS adsorption on the ZIS surface. Photogenerated e- and h+ were the main active species involved in OBS degradation in the ZIS system. This work confirmed the feasibility and could provide mechanistic insights into the degradation and defluorination of PFASs by visible-light photocatalysis.

Fungal photoinactivation doses for UV radiation and visible light-a data collection.

Nearly two million people die each year from fungal infections. Additionally, fungal crop infections jeopardize the global food supply. The use of 254 nm UVC radiation from mercury vapor lamps is a disinfection technique known to be effective against all microorganisms, and there are surveys of published UVC sensitivities. However, these mainly focus on bacteria and viruses. Therefore, a corresponding overview for fungi will be provided here, including far-UVC, UVB, UVA, and visible light, in addition to the conventional 254 nm UVC inactivation. The available literature was searched for photoinactivation data for fungi in the above-mentioned spectral ranges. To standardize the presentation, the mean log-reduction doses were retrieved and sorted by fungal species, spectral range, wavelength, and medium, among others. Additionally, the median log-reduction dose was determined for fungi in transparent liquid media. Approximately 400 evaluable individual data sets from publications over the last 100 years were compiled. Most studies were performed with 254 nm radiation from mercury vapor lamps on Aspergillus niger, Candida albicans, and Saccharomyces cerevisiae. However, the data found were highly scattered, which could be due to the experimental conditions. Even though the number of individual data sets seems large, many important fungi have not been extensively studied so far. For example, UV irradiation data does not yet exist for half of the fungal species classified as "high priority" or "medium priority" by the World Health Organization (WHO). In addition, researchers should measure the transmission of their fungal suspensions at the irradiation wavelength to avoid the undesirable effects of either absorption or scattering on irradiation results.

Visible Light-Induced Polymerization to Access Polyamides.

Visible light-induced polymerization, as a promising and green strategy, is showing great potential in preparing value-added polymers. Herein, a visible light photoredox catalysis method is reported to afford a library of polyamide with high yields (up to 99%) and high molecular weights (Mws) (up to 71 000 g mol-1). Dithioacids and diamines as the monomers, and 9-mesityl-10-methylacridinium tetrafluoroborate (Mes-Acr-MeBF4) as the organic photoredox catalyst give the polyamides with structural diversity in air under mild conditions without extra metal, base, or additives.

Organocatalyzed Carbonylation of Alkyl Halides Driven by Visible Light.

Herein, we describe a new strategy for the carbonylation of alkyl halides with different nucleophiles to generate valuable carbonyl derivatives under visible light irradiation. This method is mild, robust, highly selective, and proceeds under metal-free conditions to prepare a range of structurally diverse esters and amides in good to excellent yields. In addition, we highlight the application of this activation strategy for 13C isotopic incorporation. We propose that the reaction proceeds by a photoinduced reduction to afford radical anions from alkyl halides, which undergo subsequent single electron-oxidation to form a carbocationic intermediate. Carbon monoxide is trapped by the carbocation to generate an acylium cation, which can be attacked by a series of nucleophiles to give a range of carbonyl products.

A Comprehensive Survey on Emerging Assistive Technologies for Visually Impaired Persons: Lighting the Path with Visible Light Communications and Artificial Intelligence Innovations.

In the context in which severe visual impairment significantly affects human life, this article emphasizes the potential of Artificial Intelligence (AI) and Visible Light Communications (VLC) in developing future assistive technologies. Toward this path, the article summarizes the features of some commercial assistance solutions, and debates the characteristics of VLC and AI, emphasizing their compatibility with blind individuals' needs. Additionally, this work highlights the AI potential in the efficient early detection of eye diseases. This article also reviews the existing work oriented toward VLC integration in blind persons' assistive applications, showing the existing progress and emphasizing the high potential associated with VLC use. In the end, this work provides a roadmap toward the development of an integrated AI-based VLC assistance solution for visually impaired people, pointing out the high potential and some of the steps to follow. As far as we know, this is the first comprehensive work which focuses on the integration of AI and VLC technologies in visually impaired persons' assistance domain.

Adsorptive-Photocatalytic Composites of α-Ferrous Oxalate Supported on Activated Carbon for the Removal of Phenol under Visible Irradiation.

Adsorptive-photocatalytic composites based on activated carbon (AC) and α-ferrous oxalate dihydrate (α-FOD) were synthesized by an original two-step method and subsequently used for the removal of phenol from aqueous solutions. To obtain the composites, ferrotitaniferous black mineral sands (0.6FeTiO3·0.4Fe2O3) were first dissolved in an oxalic acid solution at ambient pressure, and further treated under hydrothermal conditions to precipitate α-FOD on the AC surface. The ratio of oxalic acid to the mineral sand precursor was tuned to obtain composites with 8.3 and 42.7 wt.% of α-FOD on the AC surface. These materials were characterized by X-ray powder diffraction, scanning electron microscopy, and the nitrogen adsorption-desorption method. The phenol removal efficiency of the composites was determined during 24 h of adsorption under dark conditions, followed by 24 h of adsorption-photocatalysis under visible light irradiation. AC/α-FOD composites with 8.3 and 42.7 wt.% of α-FOD adsorbed 60% and 51% of phenol in 24 h and reached a 90% and 96% removal efficiency after 12 h of irradiation, respectively. Given its higher photocatalytic response, the 42.7 wt.% α-FOD composite was also tested during successive cycles of adsorption and adsorption-photocatalysis. This composite exhibited a reasonable level of cyclability (~99% removal after four alternated dark/irradiated cycles of 24 h and ~68% removal after three simultaneous adsorption-photocatalysis cycles of 24 h). The promising performance of the as-prepared composites opens several opportunities for their application in the effective removal of organic micropollutants from water.

Visible Light-Responsive Crystalline B←N Host Adducts with Solvent-Induced Allosteric Effect for Guest Release.

Photo-responsive organic crystals, capable of converting light energy into chemical energy to initiate conformational transitions, present an emerging strategy for developing lightweight and versatile smart materials. However, visible light-triggered tailored guests capture and release behaviors in all-organic solids are rarely reported. Here, we introduce a photoreactive crystalline boron-nitrogen (B←N) host adduct with the ability to undergo [2+2] photocycloaddition upon 447 nm light exposure. This process facilitates single-crystal-to-single-crystal (SCSC) photodimerization in the mother liquor, maintaining the original B←N host structure. Weakened intermolecular interactions within the photodimer host contribute to fast guest release in air under irradiation. Furthermore, the dynamic B←N bonds enable reversible transformations between organic host adducts and adduct cocrystals under the solvent-induced allosteric effect. As a result, four B←N host adduct crystals containing individual alkane guest are easily obtained and exhibited the ability of photo-controlled alkane release. Therefore, the integration of photo reactivity and structural transformation within B←N host adduct enables customized capture and release of guest molecules.

LC-MS/MS-based targeted carotenoid and anthocyanidin metabolic profile of Auricularia cornea under blue and red LED light exposure.

Light exposure significantly impacted the coloration and metabolism of Auricularia cornea, although the underlying mechanisms remain unclear. This study aimed to test the apparent color and pigment metabolic profiles of A. cornea in response to red (λp = 630 nm) and blue (λp = 463 nm) visible light exposure. Colorimeter analysis showed that fruiting bodies appeared bright-white under red-light and deeper-red under blue-light, both with a yellow tinge. On the 40th day of light-exposure, bodies were collected for metabolite detection. A total of 481 metabolites were targeted analysis, resulting in 18 carotenoids and 11 anthocyanins. Under red and blue light exposure, the total carotenoids levels were 1.1652 µg/g and 1.1576 µg/g, the total anthocyanins levels were 0.0799 µg/g and 0.1286 µg/g, respectively. Four differential metabolites and three putative gene linked to the visual coloration of A. cornea were identified. This pioneering study provides new insights into the role of light in regulating A. cornea pigmentation and metabolic profile.

Macrocyclic porphyrin photocatalysts without metal chelation: A novel pathway for complete degradation of tough halophenols with longwave visible LED light source.

Halophenols are toxic and persistent pollutants in water environments which poses harm to various organisms. Due to their high stability and long residence time, ultraviolet radiation, heavy metals and oxidizing agents have been largely adopted on treating these compounds. However, these treatment methods could pose toxicity or hazardous risks to the marine environment and plant operators. In this study, a water-soluble porphyrin photocatalyst was synthesized and introduced for halophenol treatment using UV-free LED white light. The porphyrin catalyst is a macrocyclic ring consisting of pyrroles linked with methine bridges, the highly conjugated ring provided the superior functionality of visible light absorption. Surprisingly, over 99 % degradation of halophenols and over 90 % dehalogenation have been achieved without metal chelation, even higher than those of transition metal porphyrins with inclusion of Fe3+, Zn2+, Cu2+, Co2+, Ni2+, and Mn2+. Ring-opening reactions were confirmed with the formation of carboxylic acids; dicarboxylic acids like acrylic acid, and malonic acid; while fumaric acid was the main product. Total organic carbon results indicated no CO2 produced during the reaction. Triplet absorbance and scavenger studies also indicated that singlet oxygen and conduction band electrons are the main radical species for halophenol degradation. The 100-fold singlet emission quenching over triplet absorption quenching indicated that the excited electrons tend to be transferred via singlet state. This concept brings along new approaches detoxifying halophenol-related wastewater without UV, metals and other additives, which is more environmentally-friendly and sheds light to the conversion of toxic materials into useful chemical precursors.

Treatment and ecotoxicity assessment of wastewater containing organic pollutants using a new CoFe2O4/biochar photocatalyst composite.

This is the first record on literature to use biochar as support for CoFe2O4 to applicate and evaluate it as photocatalyst for degradation of organic pollutants. The support was verified by XRD, FT-IR, SEM, EDS and band gap. Composites CFO1BQ3, CFO1BQ1, and CFO3BQ1 showed 100% degradation in 60 min. This outstanding performance can be related to the drop in band gap energy and recombination rate of e¯/h + . The composites showed better efficiency when compared to pure CoFe2O4 (∼78%). This might be associate to the fact that biochar has a high concentration of phenolic, hydroxyl and carboxylic functional groups on its surface. In this reaction h+, O2•-, and •OH were the reactive species involved in the degradation. The toxicity of ponceau was tested before and after the treatment, through biochemical biomarkers in Danio rerio fish. In general, the treatment proved to be efficient in reducing ponceau toxicity in D. rerio fish.

Hectogram-Scale Synthesis of Visible Light Excitable Room Temperature Phosphorescence Carbon Dots.

Carbon dots (CDs) based room temperature phosphorescence (RTP) materials can be prepared via facile procedures and exhibit excellent photostability and biocompatibility. Furthermore, doping of hetero-atoms into CDs can afford multiple triplet levels. The RTP emission generated from the resultant CDs always displays outstanding dynamic behaviors and even can be efficiently excited by visible light. Given this, CDs-based RTP materials not only can be used for anti-counterfeiting but also exhibit great application potential in signage and illumination fields. In this contribution, a type of B, N, and P co-doped CDs are prepared in hectogram scale. Upon excitation by UV lamp and white LED, the obtained CDs emit green and yellow RTP, respectively, the lifetime of which are 851 and 481 ms, respectively. It is found that the luminescence color of the CDs can be further tuned. By controlling the degree of carbonization, the RTP color of the CDs can be facilely tuned from green to orange-red. Based on an energy transfer strategy, the luminescence color can be further tuned to red. Benefited from the dynamic and visible-excited colorful RTP emission, the application of these obtained CDs in anti-counterfeiting, fingerprint collection, and luminescent traffic signage are also explored.

N-Halosuccinimide-CeCl3 Transient Charge-Transfer Complexes as Semi Heterogeneous Photocatalyst in Cyclization of N-Propargylamides.

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide or NIS) in acetonitrile. These transient CT complexes acted as a semi-heterogeneous photocatalyst. These complexes allowed the Ce(III) ions to absorb light, turning them into strong electron donors that transferred electrons to NXS. This created halide radicals from NXS radical anions, helping to turn N-propargylamides into oxazole aldehydes. Experiments with DMPO and spin-trapping showed that a radical-based mechanism followed a single electron transfer (SET) pathway. Notably, CeCl3 was reused after the reaction without much decomposition, as it was regenerated and separated through simple filtration.

Facile synthesis of a novel CeCO3OH@(H/C-CdS) catalyst with synergistic effect of heterophase junction and heterojunction for enhanced visible-light photocatalytic degradation efficiency at room temperature.

A new CeCO3OH@(hexagonal/cubic phases-CdS) (CeCO3OH@(H/C-CdS)) composite catalyst was facilely synthesized by a simple microinjection titration-stirring method, in which CdS nanoparticles were dispersed on the surface of CeCO3OH nanolines. The optimal conditions for the preparation of composite catalysts with high photocatalytic performance were determined by single-factor experiments and response surface experiments. Under these conditions, the degradation rate of 30 mL 2.000 g/L rhodamine B (Rh B) by CeCO3OH@(H/C-CdS) in a photocatalytic reaction for 1 h at 25 °C was up to 86.81 % and its degradation rate in a photocatalytic reaction for 150 min was up to 99.62 %. The degradation rate could be maintained above 80 % even after six times recycling. Especially, the photocatalytic degradation efficiency of 2.000 g/L Rh B on the composite catalyst under sunlight and at room temperature for 30 min reached 97.66 %. Meanwhile, the large size of CeCO3OH considerably alleviated the agglomeration of CdS, providing more adsorption and active sites for visible light-mediated degradation of Rh B. Importantly, the Z-scheme charge transfer realized by CdS and CeCO3OH enhanced the efficient separation of photogenerated electrons and holes, and successfully inhibited the recombination of photogenerated electrons with holes. At the same time, owing to the low energy band difference between the two phases of CdS, charge was transferred between the hexagonal and cubic phases, leaving more effective photogenerated charge to participate in the degradation of Rh B. The synergism of the heterophase junction and heterojunction and the presence of oxygen and sulfur vacancies considerably enhanced the degradation performance of the catalyst. Thus, this study provides a new strategy for the modification and enhanced visible-light catalysis performance of CdS-based catalysts.

Visible Light Promoted de Mayo Type Reaction of Bicyclo[1.1.0]butanes.

We reported herein a visible light mediated de Mayo-type reaction between 1,3-diketones and BCB. The reaction proceeds through a [2π+2σ] cycloaddition and retro-aldol sequence, producing cis-difunctionalized cyclobutanes in high yields with good regio- and diastereoselectivity.

Visible-Light-Induced Silk Fibroin Hydrogels with Carbon Quantum Dots as Initiators for 3D Bioprinting Applications.

Digital light processing (DLP) 3D bioprinting technology has attracted increasing attention in tissue engineering in recent years. However, it still faces significant technical and operational challenges such as cell carcinogenesis caused by prolonged exposure to ultraviolet light and the presence of heavy metal ions in complex photoinitiator systems. In this study, a novel strategy is designed to introduce carbon quantum dots into visible-light-induced silk fibroin bioink as initiators (CDs/SilMA) applied for DLP 3D bioprinting technology. The incorporation of carbon quantum dots facilitates the formation of precise hydrogel structures at 415 nm visible wavelength, enabling the creation of brain, bronchus, spine, and ear models. Replacing heavy metal photoinitiators with carbon quantum dots imparts fluorescence properties to the bioink and enhances its mechanical properties. Meanwhile, the fibroin protein-based hydrogel exhibits favorable properties, such as drug loading, slow release, degradability, and biocompatibility. This is the first study to propose the application of carbon quantum dots in silk fibroin-based bioink. Moreover, the resulting product demonstrates excellent compatibility with the DLP printing process, making it promising for practical applications in various tissue engineering scenarios with specific requirements.

Design and synthesis of visible light-activatable photocaged peroxides for optical control of ROS-mediated cellular signaling.

We designed and synthesized two novel photocaged peroxide compounds, N5TBHP and N6TBHP, featuring nitrogen-containing fused ring coumarin skeletons. Notably, a tetrahydroquinoline fused coumarin derivative, N6TBHP demonstrated significantly higher photocleavage efficiency under visible light at 455 nm compared to N5TBHP, which contains an indoline fused coumarin. This process effectively releases the oxidative stress inducer tert-butylhydroperoxide (TBHP). Additionally, N6TBHP exhibits high resistance to glutathione (GSH), and its UV spectral analysis suggests enhanced intracellular stability due to reduced reactivity with GSH through self-assembly. Furthermore, N6TBHP can release an optimal amount of TBHP into cells under visible light irradiation with minimal cell damage. These properties position N6TBHP as a promising tool for advancing research in intracellular redox signaling.

Novel furfural-complexed approach to synthesizing carbon-Doped ZnO with breakthrough photocatalytic efficacy.

INTRODUCTION: The efficiency of zinc oxide (ZnO) nanoparticles for environmental decontamination is limited by their reliance on ultraviolet (UV) light and rapid charge carrier recombination. Carbon doping has been proposed to address these challenges by potentially enhancing visible light absorption and charge separation. OBJECTIVES: This study aims to introduce a novel, single-step synthesis method for carbon-doped ZnO (C-Z) nanoparticles, leveraging the decomposition of zinc nitrate hexahydrate and furfural under a nitrogen atmosphere to improve photocatalytic activity under visible light. METHODS: A series of C-Z variants (C-Z-1 to C-Z-5) and an undoped sample (ZnO-0) were synthesized. The influence of furfural on the synthesis process and doping mechanism was analyzed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS). RESULTS: XPS confirmed the integration of carbon within the ZnO matrix, and XRD indicated increased lattice dimensions owing to doping. DRS revealed bandgap narrowing, suggesting enhanced charge separation. Among the variants, C-Z-3 significantly outperformed the others, showing a 12-fold increase in the photocatalytic degradation rate of Rhodamine B compared to undoped ZnO. CONCLUSION: The developed single-step synthesis method for C-Z nanoparticles represents a major advancement in materials engineering for ecological applications. The enhanced photocatalytic activity under visible light, as demonstrated by C-Z-3, underscores the potential of these nanoparticles for environmental decontamination.

Recent Advances in Photoinduced Oxidative Cleavage of Alkenes.

Oxidative cleavage of alkenes leading to valuable carbonyl derivatives is a fundamental transformation in synthetic chemistry. In particular, ozonolysis is the mainstream method for the oxidative cleavage of alkenes that has been widely implemented in the synthesis of natural products and pharmaceutically relevant compounds. However, due to the toxicity and explosive nature of ozone, alternative approaches employing transition metals and enzymes in the presence of oxygen and/or strong oxidants have been developed. These protocols are often conducted under harsh reaction conditions that limit the substrate scope. Photochemical approaches can provide milder and more practical alternatives for this synthetically useful transformation. In this review, we outline recent visible-light-promoted oxidative cleavage reactions that involve photocatalytic activation of oxygen via electron transfer and energy transfer. Also, an emerging field featuring visible-light-promoted oxidative cleavage under anaerobic conditions is discussed. The methods highlighted in this review represent a transformative step toward more sustainable and efficient strategies for the oxidative cleavage of alkenes.

Effect of carboxyl group on photoelectrochemical performance of TiO2nanowire arrays for water splitting.

TiO2is one of the most studied semiconductor materials for the photoelectrochemical water splitting to hydrogen production, but it only responds to ultraviolet light. The introduction of organic compound is one of the common means to expand the visible light response of TiO2. In this work, rutile TiO2nanowire arrays (NWs) were grown on conductive glass by a modified solvothermal method using oleic acid as the key additive. The obtained TiO2NWs are characterized using x-ray diffraction, x-ray photoelectron spectroscopy, infrared spectroscopy and electrochemical characterization. The results show that the carboxyl groups arising from oleic acid are chemically bonded with the TiO2NWs in the form of chelating bidentate, which increases the visible light absorption range and active sites of TiO2, and reduces the transfer resistance between the photoelectrode and the electrolyte. The photocurrent density is doubled to 0.17 mA cm-2at 1.23 V vs. RHE. This work provides a novel idea for the design of metal oxide semiconductor photoanodes by adsorbing organic compounds.