Methylene Blue (MB), a frequently used cationic dye, is recognized for its persistence and probable toxicity, making its removal from wastewater an urgent environmental concern. This study reports the solar photocatalytic degradation efficiency of MB by bismuth oxybromide-green silver nanoparticles (AgNPs) as catalyst. AgNPs were produced by the green synthesis method from an invasive aquatic weed water hyacinth (Pontederia crassipes). The AgNPs were doped on Bismuth oxybromide (BiOBr) nanosheets formed on the surface of carbon fibre cloth (CFC) to form the catalyst CFC-BiOBr-Ag. Under optimum conditions of 5 mg/L of initial MB concentration and near-neutral pH, one piece of CFC-BiOBr-Ag photocatalyst (5.78 mg/L) exhibited 95.68% degradation efficiency of MB in 4h. TOC removal studies showed a removal efficiency of 74.82% after 4h, indicating the potential for mineralization of MB. Adsorption-photocatalysis-desorption study revealed complete degradation of adsorbed MB at the end of the photocatalytic degradation. Additionally, the catalyst exhibited good reusability, with more than 84.88% degradation efficiency even after five cycles of use. Under direct sunlight, the CFC-BiOBr-Ag catalyst demonstrated MB degradation efficiency of 97.52% after 3 h of treatment. MB breakdown was evidently done by the hole (h+) and the superoxide radical (O2•-). The mechanism of MB degradation was adsorption and subsequent degradation by the CFC-BiOBr-Ag photocatalyst. The prevalent degradation reactions such as demethylation, ring opening, hydroxylation, •OH radicle attack, desulfonication, hydrolysis etc. led to formation of various intermediates which further mineralized to CO2 and H2O.

The contamination of water sources by pharmaceutical pollutants presents significant environmental and health hazards, making the development of effective photocatalytic materials crucial for their removal. This research focuses on the synthesis of a novel Ag/CuS/Fe₃O₄ nanocomposite and its photocatalytic efficiency against tetracycline (TC) and diclofenac contaminants. The nanocomposite was created through a straightforward and scalable precipitation method, integrating silver nanoparticles (AgNPs) and copper sulfide (CuS) into a magnetite framework. Various analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR),ultraviolet-visible spectrophotometry (UV-Vis) and energy-dispersive X-ray spectroscopy (EDS), were employed to characterize the structural and morphological properties of the synthesized material. The photocatalytic activity was tested by degrading tetracycline and diclofenac under visible light. Results indicated a marked improvement in the photocatalytic performance of the Ag/CuS/Fe₃O₄ nanocomposite (98%photodegradation of TC 60 ppm in 30 min) compared to both pure magnetite and CuS/Fe₃O₄. The enhanced photocatalytic efficiency is attributed to the synergistic interaction between AgNPs, CuS, and Fe3O4, which improves light absorption and charge separation, thereby increasing the generation of reactive oxygen species (ROS) and promoting the degradation of the pollutants. The rate constant k of photodegradation was about 0.1 min-1 for catalyst dosages 0.02 g. Also the effect of photocatalyst dose and concentration of TC and pH of solution was tested. The modified photocatalyst was also used for simultaneous photodegradation of TC and diclofenac successfully. This study highlights the potential of the Ag/CuS/Fe₃O₄ nanocomposite as an efficient and reusable photocatalyst for eliminating pharmaceutical pollutants from water.

TiO2 is 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 TiO2 nanowire arrays (NWs) were grown on conductive glass by a modified solvothermal method using oleic acid as the key additive. The obtained TiO2 NWs 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 TiO2 NWs 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-2 at 1.23 V vs. RHE. This work provides a novel idea for the design of metal oxide semiconductor photoanodes by adsorbing organic compounds.

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.

Difunctionalizations of alkenes represent one of the most straightforward protocols to build molecular complexity due to the simultaneous construction of two vicinal bonds cross π-bond of alkenes. It is extremely attractive yet challenging to control the stereochemistry outcome of this event. Over the past years, visible-light and Ni-catalyzed asymmetric difunctionalizations of alkenes provide an environmental benign and promising solution for the construction of saturated carbon centers with the control of regio- and enantioselectivity. In this Concept, the initiative and progress of regio- and enantioselective difunctionalizations of alkenes enabled by visible-light and nickel catalysis has been summarized. Moreover, further efforts and directions for the development of visible-light mediated Ni-catalyzed asymmetric difunctionalizations of alkenes has been discussed.

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.

Cooperative CO2 photoreduction with tailored organic synthesis offers a potent avenue for harnessing concurrently generated electrons and holes, facilitating the creation of both solar fuels and specialized chemical compounds. However, controlling the crystallization and morphologies of metal-free molecular nanostructures with exceptional photocatalytic activities toward CO2 reduction remains a significant challenge. These hurdles encompass insufficient CO2 activation potential, sluggish multielectron processes, delayed charge-separation kinetics, inadequate storage of long-lived photoexcitons, unfavorable thermodynamic conditions, and the precise control of product selectivity. Here, melem oligomer 2D nanosheets (MNSs) synthesized through pyrolysis are transformed into 1D nanorods (MNRs) at room temperature with the simultaneous engineering of vacancies and morphology. Transient absorption spectral analysis reveals that vacancies in MNRs trap charges, extending charge carrier lifetimes. Additionally, carbon vacancies enhance CO2 adsorption by increasing amine functional centers. The photocatalytic performance of MNRs for CO2 reduction coupled with benzyl alcohol oxidation is approximately ten times higher (CH3OH and aromatic aldehyde production rate 27 ± 0.5 and 93 ± 0.5 mmol g-1 h-1, respectively) than for the MNSs (CH3OH and aromatic aldehyde production rate 2.9 ± 0.5 and 9 ± 0.5 mmol g-1 h-1, respectively). The CO2 reduction pathway involved the carbon-coordinated formyl pathway through the formation of *COOH and *CHO intermediates, as mapped by in situ Fourier-transform infrared spectroscopy. The superior performance of MNRs is attributed to favorable energy-level alignment, enriched amine surfaces, and unique morphology, enhancing solar-to-chemical conversion.

Near UV and visible light photodegradation can target therapeutic proteins during manufacturing and storage. While the underlying photodegradation pathways are frequently not well-understood, one important aspect of consideration is the formulation, specifically the formulation buffer. Citrate is a common buffer for biopharmaceutical formulations, which can complex with transition metals, such as Fe(III). In an aqueous solution, the exposure of such complexes to light leads to the formation of the carbon dioxide radical anion (•CO2-), a powerful reductant. However, few studies have characterized such processes in solid formulations. Here, we show that solid citrate formulations containing Fe(III) lead to the photochemical formation of •CO2-, identified through DMPO spin trapping and HPLC-MS/MS analysis. Factors such as buffers, the availability of oxygen, excipients, and manufacturing processes of solid formulations were evaluated for their effect on the formation of •CO2- and other radicals such as •OH.

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.

In the present study, we introduce a covalent organic triazine framework polymer (COTF-P) using 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with triazine-based amine. The resulting dark red COTF-P illustrated potential behavior as a photocatalyst under visible light. Due to the inadequate solar energy capture and ultrafast charge recombination of the resulting COTF-P, the prepared COTF-P has been decorated with CQDs (N-CQD and N-S-CQD) to build a Z-scheme CQDs/COTF-P heterojunction photocatalyst and utilizes as photocatalyst for the breakdown of phenanthrene (PHE) exposed to visible light. The prepared COTF-P and CQDs/COTF-P were fully characterized, analyzing the textural (N2 isotherms), structural (XRD and FTIR), chemical (EDX and XPS), morphological (FESEM and TEM), optical (DRS-UV-Vis and photoluminescence), and electrochemical properties (EIS impedance, transient photocurrent, and flat band potential). The prepared N-S-CQD/COTF-P heterojunction displayed optimum activity for the photocatalytic oxidation of PHE from water, owing to an enhanced separation of the photogenerated charges and lower bandgap value, 2.1 vs. 1.9 eV. The N-S-CQD/COTF-P heterojunction showed acceptable stability in terms of activity and structural properties after 5 cycles of reuse. The mechanism of activation highlights the importance played by superoxide radicals and hydroxyl radicals. This project sheds light on the potential use of CQDs for the decoration of polymers, extending the absorbance in the visible region and boosting the migration of charge, which boosts the activity of the resulting material.