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Two new supramolecular photocatalysts made of covalently linked Ru(II) polypyridine chromophore subunits ([Ru(bpy)3]2+-type species; bpy = 2,2′-bipyridine) and [RuL(pic)2] (L = 2,2′-bipyridine-6,6′-dicarboxylic acid; pic = 4-picoline) water oxidation catalyst subunits have been prepared. The new species, 1 and 2, contain chromophore and catalyst subunits in the molecular ratios 1:1 and 1:2, respectively. The model chromophore species [Ru(bpy)2(L1)]2+ (RuP1; L1=4-[2-(4-pyridyl)-2-hydroxyethyl]-4-methyl-2,2′-bipyridine) and [Ru(bpy)2(L2)]2+ (RuP2; L2 = 4,4′-bis[2-(4-pyridyl)-2-hydroxyethyl]-2,2′-bipyridine) have also been prepared. The absorption spectra, oxidation behavior, and luminescent properties of 1 and 2 have been studied, and the results indicate that each subunit largely maintains its own properties in the supramolecular species. However, the luminescence of the chromophore subunits is significantly quenched in 1 and 2 in comparison with the luminescence of the respective model species. Both 1 and 2 exhibit catalytic water oxidation in the presence of cerium ammonium nitrate, exhibiting an I2M mechanism, with a better efficiency than the known catalyst [RuL(pic)2] under the same experimental conditions. Upon light irradiation, in the presence of persulfate as a sacrificial acceptor agent, 1 and 2 are more efficient photocatalysts than a system made of separated [Ru(bpy)3]2+ and [RuL(pic)2] species, highlighting the advantage of using multicomponent, supramolecular species with respect to isolated species. The O–O bond formation step is I2M, even in the photo-driven process. The photocatalytic process of 2 is more efficient than that of 1, with the turnover frequency reaching a value of 1.2 s−1. A possible reason could be an increased local concentration of catalytic subunits in the needed bimolecular assembly required for the I2M mechanism in 2 with respect to 1, a consequence of the presence of two catalytic subunits in each multicomponent species 2. [ABSTRACT FROM AUTHOR]

The hetero photooxidation of sulfide under aqueous conditions is of great importance in the green synthesis of sulfoxide. This process requires a type of solid photocatalyst with the properties of high porosity and water stability, as well as photosensitivity. Herein, a stable Ir–Zr-MOF material (compound 1) with high porosity is assembled from two linear linkers of a 2-phenylquinoline-4-carboxylic acid-Ir(III) complex (Irphen) and 4,4′-stilbenedicarboxylic acid (H2SDC), and a Zr6 cluster. 1 is isostructural to JLU-Liu34 with a composition of [Zr6O4.78(OH)3.22(SDC)3.82(Irphen)0.78TFA2.8]·2.8MeOH and permanent porosity with a BET surface area of 1507 m2 g−1. 1 exhibits improved activity for the photocatalytic aerobic oxidation of sulfide to sulfoxide via blue light irradiation under aqueous conditions. Mechanism studies demonstrate that a superoxide radical is the reactive oxygen species in the sulfide photooxidation. 1 can be readily recycled and reused at least 5 times without loss of catalytic activity. This work not only provides a good strategy for the assembly of an Ir(III) complex into MOFs but also an efficient method for the green synthesis of sulfoxide. [ABSTRACT FROM AUTHOR]

• Recent advances of photocatalytic removal ARB and ARGs in wastewater are reviewed. • The sources and transformation of ARB and ARGs in wastewater are summarized. • Effect of UV-based methods on ARB and ARGs removing were discussed. • ARB and ARGs removal by TiO 2 and g-C 3 N 4 -based photocatalysts were analyzed. • Some suggestions for future research directions are proposed. Because of the recent widespread usage of antibiotics, the acquisition and dissemination of antibiotic-resistance genes (ARGs) were prevalent in the majority of habitats. Generally, the biological wastewater treatment processes used in wastewater treatment plants have a limited efficiencies of antibiotics resistant bacteria (ARB) disinfection and ARGs degradation and even promote the proliferation of ARGs. Problematically, ARB and ARGs in effluent pose potential risks if they are not further treated. Photocatalytic oxidation is considered a promising disinfection technology, where the photocatalytic process generates many free radicals that enhance the interaction between light and deoxyribonucleic acid (DNA) for ARB elimination and subsequent degradation of ARGs. This review aims to illustrate the progress of photocatalytic oxidation technology for removing antibiotics resistant (AR) from wastewater in recent years. We discuss the sources and transfer of ARGs in wastewater. The overall removal efficiencies of ultraviolet radiation (UV)/chlorination, UV/ozone, UV/H 2 O 2 , and UV/sulfate-radical based system for ARB and ARGs, as well as the experimental parameters and removal mechanisms, are systematically discussed. The contribution of photocatalytic materials based on TiO 2 and g-C 3 N 4 to the inactivation of ARB and degradation of ARGs is highlighted, producing many free radicals to attack ARB and ARGs while effectively limiting the horizontal gene transfer (HGT) in wastewater. Finally, based on the reviewed studies, future research directions are proposed to realize specific photocatalytic oxidation technology applications and overcome current challenges. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] In this work, we have described the synthesis of vanadium (V) nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (V@mpg-C 3 N 4) and their uses in photocatalytic ethylbenzene oxidation to the respective acetophenones. The mpg-C 3 N 4 serves as the support for the decoration of V NPs, through a simple impregnation method. Various advanced techniques, such as XRD, UV–vis spectrometry, HRTEM, HAADF-STEM, AC-STEM, elemental mapping, and BET surface area analysis, were employed for the characterization of V@mpg-C 3 N 4. The detailed characterization studies reveal that the V@mpg-C 3 N 4 catalyst has a medium band gap (2.78 eV), a high surface area (76.7 m2g−1), and a mesoporous nature. The V@mpg-C 3 N 4 photocatalysts demonstrated excellent performance in the light-assisted oxidation of ethylbenzene, achieving over 99 % conversion and selectivity for acetophenone in an environmentally friendly solvent (water) using a domestic light source (50 W white light). This developed synthesis strategy will be useful for synthesizing various noble and non-noble metal-based catalysts and their applications in organic transformation and environmental remediation. [ABSTRACT FROM AUTHOR]

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) into value-added chemicals offers a promising green route to bridge biomass resources with diverse industries owing to its low-cost valorization and environmental sustainability. Nevertheless, efficiently upgrading HMF into target products remains a big challenge. Herein, a microflower-like hybrid S-scheme heterojunction photocatalyst was developed via the in situ growth of layered ZnIn2S4 on NH2-MIL-125 (Ti) metal–organic framework nanosheets (denoted as ZIS/NMTs) for HMF oxidation. The thin nanosheet structure of ZIS/NMTs provided abundant heterojunction interfaces and numerous exposed active sites for charge migration and molecule adsorption. Meanwhile, systematic spectroscopic analysis and theoretical calculations comprehensively demonstrated the formation of an interface internal electric field in the ZIS/NMT S-scheme heterojunction, accelerating interfacial charge separation of photo-induced carriers. The optimal ZIS/NMT-10 photocatalyst exhibited impressive visible-light photocatalytic activity with nearly complete HMF conversion and 92.5% 5-formyl-2-furancarboxylic acid (FFCA) selectivity, which could be attributed to the synergistic effect of its two components. This study presents new insights into designing efficient heterojunction photocatalysts for converting HMF into target products and can be extended to other biomass valorization. [ABSTRACT FROM AUTHOR]

[Display omitted] • Dissociative adsorption of water is more favorable than molecular adsorption on the pristine PbTiO 3 (001) surface. • Surface O V can enhance the thermodynamic stability of dissociative adsorption of water molecule. • Water molecule can spontaneously dissociate into H atom and OH group on pristine PbTiO 3 (001) surface at room temperature. • Surface O V facilitates water molecule dissociation, resulting in high surface coverage of OH group on defective surface. In this work, combining the density functional theory (DFT) calculations and the ab initio molecular dynamics (AIMD) simulations, the water adsorption behavior, including the molecular and the dissociative adsorption on the negatively polarized (0 0 1) surface of ferroelectric PbTiO 3 was comprehensively studied. Our theoretical results show that the dissociative adsorption of water is more energetically favorable than the molecular adsorption on the pristine PbTiO 3 (0 0 1) surface. It has been also found that introducing surface oxygen vacancies (O V) can enhance the thermodynamic stability of dissociative adsorption of water molecule. The AIMD simulations demonstrate that water molecule can spontaneously dissociate into hydrogen atoms (H) and hydroxyl groups (OH) on the pristine PbTiO 3 (0 0 1) surface at room temperature. Moreover, the surface O V can effectively facilitate the dissociative adsorption of water molecules, leading to a high surface coverage of OH group, thus giving rise to a high reactivity for water splitting on defective PbTiO 3 (0 0 1) surface with O V. Our results not only comprehensively understand the reason for the photocatalytic water oxidation activity of single domain PbTiO 3 , but also shed light on the development of high performance ferroelectric photocatalysts for water splitting. [ABSTRACT FROM AUTHOR]

The aim of the present work is to investigate the photocatalytic degradation of propyl paraben (propyl para-hydroxybenzoate, PrP) using Cu2O-ZnO-NPs photocatalyst followed by the identification of the oxidation by-products. The Cu2O-ZnO-NPs material, synthesized using a green chemistry approach, was used as a photocatalyst for the removal of PrP. The nanoparticles were characterized by XRD, XRF, diffuse reflectance spectroscopy, ATG/DTG, FTIR, SEM–EDX, BET and FRX techniques. The XRD results showed that Cu2O-ZnO-NPs have a nanometer size of 24.13 nm. The DR-UV analysis showed that Cu2O-ZnO-NPs has an Eg of 2.35 eV which corresponds to the absorption of visible light. The SEM–EDX analysis showed that the ZnO has a hexagonal structure while the CuO has a monoclinic structure. The effect of variables such as propyl paraben concentration (PrP), hydrogen peroxide concentration (H2O2), catalyst dose, and the reaction temperature on the pseudo-first order reaction rate constant (kapp) of the reaction was evaluated. It was found that the degradation of PrP was governed by hydroxyl radical °OH attack and the pathways consisted of a cascade of reactions. The optimum photocatalytic degradation was obtained with an initial catalyst dose of 50 mg, pH 7, and PrP concentration of 10 mg/L. When the photocatalyst was irradiated, a significant PrP degradation was observed after 30 min of irradiation. The results suggest that Cu2O-ZnO-NPs act as a good photocatalyst for PrP degradation under visible light. [ABSTRACT FROM AUTHOR]

[Display omitted] • A chemically bonded 0D/2D Au/ZIS-V ohmic junction was prepared. • Synergistic effect of built-in electric field, Au-S bonds and Zn vacancies on dual-function photocatalysis. • Au/ZIS-V is suitable for photocatalytic selective alcohol oxidation coupled with H 2 production and CO 2 reduction. • The thermodynamics and kinetics of photoredox were simultaneously improved. • The utilization factor of photoexcited holes to electrons can reach up to 0.99. Combining photocatalytic reduction with organic synthetic oxidation in the same photocatalytic redox system can effectively utilize photoexcited electrons and holes from solar to chemical energy. Here, we stabilized 0D Au clusters on the substrate surface of Zn vacancies modified 2D ZnIn 2 S 4 (ZIS-V) nanosheets by chemically bonding Au-S interaction, forming surfactant functionalized Au/ZIS-V photocatalyst, which can not only synergistic accelerate the selective oxidation of phenylcarbinol to value-added products coupled with clean energy hydrogen production but also further drive photocatalytic CO 2 -to-CO conversion. An internal electric field of Au/ZIS-V ohmic junction and Zn vacancies synchronously promote the photoexcited charge carrier separation and transfer to optimized active sites for redox reactions. Compared with CO 2 reduction in water and the pristine ZnIn 2 S 4 , the reaction thermodynamics and kinetics of CO 2 reduction over the Au/ZIS-V were simultaneously improved about 11.09 and 45.51 times, respectively. Moreover, the photocatalytic redox mechanisms were also profoundly studied by 13CO 2 isotope tracing tests, in situ electron paramagnetic resonance (in situ EPR), in situ X-ray photoelectron spectroscopy (in situ XPS), in situ diffuse reflection infrared Fourier transform spectroscopy (in situ DRIFTS) and density functional theory (DFT) characterizations, etc. These results demonstrate the advantages of vacancies coupled with metal clusters in the synergetic enhancement of photocatalytic redox performance and have great potential applications in a wide range of environments and energy. [ABSTRACT FROM AUTHOR]

Herein, anionic (sodium dodecylbenzene sulfonate, SDBS) and cationic (cetyltrimethylammonium bromide, CTAB) surfactants are involved in the synthesis of a poly(acrylic acid-co-acrylamide) copolymer, p(AA-co-AM), containing nanoceria (CeO2). The physicochemical and optical properties of CTAB-CeO2@p(AA-co-AM) and SDBS-CeO2@p(AA-co-AM) nanocomposites can be studied using different techniques. The physicochemical properties of nanoceria-immobilized p(AA-co-AM) are significantly developed when handled with SDBS. Compared to the CTAB-CeO2@p(AA-co-AM) nanocomposite, SDBS-CeO2@p(AA-co-AM) exhibits pronounced negatively charged mesoporous surfaces with Corel reef-like morphology. SDBS-CeO2@p(AA-co-AM) contains ceria nano-cubes of ~30 nm size, evenly dispersed along a copolymeric moiety, displaying narrower energy bandgap. The photocatalytic efficiency of this nanocomposite is performed in activating persulfate-ions (PS) under visible light irradiation, yielding reactive oxygen species that effectively treat dye wastewater. Advanced SDBS-CeO2@p(AA-co-AM)/PS/Vis photocatalytic oxidation system possesses ~100% methylene blue degradation efficiency within 2 h for five consecutive purification-cycles with thorough mineralization performance. Such superior photo-degradability consults efficacious synergistic combinations gathering the nanocomposite, persulphate-ions, and visible light radiation, yielding an escalated synergy-index value (SI = 6) with intensive generation of reactive-oxidizing species (SO4•−/h+ synergistic ratio 1:5.6). Including anionic-surfactant molecules in the synthesis of metal-containing copolymer nanocomposites is indispensably profitable in the future for the treatment of industrial wastewater. [ABSTRACT FROM AUTHOR]

TiO2 thin film coatings significantly improve catalyst separation in photocatalytic processes. They can be applied in heterogeneous photocatalysis under sunlight by mixing TiO2 with other oxides, such as CeO2, for the removal of pollutants in water. Here, TiO2-CeO2 thin films deposited on borosilicate slides were analyzed and applied in solar heterogeneous photocatalysis for the oxidation of pesticides. The films were synthesized by the sol-gel method with spin coating. The waste solutions from the synthesis were used to prepare TiO2 and TiO2-CeO2 powders. These were analyzed by XRD and XPS to explain the behavior of the films. The thin films were characterized by UV-Vis spectroscopy with transmittance, UV-Vis spectroscopy with RDS, profilometry, AFM and SEM. The addition of CeO2 to TiO2 caused a decrease in the average crystal size and an increase in the strain index. The addition of a second layer made the TiO2-CeO2 thin films thinner. The CeO2 created surface and electronic defects in the titania films, which enhanced their photocatalytic properties under sunlight in the mineralization of diuron and methyl parathion. The TiO2-CeO2-5.0% single-layer thin film samples were the most active in this study and will undoubtedly be applied in larger-scale reaction systems. [ABSTRACT FROM AUTHOR]

This article presents a comprehensive examination of the combined catalytic conversion technology for nitrogen oxides (NOx) and volatile organic compounds (VOCs), which are the primary factors contributing to the formation of photochemical smog, ozone, and PM2.5. These pollutants present a significant threat to air quality and human health. The article examines the reaction mechanism and interaction between photocatalytic technology and NH3-SCR catalytic oxidation technology, highlighting the limitations of the existing techniques, including catalyst deactivation, selectivity issues, regeneration methods, and the environmental impacts of catalysts. Furthermore, the article anticipates prospective avenues for research, underscoring the necessity for the development of bifunctional catalysts capable of concurrently transforming NOx and VOCs across a broad temperature spectrum. The review encompasses a multitude of integrated catalytic techniques, including selective catalytic reduction (SCR), photocatalytic oxidation, low-temperature plasma catalytic technology, and biological purification technology. The article highlights the necessity for further research into catalyst design principles, structure–activity relationships, and performance evaluations in real industrial environments. This research is required to develop more efficient, economical, and environmentally friendly waste gas treatment technologies. The article concludes by outlining the importance of collaborative management strategies for VOC and NOx emissions and the potential of combined catalytic conversion technology in achieving these goals. [ABSTRACT FROM AUTHOR]

In the present study, we investigated the influence of surface fluorine (F) on TiO 2 for the photocatalytic oxidation (PCO) of toluene. TiO 2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO 2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO 2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO 2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO 2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation. [Display omitted] [ABSTRACT FROM AUTHOR]

Promoting the generation of triplet states is essential for developing efficient photocatalytic systems. This research presents a novel approach of host‐stabilized through‐space conjugation via the combination of covalent and non‐covalent methods. The designed building block, 4,4′‐(1,4(1,4)‐dibenzene cyclohexaphane‐1,4‐diyl)bis(1‐phenylpyridinium) chloride, features inherently stable through‐space conjugation. When this block forms a 1 : 1 host–guest complex with cucurbit[8]uril, the through‐space conjugation is further stabilized within the confined cavity. Both the generation and lifetime of triplet state are significantly increased, resulting from the host‐stabilized through‐space conjugation. Additionally, the ultrahigh binding constant of 6.58×1014 M−1 ensures the persistence of host‐stabilization effect. As a result, the host–guest complex acts as a highly efficient catalyst in the photocatalytic oxidation of thioether and aromatic alcohol. In the photodegradation of lignin, a complex natural product, the host–guest complex also exhibits high efficiency, demonstrating its robustness. This line of research is anticipated to enrich the toolbox of supramolecular photochemistry and provide a strategy for fabricating efficient supramolecular photocatalysts. [ABSTRACT FROM AUTHOR]

Poly(triazine imide) is a non-metal semiconductor material with remarkable photocatalytic properties, which was successfully employed for selective photoreactions. Currently, pristine forms of semiconductors are inefficient and rarely used as such. Instead, various composites are being composed on their base in search of more efficient means for photo-activated processes, such as hydrogen evolution, pollution remediation and selective photoreactions. In pursuit of a more efficient photoactive material catalyzing selective photooxidation of an alcohol to an aldehyde, we screened various compositions of PTI and hematite obtained in hydrothermal conditions. Although conversion rates exhibited by the best sample of the composites did not exceed those of pristine PTI, selectivity of the process was improved to 98% at the conversion rate of 99%. [ABSTRACT FROM AUTHOR]

[Display omitted] • A mCN@mPDIP molecular heterojunction is designed for facilitating intimate interface contact and promoting highly efficient interfacial charge transfer. • The S-scheme photogenerated charge transfer mechanism was revealed by in situ irradiated X-ray photoelectron spectroscopy. • The charge separation efficiency of the molecular heterojunction surpasses that of both bulk and nano heterojunctions. • The mCN@mPDIP achieves efficient aerobic oxidation of methyl phenyl sulfide into sulfoxide with a complete conversion of 99.3 % and selectivity of 99.2 %. The construction of S-scheme heterojunctions, which offers a promising approach for spatially separating photogenerated charge carriers with high redox potentials and multimolecular activation, represents a viable modification strategy in photocatalytic applications. However, the prevalent insufficient contact areas between two components result in low interface charge transfer efficiency, thereby impeding the photocatalytic performance of such heterostructures. Herein, we address this limitation by introducing a unique mCN@mPDIP molecular heterojunction through a pH-triggered molecule self-assembly eutectoid technique, enabling intimate interface contact and promoting highly efficient interfacial charge transfer following an S-scheme mechanism. Consequently, the mCN@mPDIP molecular heterojunction achieves significantly improved charge separation efficiency and higher concentration of active carriers compared to typical bCN-bPDIP bulk heterojunction and nCN/nPDIP nano heterojunction. Combined with the effective sulfide activation on mPDIP sites and O 2 activation on mCN sites, the resulting mCN@mPDIP demonstrates outstanding activity in the photocatalytic aerobic oxidation of sulfides into sulfoxides without any redox mediators. [ABSTRACT FROM AUTHOR]

Constructing 3D functional covalent organic frameworks (COFs) with both robust linkage and planar macrocycle building blocks still remains a challenge due to the difficulty in adjusting both the crystallinity and the dominant 2D structures. In addition, it is also challenging to selectively convert inert C(sp3)–H bonds into value-added chemicals. Herein, robust 3D COFs, USTB-28–M (M=Co, Ni, Cu), have been polymerized from the nucleophilic aromatic substitution reaction of D 3h-symmetric 2,3,6,7,14,15-hexahydroxyltriptycene with D 4h-symmetric hexadecafluorophthalocyanine (MPcF16) under solvothermal conditions. These chemically stable dioxin-linked COFs show isostructural tbo topology made up of three kinds of polyhedron subunits, exhibiting high Brunauer−Emmett−Teller surface areas of ≤1477 m2 g−1. In particular, the multiple polyhedron subunits in USTB-28–M could trap N -hydroxyphthalimide at their corners for easily forming stable phthalimide- N -oxyl radicals under visible-light irradiation. The generated radicals efficiently promote the aerobic oxidation of alkyl benzenes with an inert C(sp3)–H bond into various ketones. Among the three investigated COFs, the USTB-28–Co radical initiator exhibits the best photocatalytic oxidation activity, converting ethylbenzene into acetophenone with a turnover frequency of 63 h−1, which is much higher than those of the monomer CoPcF16 (8 h−1) and 2D dioxin-linked counterparts (13 h−1). This is due to the much prolonged lifetime of the excited state for USTB-28–Co based on the femtosecond transient absorption result. The present work not only presents 3D functional COFs with robust connection and permanent porosity, but also illustrates the uniqueness of porous structures of 3D COFs for high-performance photocatalysis. [ABSTRACT FROM AUTHOR]

Novel S-scheme heterojunction interface composite (MnMgPO4@C3N4) of bimetallic phosphate MnMgPO4 and C3N4 with different proportions was successfully constructed in this work. The nanosheet surface structure and the integration interface of two materials endowed the composite heterojunctions with superior visible light absorption and improved photogenerated carrier transfer, boosting the photocatalytic hydrogen production and degradation performance. The interface composite (5C5MMP) with the optimal mass ratio (MnMgPO4/C3N4 = 5/5) achieved the strongest photocatalytic potency. The hydrogen evolution rate was about 3.595 mmol·g−1·h−1, and the pollutants of methylene blue (MB), oxytetracycline (OTC), and tetracycline (TE) were almost entirely degraded within 40 min. The degradation rates were approximately 97.1% (MB), 95.4% (OTC), and 99.7% (TE). Notably, the heterojunction interface composite displayed exceptional photocatalytic stability and structural durability. The photocatalytic mechanism revealed that the 5C5MMP heterojunction interface exhibited the strongest photocurrent response, the least electron transfer resistance, and the lowest carrier recombination rate, resulting in exceptional photocatalytic performance. Furthermore, both C3N4 and MgMnPO4 were identified as n-type semiconductors. The optimized band structure of the composite photocatalyst interface and the enhanced charge carrier separation enabled the 5C5MMP photocatalytic system to generate more reactive photogenerated electrons for reduction and holes for oxidation, significantly accelerating the photocatalytic hydrogen production and pollutant degradation. By proposing an S-scheme heterojunction interface composite, this research offers an innovative strategy for designing efficient composite photocatalysts and underscores the feasibility of using bimetallic phosphate composites to enhance hydrogen production and pollutant removal. [ABSTRACT FROM AUTHOR]

Photocatalysis has emerged as an effective approach to sustainably convert biomass into value-added products. CoSe2 is a promising non-precious, efficient cocatalyst for photooxidation, which can facilitate the separation of photogenerated electron–holes, increase the reaction rates, and enhance photocatalytic efficiency. In this work, we synthesized a stable and efficient photocatalysis system of CoSe2/g-C3N4 through attaching CoSe2 on g-C3N4 sheets, with a yield of 50.12% for the selective photooxidation of xylose to xylonic acid. Under light illumination, the photogenerated electrons were prone to migrating from g-C3N4 to CoSe2 due to the higher work function of CoSe2, resulting in the accelerated separation of photogenerated electron–holes and the promoted photooxidation. Herein, this study reveals the unique function of CoSe2, which can significantly promote oxygen adsorption, work as an electron sink and accelerate the generation of ·O2−, thereby improving the selectivity toward xylonic acid over other by-products. This work provides useful insights into the design of selective photocatalysts by engineering g-C3N4 for biomass high-value utilization. [ABSTRACT FROM AUTHOR]

Here, a molecular semiconductor composite was assembled by integrating atomically precise Ti12-oxo clusters and phosphotungstic acid (PTA) into a cocrystal system. A molecular heterojunction was demonstrated to form between the two units, which allows the charge separation efficiency to be enhanced, resulting in a two-fold increase in photocatalytic activity for cyclohexene oxidation compared to the physically mixed composite. [ABSTRACT FROM AUTHOR]

The valorization of toluene offers a dual solution by addressing its environmental impact while also facilitating the synthesis of a diverse array of valuable fine chemicals and pharmaceutical intermediates, thus ensuring both ecological sustainability and economic viability. We report herein a synergistic approach that harmonizes hydrogen atom transfer (HAT) process with the generation of reactive oxygen species (ROS) under mild condition and low catalyst loading, which enables the efficient synthesis of a broad spectrum of esteemed benzoic acid derivatives and aryl ketones through the photocatalytic oxidation of toluene derivatives. Mechanistic elucidation reveals that the HAT reagent anthraquinone has both the capabilities to abstract hydrogen atoms and the ability to generate singlet oxygen (1O2) during energy transfer with triplet oxygen (3O2), and the combination of these two potencies significantly improves the catalytic efficiency of the reaction. This study not only introduces the amalgamation of HAT with ROS generation but also delineates a systematic approach for the selection of HAT reagents with energy transfer proficiency for ROS generation in catalytic oxidation reactions. [ABSTRACT FROM AUTHOR]

Directly converting methane to methanol with solar light and eco‐friendly oxidants is challenging due to single‐step conversion process where the designed active sites commonly cleave C─H bonds in both methane and methanol. Herein, a novel method is proposed to break activity‐selectivity trade‐off in methane conversion to methanol through interface engineering. Taking BiOI/BN as a proof‐of‐concept model, it's discovered that engineered interface provides distinct active sites for methane activation and overoxidation products photoreduction. Based on in situ infrared spectroscopy, ultrafast laser spectroscopy, and theoretical calculations, it is unlocked that the engineered interface induces the passivation of original trap states in BiOI component, greatly hindering ultrafast trap‐mediated recombination of photo‐induced carriers (≈39.7 ps). Benefiting from it, long‐lived electrons could directly participate in active radicals generation, ensuring effective methane activation. Subsequently, overoxidation carbon intermediates and protons are captured by active sites from the BN component and rapidly accumulated on the surface. This enables effective injection of electrons into bonding orbitals of C─H bonds in methanol, accelerating the occurrence of C─H re‐bonding process. Ultrafast photo‐induced charge and carbon intermediates transfer at interfaces results in high methane conversion rate of 15.5% under atmospheric pressure and maintains methanol selectivity of 86.4% for 24 h long‐time reaction process. [ABSTRACT FROM AUTHOR]

To develop a facile method to prepare an efficient photocatalyst for removing element Hg0 with highly toxic, the coloured TiO2 were prepared through calcining ethanol impregnation method at mild temperature, which is economical and simple and conducive to large-scale industrial promotion. The as-prepared samples were characterised by XRD, SEM, TEM, BET, XPS, EPR, UV-vis etc. and evaluated for the effect of oxygen vacancy concentration on the photocatalytic activity through the removal of zero-valent (Hg0) mercury. The photocatalytic mercury removal efficiency of T200 reached 62.3%, 3 times higher than that of P25. And the related mechanism explanation is proved. [ABSTRACT FROM AUTHOR]

All‐inorganic cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite quantum dots (PeQDs) are successfully incorporated within the cages of zirconium‐based UiO‐series metal–organic frameworks (MOFs) using in situ ship‐in‐a‐bottle method at room temperature under ambient conditions. The resulting mBPP‐MOF, which includes the 4,4′‐(2,2′‐bipyridyl‐5,5′‐diyl)dibenzoic acid (H2BPP) linker, features a larger cavity size than UiO‐66 and UiO‐67‐bpy, allowing for uniform accommodation of PeQDs within its cages. This PeQDs@MOF hybrid heterostructure enhances the separation and transfer of photogenerated charges, enabling the synthesized CsPbBr3@mBPP‐MOF to demonstrate highly selective and stable performance in the photocatalytic oxidation of toluene under visible light irradiation at 395 nm. This advancement represents a potential breakthrough in organic photocatalysis due to the material's low cost, ease of processing, high efficiency, and tunable bandgap. [ABSTRACT FROM AUTHOR]

Photocatalytic CH4 oxidation to ethanol with high selectivity is attractive but substantially challenging. The activation of inert C−H bonds at ambient conditions requires highly reactive oxygen species like hydroxyl radicals (⋅OH), while the presence of those oxidative species also facilitates fast formation of C1 products, instead of the kinetically sluggish C−C coupling to produce ethanol. Herein, we developed a BiVO4 photocatalyst with surface functionalization of Au nanoparticles (BiVO4@Au), which not only enables photogeneration of ⋅OH to activate CH4 into ⋅CH3, but also in situ consumes those ⋅OH species to retard their further attack on ⋅CH3, resulting in an enhanced ⋅CH3/⋅OH ratio and facilitating C−C coupling toward ethanol. The ⋅CH3/⋅OH ratio is further improved by transporting CH4 via a gas‐diffusion layer to the photocatalytic interface, leading to even higher ethanol selectivity and production rates. At ambient conditions and without photosensitizers or sacrificial agents, the BiVO4@Au photocatalyst exhibited an outstanding CH4‐to‐ethanol conversion performance, including a peak ethanol yield of 680 μmol ⋅ g−1 ⋅ h−1, a high selectivity of 86 %, and a stable photoconversion of >100 h, substantially exceeding most of the previous reports. Our work suggests an attractive approach of in situ generation and modulation of the ⋅OH levels for photocatalytic CH4 conversion toward multi‐carbon products. [ABSTRACT FROM AUTHOR]

SrNbO2N is a promising narrow‐bandgap semiconductor for sunlight‐driven water splitting but is generally subject to insufficient photocarrier separation and severe photocorrosion. Here, the targeted single‐crystalline SrNbO2N nanobelts are passivated by consecutive annealing in O2 and N2/NH4F to approach the right N/O ratio (1/2) and anion content (O + N = 60 at%). The passivation measures lead to both a low concentration (≈2.2 × 1015 cm−3) of defects including VO, Nb3+, Nb4+ for efficient photocarrier separation and unique fluorine‐rich, nitrogen‐poor surface with low surface energy for high stability against photocorrosion. Notably, the passivated SrNbO2N nanobelts deliver the highest values of photocurrent density of 4.5 mA cm−2 at 1.23 V versus RHE and stable photocatalytic (PC) Z‐scheme overall water splitting activity of ≈10 µmol h−1 H2 evolution under AM 1.5G illumination when used as photoanode materials for photoelectrochemical (PEC) water oxidation and the photocatalytic O2‐evolution moiety, respectively. These findings provide not only an effective guideline to upgrade the activity and stability of SrNbO2N but also fresh mechanistic insights into the role of passivation measures. [ABSTRACT FROM AUTHOR]

SnS nanoparticles (NPs) were synthesized at different reaction temperatures in the range of 150℃-180℃ (in step size of 10℃) via hydrothermal method using Urea as complexing agent. The structural, morphological, and optical properties of the synthesized nanoparticles were investigated using X-ray diffraction analysis (XRD), Energy-dispersive X-Ray analysis (EDS), and UV–VIS by diffuse reflectance spectroscopy. Analysis of the XRD spectra for synthesized SnS nanoparticles at different reaction temperature are in good agreement with JCPDS card number 001–0984 with preferred orientation of grains along (0 1 3) plane. The EDS analysis suggests that SnS nanoparticles are tin deficient. The energy band gap estimated for SnS nanoparticles synthesized at different reaction temperature are in the range of 1.24 eV to 1.27 eV. Synthesized SnS nanoparticles prepared at reaction temperature of 170℃ were used for photocatalytic degradation of methylene blue (MB) dye under visible light irradiation. The Average photo degradation efficiencies of the SnS NPs for MB dye were found to be 72% for an irradiation time of 150 min. The higher efficiency of SnS nanoparticles may be due to deficiency of tin that is capable of enhanced adsorption sites for photocatalytic oxidation of MB. [ABSTRACT FROM AUTHOR]

[Display omitted] The lack of compactness in heterojunction interfaces and poor charge separation is a great challenge in developing high-efficiency heterojunction photocatalysts. Herein, a novel Bi 4 Ti 3 O 12 -BiPO 4 heterojunction was successfully prepared for the first time by epitaxial growth of BiPO 4 on the surface of Bi 4 Ti 3 O 12 nanosheets. The optimized Bi 4 Ti 3 O 12 -BiPO 4 -0.5 increased the NO oxidation efficiency to 73.05%, surpassing pure Bi 4 Ti 3 O 12 (63.45%) and BiPO 4 (8.35%). Experiments and theoretical calculations indicated that the closely contacted heterointerface between BTO and BPO promoted the generation of the built-in electric field, which led to the formation of the Z- scheme transfer pathway for the photogenerated carriers. Therefore, the separation of photogenerated carriers was facilitated while retaining high redox potential, generating more ·O 2 – and ·OH to participate in NO oxidation. Furthermore, the adsorption of NO and O 2 was enhanced by introducing BiPO 4 , further improving the photocatalytic NO oxidation performance. This work emphasizes the critical role of heterointerface in accelerating charge transfer, providing a basis for the design and construction of tightly contacted heterojunction photocatalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel phosphorescence light-harvesting system with sequential two-step energy transfer processes was constructed. • The tunable multicolor emission was employed for the information anti-counterfeiting and storage. • The sequential two-step energy transfer processes facilitate the conversion of photosensitizer types. • The PLHS was employed to enhance the photooxidation of styrene derivatives and CDC reaction. Making full use of the captured energy by phosphorescence light-harvesting systems (PLHSs) and the tunable photoluminescence in energy transfer process to realize the multiple applications is still the challenge of PLHSs research. In this study, we have successfully constructed a highly effective PLHS with tunable multicolor luminescence and efficient conversion of photosensitizer types, which can further be used in photocatalytic organic conversion, information anti-counterfeiting and storage. The supramolecular polymer of BDBP-CB[8], which is generated by cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)-pyridine derivative (BDBP), realizes a phosphorescence emission and a change in luminescence color. Notably, white light emission was achieved and the logic gate systems were constructed utilizing the application of adjustable luminescence color. More interestingly, PLHS can be constructed by employing BDBP-CB[8] as energy donors, Sulforhodamine 101 (SR101) and Cyanine5 (Cy5) as energy acceptors, which results in a remarkably tunable multicolor photoluminescence to achieve the information storage. Furthermore, we have also found that BDBP-CB[8] can serve as type II photosensitizer for the effective production of singlet oxygen (1O 2) during the photooxidation process of styrene in aqueous environments, attaining a remarkable output rate reaching as high as 89 %. Particularly, compared with 1O 2 produced by type II photosensitizer BDBP-CB[8], the construction of PLHS can effectively convert type II photosensitizer to type I photosensitizer and efficiently generate superoxide anion radical (O 2 •−), which can be used for photocatalytic cross-dehydrogenative coupling (CDC) reaction in the aqueous solution with a yield of 90 %. Thus, we have created a PLHS that not only achieves tunable multicolor emission for information anti-counterfeiting and storage, but also realizes the conversion of reactive oxygen species (ROS) for different types photocatalytic oxidation reactions. [ABSTRACT FROM AUTHOR]

The novel Molecular Cobalt Phthalocyanine modified MIL-68(In)-NH 2 S-scheme Heterojunction exhibit excellent NO oxidation performance with low toxic NO 2 generation. The enhanced activity can be attributed to the Strong O 2 Activation and Enhanced Built-in electric fields [Display omitted] • Molecular-dispersed CoPc/MIL-68(In)–NH 2 heterojunction with Co-N4(II) sites has been successfully synthesized. • The enhanced built-in electric field promote an efficient S-scheme charge transfer. • The Co-N4(II) sites displays bifunctional effects for capturing photoexcited electrons and promoting the O 2 activation. • Improved NO oxidation efficiency and suppression of toxic by-products are achieved. The efficiency of photocatalytic Nitric Oxide(NO) oxidation is limited by the lack of oxygen(O 2) active sites and poor charge carrier separation. To address this challenge, we developed a molecular Cobalt Phthalocyanine modified MIL-68(In)–NH 2 photocatalyst with a robust Built-in electric field(BIEF). In the 2 % CoPc-MIN sample, the BIEF strength is increased by 3.54 times and 5.83 times compared to pristine CoPc and MIL-68(In)–NH 2 , respectively. This BIEF facilitates the efficient S-scheme charge transfer, thereby enhancing photogenerated carrier separation. Additionally, the Co-N4(II) sites in CoPc can effectively trap the separated photoexcited electrons in the S-scheme system. In addition, the Co-N4(II) sites can also serve as active sites for O 2 adsorption and activation, promoting the generation of superoxide radical (O 2 –), thereby driving the direct conversion of NO to nitrate(NO 3 –). Consequently, the 2 % CoPc-MIN sample exhibits a remarkable photocatalytic NO removal efficiency of 79.37 % while effectively suppressing the formation of harmful by-product nitrogen dioxide(NO 2) to below 3.5 ppb. This study provides a feasible strategy for designing high-efficiency O 2 activation photocatalysts for NO oxidation. [ABSTRACT FROM AUTHOR]

Zeolites are a class of porous aluminosilicates possessing high surface area, good hydrothermal stability, strong sorption, and high ion-exchanging potential, and which frequently serve as efficient catalytic materials. The composites which integrate zeolite with alternative substances like metal oxides or carbon-based materials steadily outperform individual constituents. Recently, the application of zeolite-based composites in the field of photocatalytic oxidation and electrocatalytic oxidation/reduction, which is mainly focused on pollution treatment in sewage and air, have garnered significant attention. Several synthesis strategies for zeolite-based composites including post-treatment and in situ hydrothermal synthesis methods are explicated. Meanwhile, multifarious types of zeolite-based photoelectric catalytic composites are also summarized. Finally, we highlight the advancements improving the performance of zeolite-based composites in the photocatalytic treatment of organic pollutants in wastewater and the electrocatalytic reduction of CO2 and organics. [ABSTRACT FROM AUTHOR]