Search

This study investigates the impact of biaxial strain on monolayer black phosphorus (BP) through first-principles calculations, confirming its stability and subsequently modifying its photocatalytic performance. Under biaxial strain, BP exhibits a direct bandgap suitable for photocatalytic hydrogen production during water splitting, albeit with limitations due to its valence band maximum edge. A distinctive GaN/BP heterojunction is proposed, featuring a direct bandgap and advantageous band edge positions conducive to efficient photocatalytic overall water splitting. Under the influence of biaxial strain, the heterojunction type undergoes a transition from direct type-I to direct type-II and Z, augmenting the separation of photoexcited electrons and holes and markedly enhancing the efficiency of photocatalytic hydrogen production. Furthermore, the heterojunction exhibits commendable capabilities in absorbing visible light. This research provides a promising avenue to surmount the constraints associated with monolayer BP in photocatalysis, offering valuable insights for the development of efficient photocatalytic materials. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) are promising candidate materials for photo-driven processes. Their crystalline and tunable structure makes them well-suited for placing photoactive molecules at controlled distances and orientations that support processes such as light harvesting and photocatalysis. In order to optimize their performance, it is important to understand how these molecules evolve shortly after photoexcitation. Here, we use resonance Raman intensity analysis (RRIA) to quantify the excited state nuclear distortions of four modified UiO-68 MOFs. We find that stretching vibrations localized on the central ring within the terphenyl linker are most distorted upon interaction with light. We use a combined computational and experimental approach to create a picture of the early excited state structure of the MOFs upon photoactivation. Overall, we show that RRIA is an effective method to probe the excited state structure of photoactive MOFs and can guide the synthesis and optimization of photoactive designs. [ABSTRACT FROM AUTHOR]

The photochemical generation of nicotinamide cofactor 1,4-NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4'-COOH-bpy)Cl2 to produce enzymatically active NADH. This model subsystem facilitates easy product isolation and achieves a turnover frequency (TOF) of 175 h-1, one of the highest efficiencies reported for inorganic photosensitizer-based nicotinamide cofactor generation. Charge transfer kinetics, fundamental for catalytic solar energy conversion, range from 106 to 108 s-1 for this system highlighting the superior electron transfer capabilities of NRs. This model ensures efficient cofactor production and offers critical insights into advancing systems that mimic natural photosynthesis for sustainable solar-to-chemical synthesis.

Photocatalysis is a promising concept for the direct conversion of solar energy into fuels and chemicals. The design, experimental protocol, and performance of a multimodal and versatile flow reactor for the characterization of powdered and immobilized photocatalysts are herein presented. Ultimately, this instrument enables rigorous evaluation of photocatalysis performance metrics. The apparatus quantifies transient gas-phase reaction products via online real-time gas analyzer mass spectrometry (RTGA-MS). For H2, the most challenging gas, the photocatalytic system's RTGA-MS gas detection sensitivity spans over three orders of magnitude and can detect down to tens of parts per million under atmospheric conditions. Using Pt nanoparticles supported on anatase TiO2 photocatalyst via wet impregnation, the instrument's capability for the characterization of photocatalytic H2 evolution is demonstrated, resulting in an apparent quantum yield (AQY) of 48.1% ± 0.9% at 320 nm, 45.7% ± 0.3% at 340 nm and 31% ± 1% at 360 nm. The photodeposition of Pt on anatase TiO2 was employed to demonstrate the instrument's capability to track the transient behavior of photocatalysts, resulting in an improved 55% ± 2% AQY for H2 evolution at 340 nm from aqueous methanol. This photocatalytic instrument enables systematic study of a wide variety of photocatalytic reactions such as water splitting and CO2 reduction to valuable C2+ fuels and chemicals. [ABSTRACT FROM AUTHOR]

Carbon-based functional nanocomposites have emerged as potent antimicrobial agents and can be exploited as a viable option to overcome antibiotic resistance of bacterial strains. In the present study, graphitic carbon nitride nanosheets are prepared by controlled calcination of urea. Spectroscopic measurements show that the nanosheets consist of abundant carbonyl groups and exhibit apparent photocatalytic activity under UV photoirradiation towards the selective production of singlet oxygen. Therefore, the nanosheets can effectively damage the bacterial cell membranes and inhibit the growth of bacterial cells, such as Gram-negative Escherichia coli, as confirmed in photodynamic, fluorescence microscopy, and scanning electron microscopy measurements. The results from this research highlight the unique potential of carbon nitride derivatives as potent antimicrobial agents.

Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal‐covalent organic framework (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π‐conjugated vinylene‐linked multivariate donor‐π‐acceptor MCOF (D‐π‐A, termed UJN‐1) by integrating benzyl cyanides linker with multiple functional building blocks of electron‐rich triphenylamine and electron‐deficient copper‐cyclic trinuclear units (Cu‐CTUs) moieties, featuring with strong intramolecular charge separation driving force, extended conjugation degree of skeleton, and abundant active sites. The incorporation of Cu‐CTUs acceptor with electron‐withdrawing ability and concomitantly giant charge separation driving force can efficiently accelerate the photogenerated electrons transfer from triphenylamine to Cu‐CTUs, revealing by experiments and theoretical calculations. Benefiting from the synergistically effect of D‐π‐A configuration and vinylene linkage, the highly‐efficient charge spatial separation is achieved. Consequently, UJN‐1 exhibits an excellent CO formation rate of 114.8 μmol g−1 in 4 h without any co‐catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs with imine‐linked (UJN‐2, 28.9 μmol g−1) and vinylene‐linked COF without Cu‐CTU active sites (UJN‐3, 50.0 μmol g−1), emphasizing the role of charge separation driving force and linkage chemistry in designing novel COFs‐based photocatalyst. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H2O2) production. However, the construction of COFs with new active sites, high photoactivity, and wide‐range light absorption for efficient H2O2 production remains challenging. Herein, we present the synthesis of a novel azobenzene‐bridged 2D COF (COF‐TPT‐Azo) with excellent performance on photocatalytic H2O2 production under alkaline conditions. Notably, although COF‐TPT‐Azo differs by only one atom (−N=N− vs. −C=N−) from its corresponding imine‐linked counterpart (COF‐TPT‐TPA), COF‐TPT‐Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal‐free photocatalyst, COF‐TPT‐Azo achieves a high photocatalytic H2O2 production rate up to 1498 μmol g−1 h−1 at pH = 11, which is 7.9 times higher than that of COF‐TPT‐TPA. Further density functional theory (DFT) calculations reveal that the −N=N− linkages are the active sites for photocatalysis. This work provides new prospects for developing high‐performance COF‐based photocatalysts. [ABSTRACT FROM AUTHOR]

Photocatalytic utilization of methanol and nitrate as carbon and nitrogen sources for the direct synthesis of amino acids could provide a sustainable way for the valorization of green "liquid sunlight" and nitrate waste. In this study, we develop an efficient photochemical method to synthesize glycine directly from methanol and nitrate, which cascades the C−C coupling to form glycol, nitrate reduction to NH3, and finally C−N coupling to generate glycine. Interestingly, the involved photocatalytic tandem reactions show a synergistic effect, in which the presence of nitrate is the dominant factor to enable the overall reaction and reach high synthetic efficiency. Ba2+−TiO2 nanoparticles are confirmed as a feasible and efficient catalyst system for the photosynthesis of glycine with a remarkable glycine photosynthesis rate of 870 μmol gcat−1 h−1 under optimal conditions. This work establishes a novel catalytic system for amino acid synthesis from methanol and nitrate under mild conditions. These results also allow us to further suppose the formation pathways of amino acids on the primitive earth, as an extension to proposals based on the Miller‐Urey experiments. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid porous materials (OIHMs) inherit the unique properties from both organic and inorganic components, and the flexibility in the incorporation of functional groups renders the OIHMs an ideal platform for the construction of catalytic materials with multiple active sites. The preparation of OIHMs with precise locations of organic–inorganic components and tunable structures is one of the important topics for the catalytic application of OIHMs, but it is still very challenging. In this feature article, we describe our work related to the preparation of OIHMs via confining active sites in the nanostructure and a layer-by-layer assembly method and their applications in acid–base catalysis, catalytic hydrogenation and photocatalysis with a focus on the elucidation of the synergistic effects of different active sites and the unique properties of OIHMs in catalysis. [ABSTRACT FROM AUTHOR]

The photocatalytic activity of photocatalysts can be enhanced by cation doping, and the dopant concentration plays a key role in achieving high efficiency. This study explores the impact of copper (Cu) doping at concentrations ranging from 0% to 10% on the microstructural, optical, electronic, and photocatalytic properties of zinc oxide (ZnO) nanostructures. The x-ray diffraction analysis shows a non-linear alteration in the lattice parameters with increasing the Cu content and the formation of CuO as a secondary phase at the Cu concentration of >3%. Density functional theory calculations provide insights into the change in the electronic structures of ZnO induced by Cu doping, leading to the formation of localized d electronic levels above the valence band maximum. The modulation of the electronic structure of ZnO by Cu doping facilitates the visible light absorption via O 2p → Cu 3d and Cu 3d → Zn 2p transitions. Photoluminescence spectroscopy reveals a quenching of the defect-related emission peak at approximately 570 nm for all Cu-doped ZnO nanostructures, indicating a reduction in the structural and other defects. The photocatalytic activity tests confirm that the ZnO nanostructures doped with 3% Cu exhibit the highest efficiency compared to other samples due to the suitable band-edge position and visible light absorption. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Photocatalytic aerobic oxidative desulfurization (PAODS) is a sustainable alternative technology to traditional, energy‐intensive fuel desulfurization methods. Nonetheless, its advancement is hindered by the notable challenge of inadequate electron‐hole separation efficiency within the existing catalytic systems. Herein, a Janus 2D/2D heterostructure composed of Co3O4 and CoMoO4 is reported for the PAODS of thiophenic sulfides. Through a combination of detailed experimental characterizations and density functional theory (DFT) calculations, we elucidate the formation of a type II p‐n heterojunction in the catalyst, significantly enhancing electron‐hole separation through electric field force and reducing the possibility of electron‐hole recombination due to the spatial separation of redox centres. The photocatalyst exhibits exceptional activity and demonstrates an impressive performance of 10.4 mmol·g–1·h–1 in the oxidation of dibenzothiophene (DBT). Moreover, the photocatalyst demonstrates profound desulfurization capabilities in real diesel, reinforcing its promising prospects for industrial application. These discoveries provide invaluable insights, both scientifically and practically, towards the development of advanced photocatalysts for PAODS processes. [ABSTRACT FROM AUTHOR]

Solar hydrogen production with semiconductor photocatalyst particles typically requires co‐catalysts, but since co‐catalysts are often deposited in situ, the rate of their nucleation/growth and role in parasitic light absorption are not well controlled. Herein a halted photodeposition‐dialysis method is introduced that affords unprecedented control over platinum (Pt) co‐catalyst loading and morphology on bulk heterojunction organic semiconductor photocatalyst nanoparticles. Pt loading and surface distribution are controlled by tuning the initial Pt precursor concentration and photodeposition time followed by removal of unreacted Pt precursor via dialysis. Applying this method with typical Pt deposition conditions gives a max H2 evolution rate of 140 mmol h−1 g−1 (based on semiconductor mass) with only 15.2 wt.% Pt deposited and suggests an optimum loading of <20 wt.% Pt, above which parasitic light absorption decreases the H2 evolution rate. Moreover, a peak H2 evolution >30 mmol h−1 g−1 is achieved with a Pt loading of only 1.01 wt.% by tuning the deposition conditions to favor a more uniform Pt coverage with small clusters and single atoms over larger Pt NPs. This represents a performance more than eight times higher compared to typical Pt photodepositions (based on Pt) and gives critical insights into optimizing performance. [ABSTRACT FROM AUTHOR]

Herein, we report the impact of external perturbation on the photocatalytic performance of g-C 3 N 4 /CoN 4 heterojunction and concomitant transition from type-I to type-II. The state-of-the-art theoretical modeling presented here is the first study on dynamic role of strain and electric field on g-C 3 N 4 /CoN 4 heterojunction and its potential application as a solar-driven water splitting reaction. Utilizing the density functional theory (DFT) calculation, V. N. et al. recently reported the photocatalytic activity of g-C 3 N 4 /MN 4 (M = Mn, Fe and Co) heterojunction [J. Comput. Chem. 2024 , 45 , 2518-2529, https://doi.org/10.1002/jcc.2746412 ] and subsequently established g-C 3 N 4 /CoN 4 as a type I heterojunction for photocatalytic water splitting reaction [Phys. Chem. Chem. Phys. 2024 , 26 , 21117–21133]. In the present study, we applied external perturbation in the form of mechanical strain, electric field and evaluated the electronic structure properties of the system along with the detailed examination of concomitant optical and magnetic properties of g-C 3 N 4 /CoN 4 heterojunction. The switching of photocatalytic feature from type I to type II originates due to the crossover between valence band maxima (VBM) of g-C 3 N 4 and CoN 4 in presence of external perturbation. Notably, the resulting system acts as a type II photocatalyst for water splitting reaction while applying compressive (negative) strain of −2 to −6% and an electric field of −0.5 and +0.5 V/Å, respectively. Accumulation of photogenerated electrons and holes separately in g-C 3 N 4 and CoN 4 units confirms the perceptible separation of charge carriers and thereby reduces the recombination compared to un-perturbed system. A red-shifted absorption maximum (689 nm), superior charge transfer (0.9e), and clear separation of photogenerated electrons and holes are the origin of enhanced photocatalytic efficiency of g-C 3 N 4 /CoN 4 heterojunction in the presence of external perturbation. We believe that our work will provide enough evidence to the experimentalists to achieve such a system in practice leading to human-friendly applications. Type II g-C 3 N 4 /CoN 4 heterostructure fabricated by an external perturbation strategy for efficient photocatalytic water splitting reaction. [Display omitted] • Density Functional Theory. • Theoretical Modelling of g-C 3 N 4 /CoN 4 heterojunction in presence of biaxial strain and electric field. • Photocatalyst for water splitting reaction. • Valence band crossover of g-C 3 N 4 and CoN 4 units. • Enhanced efficiency of solar energy conversion within the visible spectrum. [ABSTRACT FROM AUTHOR]

g-C 3 N 4 is a promising metal-free photocatalyst for hydrogen production, whose application is difficult due to the low mobility of charge carriers and rapid electron-hole recombination. Here we propose a new route to improve its response to simulated sunlight and prevent electron-hole recombination by grafting mixed Ag–NiO (1:1 nominal Ag/NiO weight ratio) materials, as an alternative to platinum group metal co-catalysts. g-C 3 N 4 was prepared by urea pyrolysis, whereas Ag–NiO was prepared by a co-precipitation method, and then the composites were prepared by physical mixing using sonication-grinding. The presence of Ag–NiO on the surface plays a key role in accepting excited electrons and enhancing their lifetime for a subsequent reduction of protons to hydrogen. Hydrogen production was carried out from the photoreforming of ethanol under simulated sunlight. The results revealed that 2% (Ag–NiO)/g-C 3 N 4 is effective among others with 5.2 times higher H 2 production than unmodified g-C 3 N 4. The percentage of ethanol in the ethanol/water ratio is very important as we have found that with increasing its quantity, the evolution of hydrogen becomes significant. • New series of g-C 3 N 4 photocatalysts modified with mixed Ag–NiO. • Innovative synthesis of isolated Ag–NiO and (Ag–NiO)/g-C 3 N 4 composite. • Ag–NiO significantly reduces electron-hole recombination. • The optimal composite is 2% (Ag–NiO)/g-C 3 N 4. • Hydrogen evolution via ethanol photoreforming under simulated sunlight. [ABSTRACT FROM AUTHOR]

Nitrogenous chemicals are widely used in the synthesis of medicines, fine chemicals, polymers, and agrochemicals. Biomass and its derived molecules are particularly prominent and provide a green and sustainable production route to nitrogenous chemicals because of their substantial reserves, renewability, and environmental friendliness. Great efforts have been made in the catalytic amination of biomass-derived molecules to fabricate nitrogenous chemicals through C–N bond formation. This review summarizes recent progress made in the catalytic amination of biomass-derived molecules including 5-hydroxymethylfurfural (HMF), furfural (FF), levulinic acid (LA), lignin derivatives and α-keto acids based on the strategies of thermocatalysis, electrocatalysis and photocatalysis. Special attention is paid to advanced catalysts, key intermediates, and detailed reaction pathways in different green catalytic systems, and to discussions of the structure–activity relationships and reaction mechanisms. It ends by listing current challenges in the design and synthesis of biomass-derived nitrogenous compounds and proposes perspectives for future research and development. [ABSTRACT FROM AUTHOR]

The current research introduces a novel in-situ and visibly-active heterojunction formation concept to fabricate a sustainable antimicrobial cementitious material. To achieve this, cement mortar incorporating iron-rich industrial waste products (FWPs) was outer-coated with photocatalyst Titanium dioxide (TiO 2). The proposed technique forms a novel surface-active Fe 2 TiO 5 heterojunction oxide layer, which considerably improves the photocatalytic and antimicrobial properties of TiO 2 under the visible spectrum of light. Primarily, the study evaluated the structural suitability of the developed iron-rich cementitious material in terms of its durability and strength properties. The findings indicate that the iron-rich cementitious material performed better than conventional cementitious material. After this, the effectiveness and novelty of the proposed research were examined, such that the Fe 2 TiO 5 photocomposite was subjected to detailed microscopic investigations such as XRD, HRTEM, UV-DRS, XPS, FESEM, etc. The results verified the production of the inherent Fe 2 TiO 5 heterojunction through the presence of Fe in the photocatalyst TiO 2 lattice via the formation of ITO complex bonds. It also revealed that the Fe 2 TiO 5 photocomposite functions effectively under visible light with an energy band gap of 2.57 eV. The antimicrobial activity of the Fe 2 TiO 5 photocomposite was also assessed by neutralizing E.coli bioaerosols. The disinfection results indicated that the Fe 2 TiO 5 photocomposite exhibits excellent antimicrobial properties. It achieved 69.33 % and 95–98 % antibacterial efficiency under dark and visible light, respectively. Thus, the study establishes a Fe 2 TiO 5 photocomposite material that combines photocatalytic and antimicrobial properties, making it suitable for use as a sustainable building material. Also, it contributes to environmental sustainability by promoting a circular economy and green building practices. • The design and manufacturing of an antibacterial and photocatalytic sustainable building material. • Utilization of cement mortar incorporating FWPs to make the surface active Fe 2 TiO 5 heterojunction photocomposite. • Fe from FWPs enhances TiO 2 's photocatalytic action via the inherent concept of Fe 2 TiO 5 heterojunction formation. • The Fe 2 TiO 5 photocomposite potentially inactivates E.coli bioaerosols under visible light. [ABSTRACT FROM AUTHOR]

Polymeric composite materials are in great demand in biomedical and water treatment applications. This is because they possess distinct characteristics and can fulfill specific biomedical needs, in addition to their ability to degrade dyes. This study successfully synthesized sustainable strontium titanate (STO) particles with an average size of 120 nm using the solid-state method. When these STO particles were mixed into a PCL-based polyurethane matrix, the matrix became hydrophilic with a contact angle of 58.60° and its mechanical strength enhanced by 320%. The morphology and surface roughness of the films were determined using FESEM and AFM techniques. The antibacterial studies of polymeric composites film against E. coli, Klebsiella pneumonia, and S. aureus , showing good zone growth, and showing enhanced swelling properties of 270% for wound healing and biomedical applications. The photocatalytic performance of the STO by degrading Methyl Orange (MO) and Congo Red (CR) under UV light, achieving degradation efficiencies of 92.25% for MO and 62.5% for CR over 150 min. These findings suggest that PU scaffolds and STO are suitable for biological and water treatment in industrial applications. [Display omitted] [ABSTRACT FROM AUTHOR]

Photocatalytic conversion of CO 2 into valuable fuels is considered a promising approach for the development of sustainable and renewable energy sources. In this study, we utilized Mo-MOF as a precursor to obtain MoO 3 by pyrolytic derivatization and treated it to obtain MOF-MoO 3-x containing oxygen vacancies as a catalyst for the photocatalytic reduction of CO 2 to CO. MOF derivatization altered the morphology of the MoO 3 , which made the formation of oxygen vacancies easier and facilitated the separation of electron-hole pairs. Meanwhile, the increased specific surface area and the appearance of surface oxygen vacancies enhanced the CO 2 adsorption and activation capabilities of MOF-MoO 3-x. As a result, MOF-MoO 3-x demonstrated a significant enhances in the photoreduction activity of CO 2. Its CO yield was 29.1 μmolg−1h−1, which was 3.7 times higher than that of MOF-MoO 3 and 2.4 times higher than that of H-MoO 3-x. This innovative strategy may provide a new avenue for improving the comprehensive performance of photocatalysts and developing renewable energy sources. MOF-MoO 3-x photocatalytic material derived from Mo-MOF precursor and prepared by ascorbic acid reduction. Compared to the H-MoO 3-x obtained by hydrothermal method, the MOF structure promoted the formation of oxygen defects, the yield of CO reduction by MOF-MoO 3-x had been significantly improved. [Display omitted] [ABSTRACT FROM AUTHOR]

In recent times, there has been a pressing need to discover or manufacture a unique material that can serve as a photocatalyst for organic pollutants that are incapable of degradation. Pure Bi 2 O 3 and Co, Cd co-doped Bi 2 - 2x Co x Cd x O 3 (x = 0.8) nanoparticles were synthesized using the chemical co-precipitation method, but the new approach involves fabricating 10 % reduced graphene oxide Bi 2 - 2x Co x Cd x O 3 /rGO nanocomposites via the ultra-sonication route. This study investigated the effects of Co, Cd, and r-GO doping on the optical, electrochemical, structural, and photocatalytic properties of bismuth oxide. The synthesized nanomaterials were analyzed using X-ray diffraction (XRD), cyclic voltammetry, ultraviolet–visible (UV–Vis), Fourier transform infrared (FTIR), photoluminescence (PL), and Raman spectroscopy. The XRD patterns showed the formation of a monophasic monoclinic structure belonging to space group P21/c, with an average crystallite size estimated around 22–41 nm. According to the UV–visible study, the bandgap energy of Bi 2 O 3 NPs, Bi 2 - 2x Co x Cd x O 3 NPs, and Bi 2 - 2x Co x Cd x O 3 /rGO nanocomposites were 2.64 eV, 2.37 eV and 2.06eV respectively. The cyclic voltammetry technique was used to evaluate the functioning electrodes. In contrast to un-doped Bi 2 O 3 , the synergistic effects of Co, Cd, and r-GO on the substituted material increased the specific capacitance. The pure Bi 2 O 3 , doped Bi 2 - 2x Co x Cd x O 3, and Bi 2 - 2x Co x Cd x O 3 /rGO photocatalyst degraded 62 %, 85 %, and 95.4 % respectively of RB-5 dye after 105 min of sunlight. The phytotoxicity analysis examined the germination of Hordeum vulgare seeds in treated and untreated RB-5 dyes. Additionally, scavenging investigations using reactive species trapping to confirm the dominant reactive species were evaluated. Bi 2 - 2x Co x Cd x O 3 /rGO nanocomposites are better at photocatalysis and have a narrow bandgap, which makes them useful as solar-active photocatalysts for getting rid of dyes in wastewater. In future, their composites with conducting polymers may improve their electrochemical and photocatalytic behaviour as well. [ABSTRACT FROM AUTHOR]

Due to the advancement of industrialization, water pollution has become an alarming global issue. Many organic dyes, such as crystal violet and rhodamine B, present in industrial wastewater are causing severe health problems. Both of these dyes are carcinogenic. For their degradation, ferrites are synthesized in this research. Ferrites have high absorbing potential in visible regions and fast movement of charge carrier species. Therefore, the ferrites are potentially used in photocatalysis to purify contaminated water. Graphitic carbon nitride shows enhanced separation of charges, which lowers the rate of recombination of charge carrier species. Lithium nickel ferrite, lithium nickel ferrite doped with terbium, and its composite with graphitic carbon nitride (g-C 3 N 4) are synthesized by sol-gel and ultra-sonication methods, respectively. The prepared samples are analyzed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), Electrochemical impedance spectroscopy (EIS), and Mott-Schottky analysis. The bandgap of LiNiFe 2 O 4 and LiNiTbFe 2 O 4 was 2.35 eV, and 1.87 eV, respectively. LiNiTbFe 2 O 4 @g-C 3 N 4 degraded 86 % crystal violet and 83 % rhodamine B in 120 min. The LiNiTbFe 2 O 4 @g-C 3 N 4 composite showed the maximum degradation and can be potentially used in wastewater treatment. [ABSTRACT FROM AUTHOR]

Cotton textiles play a universal role in everyday life, but they are prone to stain and serve as a primary channel for transmitting viruses and bacteria. The photocatalytic/antibacterial coatings are highly effective in addressing bacterial contamination on fabrics, although their efficacy diminishes with continuous use and washing. Here, insights are provided into the attachment of LiNbO 3 on cotton surfaces using eco-friendly chemical activators to promote resistance to washing cycles, self-cleaning, and bactericide textiles. LiNbO 3 nanoparticles were synthesized by low-temperature hydrothermal synthesis and directly applied to cotton fabric using immersion. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) N 2 adsorption, diffuse reflectance for band gap determination, and Raman spectroscopy. A simple and effective impregnation method was used, promoting an ester-bond attachment between the cotton surface and the activators. Microscopy analysis (SEM) confirmed the successful deposition of the nanoparticles on cotton fabric. The LiNbO 3 coating consisted of transparent layers and did not change the properties of cotton. Methylene blue stains are generally eliminated under UV light after 2 h using nanoparticles and activators. Antibacterial properties were evaluated under visible light through direct contact with bacterial suspensions and culturing. The coated cotton fabric that was activated with oxalic acid exhibited significant photocatalytic antibacterial activity against both Escherichia coli (gram-negative) and Staphylococcus aureus (gram-positive) bacteria, with bacterial reduction rate above 97 %, even after 10 washing cycles. This performance can be attributed to the effective coupling of LiNbO 3 with oxalic acid in the cotton's surface and its resistance to washing out. This study's novel synthesis and coating method offers an environmentally friendly, cost-effective, and straightforward approach for producing LiNbO 3 self-cleaning and antibacterial surface-activated cotton. [ABSTRACT FROM AUTHOR]

The field of bioorthogonal chemistry has revolutionized our ability to interrogate and manipulate biological systems at the molecular level. However, the range of chemical reactions that can operate efficiently in biological environments without interfering with the native cellular machinery, remains limited. In this context, the rapidly growing area of photocatalysis offers a promising avenue for developing new type of bioorthogonal tools. The inherent mildness, tunability, chemoselectivity, and external controllability of photocatalytic transformations make them particularly well‐suited for applications in biological and living systems. This minireview summarizes recent advances in bioorthogonal photocatalytic technologies, with a particular focus on their potential to enable the selective generation of designed products within biologically relevant or living settings. [ABSTRACT FROM AUTHOR]

Herein, we disclose a simple copper‐catalyzed method for enantioselective allylic C(sp3)−H oxidation of unsymmetrical acyclic alkenes, specifically 1‐aryl‐2‐alkyl alkenes. The C−H substrates are used in limiting amounts, and the products are obtained with high enantioselectivity, E/Z‐selectivity, and regioselectivity. The method exhibits broad functional group tolerance, and E/Z‐alkene mixtures are suitable C−H substrates. The transformation is enabled by light irradiation, which sustains the enantioselective copper catalysis by photoinduced oxidant homolysis. [ABSTRACT FROM AUTHOR]

Many photocatalysts were initially developed or used as emitters for organic light emitting diodes (OLEDs). This feature article summarizes the different generations of OLED emitters and connects the photophysical processes with those relevant for photocatalysis. The focus is on the general properties OLED emitters and photocatalysts are designed for and how photocatalysis has benefitted from OLED research. Sometimes optimization of an OLED emitter leads to a better photocatalyst while some properties are optimized into opposite directions. To discover new classes of photocatalysts in the future it is important to consider what good OLED emitters and good photocatalyst have in common and where they diverge. Within recent years, fully organic thermally activated delayed fluorescence (TADF) emitters had the most significant impact in both fields and thus are discussed with specific focus. [ABSTRACT FROM AUTHOR]

This study examines the effect of TiO₂ doping on the catalytic performance of copper ferrite (CuFe₂O₄) nanoparticles in degrading methyl green dye under visible light. Copper ferrite nanoparticles were synthesized and doped with varying TiO₂ concentrations. The catalysts were characterized using XRD, SEM, EDX, and BET surface area analysis. The TiO₂-doped copper ferrite catalysts showed significantly enhanced catalytic activity compared to undoped copper ferrite. The optimal doping concentration of 10 wt% TiO₂ achieved a degradation efficiency of 92 % for methyl green dye after 60 min of irradiation. The BET surface area increased with TiO₂ doping, contributing to the improved catalytic performance. Reusability tests over five cycles indicated a slight decrease in efficiency, attributed to the loss of active sites. These results indicate that TiO₂ doping effectively enhances the catalytic properties of copper ferrite, making it a viable option for environmental remediation. [ABSTRACT FROM AUTHOR]

The rampant misuse of organic dyes has exacerbated environmental pollution to an alarming degree. SrBi 4 Ti 4 O 15 , a layered perovskite semiconductor material, demonstrates considerable potential in the degradation of organic dyes, and efforts have been made to enhance its photocatalytic efficiency. In this study, La3+ doping was utilized to synthesize SrBi 4-x La x Ti 4 O 15 (x = 0, 0.10, 0.15, 0.25, 0.40) nanosheet photocatalysts, and their photocatalytic performance and underlying mechanisms were comprehensively investigated. XRD and Raman spectroscopy revealed that La3+ doping replaced Bi3+ at the A-site, resulting in a reduction of the interlayer spacing of [TiO 6 ] octahedra. Combined with DFT calculations, La3+ doping was found to widen the band gap of SrBi 4 Ti 4 O 15 and raise the Fermi level. Additionally, La3+ doping significantly increased the ratio of the Ti 3d component at the bottom of the conduction band, favoring the migration of photogenerated electrons along the [TiO 6 ] octahedra and accelerating the separation of photogenerated carriers. SEM and BET analyses revealed that La3+ doping not only increased the size of the nanosheets but also significantly enhanced their specific surface area, thereby exposing more active sites. Degradation experiments of Rhodamine B (Rh B) under UV light demonstrated that the photocatalytic efficiency of SrBi 3.75 La 0.25 Ti 4 O 15 (k = 0.0514 min-1) was 2.66 times higher than that of the original SrBi 4 Ti 4 O 15 (k = 0.0193 min-1). The theoretical degradation pathway of Rh B was elucidated using LC-MS analysis and the developmental toxicity of potential intermediates was analyzed. Moreover, the SrBi 3.75 La 0.25 Ti 4 O 15 photocatalyst also exhibited excellent degradation efficacy against Methylene Blue (MB), Crystal Violet (CV), and Methyl Orange (MO). This study provides both theoretical and experimental insights into improving the photocatalytic performance of SrBi 4 Ti 4 O 15 , thereby enhancing its potential for industrial application. [Display omitted] [ABSTRACT FROM AUTHOR]

Mesoporous catalysts with a high specific surface area, accessible pore structures, and appropriate band edges are desirable for optimal charge transfer across the interfaces, suppress electron‐hole recombination, and promote redox reactions at the active sites. The present study demonstrates the rational design of mesoporous ZnFe2O4@g‐C3N4 magnetic nanocomposites (MNCs) with different pore sizes and pore volumes following a combination of facile thermal itching and thermal impregnation methods. The MNCs preserve the structural, morphological, and physical attributes of their counterparts while ensuring their effectiveness and superior catalytic capabilities. The morphological analysis confirms the successful grafting and confinement of ZnFe2O4 nanoparticles with the polymeric g‐C3N4 nanosheets to form heterojunctions with numerous interfaces. The MNCs possess uniformly distributed small mesopores (pore size <4 nm), ample active sites, and a high specific surface area of 62.50 m2/g. The mesoporous ZnFe2O4@g‐C3N4 notably improve hydrogen evolution rate and methylene blue dye degradation. The optimal loading weight of ZnFe2O4 is 20 %, in which the MNCs display the highest hydrogen evolution rate of 1752 μmol g−1 h−1 and photo‐Fenton dye degradation rate constants of 0.147 min−1, upon solar‐light illumination. Furthermore, the photocatalysts demonstrate recyclability over five consecutive cycles, confirming their stability, while easy separation using a simple magnet underscores practical utility. [ABSTRACT FROM AUTHOR]

In this study, MgAlFe‐layered double hydroxide (LDH) was prepared using the co‐precipitation method, and its performance as a photocatalyst for methylene blue (MB) degradation was evaluated. XRD and FTIR analyses confirmed the crystalline structure and successful incorporation of Al into the LDH layers. SEM and TEM images revealed a uniform morphology and layered structure and UV–vis DRS analysis showed that MgAlFe‐LDH has an appropriate band gap for visible light absorption. Photoluminescence studies indicated good charge separation, reducing electron‐hole recombination and enhancing photocatalytic performance. The effects of the Mg/Al/Fe molar ratio, illumination time, catalyst dosage, MB concentration, and pH on the degradation efficiency were examined. Optimized conditions of Mg/Al/Fe molar ratio 3:0.9:0.1, 180 min illumination, 10 mg L⁻¹ catalyst, 20 mg L⁻¹ MB, and pH 13 yielded a remarkable 90.4% MB degradation efficiency. The primary active species in the photocatalytic reaction were identified as hydroxyl radicals (·OH) and holes (h⁺). The incorporation of ternary LDH enhances the photocatalytic performance due to its high stability, versatility, and ability to integrate multiple metal cations. This study broadens the application of LDH in treating organic dye wastewater and provides new insights into the photocatalytic degradation of MB. [ABSTRACT FROM AUTHOR]

A facile wet chemical approach was adopted to synthesize zinc oxide, titanium dioxide, and iron (II, III) oxide, followed by the synthesis of ZnO–TiO2–Fe3O4 nanocomposite via physical mixing. The synthesized nanoparticles were characterized using X‐ray diffraction, UV–visible spectroscopy, vibrating sample magnetometry, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy to investigate various physical and chemical characteristics of the prepared samples. Furthermore, the catalytic reduction of methylene blue (MB) and rhodamine B (Rh B) dyes was carried out using prepared nanomaterials as catalysts under UV–visible light illumination. It was observed that the degradation efficiency of the nanocomposite was equivalent to or slightly better than TiO2 nanoparticles and higher than ZnO nanoparticles against both dye solutions. Its removal efficiency using an external magnetic field is much higher than that of the constituent nanoparticles, owing to its higher saturation magnetization. So, the obtained results suggest that the produced nanocomposite can be employed as a high‐potential catalyst for reducing organic dyes and pollutants in wastewater treatments. [ABSTRACT FROM AUTHOR]

The article reports the synthesis of an ordered mesoporous network of heterophase TiO2 monoliths as a visible light-responsive photocatalyst using tri-block copolymers of Pluronic F108, P123 and F127 as structure-directing agents (SDAs) and temperature-controlled calcination (450–650 °C) has been carried out by direct templating-assisted hydrothermal approach. The structural/surface morphology and topographical properties of the photocatalyst are characterized using FE-SEM-EDAX, HR-TEM-SAED, p-XRD, VB-XPS, PLS, TG/DTA, UV-Vis-DRS, BET/BJH and zeta potential analysis. The undoped heterophase mesoporous TiO2 monoliths with in-built lattice/surface defects exhibit visible light photocatalytic properties, successfully dissipating Reactive Brown 10 (RB-10) dye. The influence of physicochemical parameters, such as SDAs, temperature, pH, dye concentration, catalyst dosage, photosensitizers and light intensities, are optimized for maximum photocatalytic performance at a shorter timespan. The F127-assisted mesoporous TiO2 monolith (550 °C) exhibits superior degradation kinetics (15 min) for RB-10 dye solution (20 ppm) at pH 2.0–3.0 using a photocatalyst dosage of 50 mg and 2 mM of KBrO3, irradiated with 150 W/cm2 tungsten lamp. The photocatalysts are fabricated without complicated chemical modifications and display topmost efficiency in quickly decontaminating persistent pollutants. The photoproducts from RB-10 photocatalytic degradation are investigated using HR-MS analysis. The photocatalyst can be reused efficiently for six cycles, even under extreme conditions. [ABSTRACT FROM AUTHOR]

This research investigates a novel nanocomposite material composed of reduced graphene oxide (rGO) and nickel-5,15-bisdodecylporphyrin (Ni-BDP) nanoparticles for the effective removal of methyl orange (MO), a harmful synthetic dye, from water. The structure and composition of the synthesized rGO/Ni-BDP nanocomposite were characterized using high-resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and ultraviolet-visible (UV-Vis) spectroscopy. The study demonstrates the material's efficacy as both a catalyst and adsorbent for MO removal. Optimal performance was observed at pH 3.0, where the positively charged nanocomposite surface facilitated strong interactions with negatively charged MO molecules, leading to enhanced photocatalytic activity. Under these conditions, 0.01 g of the nanocomposite achieved an impressive 86.2% MO removal efficiency. Furthermore, the study explored the reusability of the rGO/Ni-BDP nanocomposite in repeated cycles of photocatalytic MO degradation under visible light irradiation. While exhibiting some decrease in efficiency over five cycles, the nanocomposite maintained a respectable degradation rate even after multiple uses. Finally, the antimicrobial properties of the nanocomposite were evaluated against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria exhibiting a zone of inhibition measuring 23 mm and 26, respectively. The minimum inhibitory concentration (MIC) values of 2.50 µg/ml and 1.25 µg/ml for Escherichia coli and Staphylococcus aureus, respectively. The results revealed significant antibacterial activity, demonstrating the broad-spectrum efficacy of the rGO/Ni-BDP nanocomposite. This research underscores the potential of the rGO/Ni-BDP nanocomposite as a versatile material for environmental remediation and antibacterial applications. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The first catalytic asymmetric total synthesis of (+)‐propolisbenzofuran B, enabled by a highly enantioselective rhodium‐catalyzed hydrogenation of a tetrasubstituted olefin, was described. Other noteworthy aspects include the construction of the central hydrodibenzo[b,d]furan core through a sequence of Zn(II)‐mediated regioselective benzofuran formation and Dieckmann condensation, as well as C‐H oxidations, involving a visible light‐induced Fe(III)‐catalyzed benzylic C(sp3)‐H oxidation. Additionally, the absolute configuration was confirmed by X‐ray analysis of a carbonate intermediate. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Development of heterogeneous molecular photocatalysts for promising light‐driven hydrogen evolution reaction (HER) is highly demanding but still challenging. Here, we report the blue‐greenish emitting dinuclear metal–organic halides as photocatalyst by incorporating site‐specific single copper(I) atoms that exhibit an efficient carbon‐negative H2 production. Interestingly, the electronic properties, including the spin and charge density of central Cu(I) active site, can be triggered by substituent modulation in metal–organic halides, which greatly affect the exciton dissociation kinetics and thus the HER reactivity. The optimized spin density in these heterogeneous photocatalysts drastically boosts the hydrogen production rate from 1250 to 3130 μmol·g–1·h–1. Our molecular strategy provides a platform that rationally facilitates electronic modulation of copper(I) atoms, tunes the macroscopic optoelectronic properties of photocatalysts and boosts carbon‐negative HER activity, extending the boundaries of conventional molecular‐based photocatalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A novel method for synthesizing α‐oxygen organoboron compounds has been developed through acylsilane‐based carbene insertion reactions into C—B bonds. As coupling partners, readily available organoboron compounds (alkenyl, allyl, and allenyl B(pin)) were employed. Based on the substrates, pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process (from carbon to boron) would occur, delivering the α‐oxygen organoboron compounds with great diversities. Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process. Besides, no matter which isomer of substrate (Z or E) was used, the reaction with β‐aryl‐substituted alkenyl B(pin) affords both isomers of products (Z and E, separable through column chromatography). Trapping experiments indicated the triplet energy transfer process was involved. [ABSTRACT FROM AUTHOR]

In this study, nanocomposites of g‐C3N4/MN4 (where M is Mn, Fe and Co) have been designed using advanced density functional theory (DFT) calculations. A comprehensive analysis was conducted on the geometry, electronic, optical properties, work function, charge transfer interaction and adhesion energy of the g‐C3N4/MN4 heterostructures and concluded that g‐C3N4/FeN4 and g‐C3N4/CoN4 heterojunctions exhibit higher photocatalytic performance than individual units. The better photocatalytic activity can be attributed mainly by two facts; (i) the visible light absorption of both g‐C3N4/FeN4 and g‐C3N4/CoN4 interfaces are higher compared to its isolated analogs and (ii) a significant enhancement of band gap energy in g‐C3N4/FeN4 and g‐C3N4/CoN4 heterostructures limited the electron–hole recombination significantly. The potential of the g‐C3N4/MN4 heterojunctions as a photocatalyst for the water splitting reaction was assessed by examining its band alignment for water splitting reaction. Importantly, while the electronic and magnetic properties of MN4 systems were studied, this is the first example of inclusion of MN4 on graphene‐based material (g‐C3N4) for studying the photocatalytic activity. The state of the art DFT calculations emphasis that g‐C3N4/FeN4 and g‐C3N4/CoN4 heterojunctions are half metallic photocatalysts, which is limited till date. [ABSTRACT FROM AUTHOR]

In the present research, it is reported that ball milling technique can be applied to enhance the photocatalytic properties of MnO and ZrO 2 metal oxide powders (MZOx) furthermore the fabricated photocatalyst can be used for the degradation of tetracycline (TTC). XRD analyses revealed that increasing the milling time resulted in the formation of a pure metallic Mn crystal phase, which boosted the antibiotic degradation rate. It was confirmed by SEM technique that the morphological structures of the particles were generally small and uniform. The band gap energy was calculated as 3.70 eV for the hybrid metal oxide. Additionally, the adsorptive and photoluminescence features were illuminated via DRS and PL analyses. The effect of milling time had a major impact on the photodegradation rate of TTC, and the 8 h milling sample (MZOx-8h) exhibited the highest catalytic degradation activity (79.4 %). Low photocatalytic activity was obtained at acidic pHs and increased at alkaline pHs. The presence of H 2 O 2 sharply decreased photocatalytic process time (60 min) and 94.3 % of the TTC was degraded at 7.5 mM H 2 O 2. The photocatalytic degradation process proceeded through superoxide radicals and was supported by holes. The stability of MZOx-8h almost remained constant (70.02 %) even after seven cycles. It was determined that the presence of oxalic acid positively affected the progress of TTC degradation reactions. Further, practical application areas were investigated and MZOx-8h doped on support materials was found to be suitable for such applications in proportion to the doping ratio. Finally, it was demonstrated that MZOx-8h exhibited remarkable performance in photocatalytic reactions of different types of organic pollutants. The synergistic nature of MnO and ZrO 2 with the contribution of ball milling time effect resulted in high photocatalytic activity. • High purity metallic Mn phase was successfully synthesized by ball-milling. • MZOx was used for the first time in TTC photodegradation. • TTC degradation was stable in the seventh cycle. • The different organic pollutants were removed with high efficiency. [ABSTRACT FROM AUTHOR]

The study successfully enabled the creation of ceramic surfaces with multi functionalities, including superhydrophilicity, self-cleaning, antibacterial properties, and photocatalytic activity, by applying a glaze composition rich in nano ZnO/Cu–ZnO and utilizing surface chemistry and unique texturing on porcelain tiles. The tiles, coated with unique glaze compositions, were fired in an industrial furnace and heat treated. The crystalline phases and surface morphology of glazed surfaces were systematically evaluated using XRD, SEM, FT-IR, drop shape analyzer, and surface roughness profilometer. Key-factors affecting the wettability, self-clean ability, photocatalytic activity and antibacterial efficacy were discussed. Adding nano Cu into the glaze mixture that is rich in ZnO improves the evolution of zincite crystals, increases the specific surface energy, decreases surface roughness, provide superhydrophilicity and promotes the antibacterial effectiveness and photocatalytic activity. Superhydrophilic surfaces doped with nano Cu–ZnO display antibacterial characteristics that do not require UV or visible light. The quick achievement of complete self-cleaning, up to 100 %, is due to the presence of nano Cu particles in its structure. Hydrophilicity has the ability to improve the efficiency of photocatalysis. If a surface exhibits superhydrophilic properties, it shows exceptional photocatalytic performance. A surface that is solely photohydrophilic may not maintain self-cleaning. Hydrophilicity may be more important than photocatalysis in the self-cleaning effect. [ABSTRACT FROM AUTHOR]

[Display omitted] • Combining tetragonal BTO nanoparticles and 2D MXene nanosheets creates BTO-MX, which can degrade 90 % of RhB in 15 min. • MXene nanosheets enhance electrical conductivity and energy conversion rate during advanced oxidation process. • The heterogeneous structure of BTO-MX provides sufficient active sites, aiding in the adsorption and degradation of RhB. • The synergistically piezo-photocatalytic properties enabled by efficient carrier generation and separation in BTO-MX. Piezo-photocatalysis combines photocatalysis and piezoelectric effects to enhance catalytic efficiency by creating an internal electric field in the photocatalyst, improving carrier separation and overall performance. This study presents a high-performance piezo-photocatalyst for efficient dye degradation using a synergistic barium titanate (BTO)-MXene composite. The composite was synthesized via a facile method, combining the unique properties of BTO nanoparticles with the high conductivity of MXene. The structural and morphological analysis confirmed the successful formation of the composite, with well-dispersed BTO nanoparticles on the MXene surface. The piezo-photocatalytic activity of the composite was evaluated using a typical dye solution (Rhodamine B: RhB) under ultraviolet irradiation and mechanical agitation. The results revealed a remarkable enhancement in dye degradation (90 % in 15 min for piezo-photocatalysis) compared to individual stimuli (58.2 % for photocatalysis and 95.8 % in 90 min for piezocatalysis), highlighting the synergistic effects between BTO and MXene. The enhanced catalytic performance was attributed to the efficient charge separation and transfer facilitated by the composite's structure, leading to increased reactive species generation and dye molecule degradation. Furthermore, the composite exhibited excellent stability and reusability, showcasing its potential for practical applications in wastewater treatment. Overall, this work represents a promising strategy for designing high-performance synergistic catalysts, addressing the pressing need for sustainable solutions in environmental remediation. [ABSTRACT FROM AUTHOR]

Properly designed interfacial electric fields between CdS and Bi 2 MoO 6 can effectively promote carrier separation and then enhance photocatalytic CO 2 reduction. [Display omitted] • CdS/Bi 2 MoO 6 composite materials were synthesized by in-situ growth method. • CdS/Bi 2 MoO 6 exhibits excellent photocatalytic CO 2 reduction performance. • Properly designed interfacial electric fields and interfacial chemical bonds can effectively promote carrier separation. • The photo-corrosion is effectively suppressed in this photocatalytic system. Constructing strong interfacial electric fields to enhance the surface charge transport kinetics is an effective strategy for promoting CO 2 conversion. Herein, we present the fabrication of CdS-Bi 2 MoO 6 Z-scheme heterojunctions with a robust internal electric field (IEF) using an in situ growth technique, establishing chemical bonding between the components. The IEF at the interface can offer an impetus for the segregation and transportation of photogenerated carriers, while the Cd-O chemical bonding mode acts as a rapid conduit for these carriers, thereby reducing the charge transfer distance. As a result, the Z-scheme charge transfer is accelerated due to the synergistic influence of these two factors. Therefore, the optimized CdS/Bi 2 MoO 6 Z-scheme heterojunction possesses significantly enhanced dynamic carrier mobility, thus promoting the conversion of CO 2 to CO without the need for additional co-catalysts or sacrificial agents. This optimization yields a remarkable CO selectivity of up to 97%. Meanwhile, the expedited Z-scheme charge transfer mechanism is validated through X-ray photoelectron spectroscopy, Kelvin probe force microscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. [ABSTRACT FROM AUTHOR]

Two‐dimensional (2D) semiconductors with unique structures and surface physicochemical characteristics have been extensively employed for efficient photocatalysis. Recently, surface coordination activation interactions have obtained attention in promoting photocatalytic efficiency as they establish bridges between reactants and photocatalysts. Accordingly, a burgeoning trend in the design of 2D photocatalysts is regulating the surface active centers for coordinating with reactants. These attempts have developed various effective strategies to optimize the 2D photocatalysts and provide in‐depth insights into the structure‐function relationship for heterogeneous photocatalysis. Herein, we summarize recent advances in surface engineering in designing efficient 2D photocatalysts, focusing on coordination activation. We emphasize the advantages of coordination activation as a versatile medium for engineering the surface of photocatalysts. In particular, the discussion includes various strategies for surface engineering and the structure‐function relationship in photocatalysis. This work systematically concludes the significance and future challenges of coordination activation in the surface functionalization of 2D photocatalysis, shedding light on the design of next‐generation photocatalysts. [ABSTRACT FROM AUTHOR]

Here, we present the synthesis of polysubstituted chalcogenofurans involving an oxidative cycloaddition between 1,3‐diones and chalcogenoalkynes. The method utilizes blue LEDs as a clean energy source, methylene blue as a photocatalyst – an inexpensive and non‐toxic dye – and ammonium persulfate as an oxidant, all conducted at room temperature. This benign protocol enables access to a wide range of chalcogenofurans with good to excellent yields and outstanding regioselectivity. Only one regioisomer was obtained, indicating strong radical stabilization by the chalcogen atom. Various functionalities in both alkynes and 1,3‐diones demonstrated amenability to the developed reaction. A mechanistic understanding, derived from control experiments and the detection of radical intermediates, suggests that a radical forms at the carbon‐2 position of the 1,3‐dione, which subsequently adds to the chalcogenoalkyne, resulting in the formation of an olefinic intermediate. Following this, an intramolecular radical addition occurs, which, upon photoredox cycle closure, leads to the formation of the desired products. [ABSTRACT FROM AUTHOR]

Two novel metal‐free organic dyes, namely the mono‐anchoring KMT1 and di‐anchoring KMT2 dyes, have been synthesized to function as photosensitizers for utilizing in photocatalytic hydrogen production systems. They adopt the donor‐donor‐π‐acceptor and donor‐donor‐(−π‐acceptor)2 configurations, respectively, featuring triphenylamine and fluorene moieties as electron donors, thiophene as the π‐bridges and cyanoacrylic acid as the acceptors/anchoring groups. It was found that the photocatalytic performance of the di‐anchoring dye significantly outperforms that of its mono‐anchoring counterpart. KMT2‐based photocatalytic system demonstrated remarkable performance, producing 3520 μmol (84.9 mL) of hydrogen over a span of 257 hours under blue light irradiation, with a turnover number (TON) of 56300, a turnover frequency (TOFi) of 1862.7 h−1, an initial hydrogen production activity (activityi) of 1164180 and an apparent quantum yield (AQYi %) of 19.9. This performance is among the top‐tier when compared to other dyes used in similar photocatalytic systems. The results clearly illustrate that the di‐anchoring dye possesses several advantages, including a broad absorption spectrum, higher absorptivity, and a relatively slower charge recombination rate. These attributes collectively contribute to its superior overall performance in photocatalysis. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting for hydrogen evolution is a highly topical subject in academic research and a promising approach for sustainable fuel production from solar energy. Due to the mismatched energy diagram of the photosensitizer (especially semiconductor‐based materials where band‐edge engineering is not trivial) and the redox potential of the half‐reactions of water splitting, photocatalytic H2 generation from water splitting is usually accelerated by the addition of hole scavengers, i.e. sacrificial reagents such as alcohols, amines, and thiols. However, the source of the protons of the evolved H2 is often neglected, and it is questionable whether such systems are really water splitting. Here, we discuss recent reports on sacrificial reagent‐assisted photocatalytic water splitting and present our recent findings, which showcase that the sacrificial reagent in the investigated photocatalytic water splitting systems inherently undergoes acceptorless dehydrogenation, with H2O serving as the proton shuttle, the amount of which doesn't change during the course of the reaction. [ABSTRACT FROM AUTHOR]

Semiconductor heterojunctions have garnered extensive interest in photocatalytic hydrogen generation, yet the limited light absorption and charge transfer efficiencies still restrict the photocatalytic performance. The topological insulator has unique surface states and high‐mobility electrons, demonstrating the significant potential for enhancing photocatalysis. Herein, a ternary photocatalyst based on a topological insulator, in which CdS and ZnS nanoparticles are grown on Bi2Se3 nanotube, is prepared for efficient photocatalysis driven by topological surface state for the first time. Under simulated solar light irradiation, the CdS/ZnS/Bi2Se3 nanotubes display a robust photocatalytic hydrogen production rate of 7.13 mmol h−1 g−1, which is 69.2 times of CdS and comparable to many CdS‐based photocatalysts. The unique hollow structure, topological surface state of Bi2Se3, and cooperative bandgap excitations of the three components endow the hybrids with wide light response to harvest solar energy. Meanwhile, the multichannel charge transfer facilitated by topological surface state and internal electric fields within the hybrids effectively suppresses the recombination of the photogenerated charge carriers. This mechanism maintains a high concentration of stable electrons on Bi2Se3, resulting in highly efficient hydrogen production. This work provides a new inspiration for designing heterojunction photocatalysts based on topological insulators for high‐efficiency solar‐driven energy conversion. [ABSTRACT FROM AUTHOR]

The need for carbon‐neutralization technologies has prompted significant interest in developing materials for CO2 reduction. Donor–acceptor (D–A) based flexible porous coordination polymers {[Zn(o‐phen)(ndc)].(guest)}n, (guest = anthracene = 1‐Ant, and pyrene = 1‐Pyr) are reported as photocatalysts for CO2RR, yielding higher order CH4 product. Electron‐rich anthracene (Ant) and pyrene (Pyr) guests are confined within nanopores, forming D–A charge transfer (CT) complexes with o‐phen ligand of the host. CT interaction enhances visible light absorption and modulates excitonic properties of the photocatalyst by electronic push‐pull effect (exciton binding energy 87 meV for 1‐Ant and 104 meV for 1‐Pyr). Electron donation capability varies from Pyr to Ant, affecting catalytic properties; 1‐Ant yields 1.24 mmolg−1 of CH4 (0.47 mmolg−1 for 1‐Pyr) with CO as minor product. A mixed‐metal multivariate PCP {[Zn0.55Co0.45(o‐phen)(ndc)].(Ant)}n, (1′‐Ant) prepared based on solid‐solution approach by substituting Zn(II) with redox‐active Co(II) enhances CH4 production (2.79 mmolg−1, ≈94% selectivity). D–A CT complex harvests visible light and channels electrons to Co(II) for CO2RR. In situ DRIFTS and theoretical studies elucidate Co(II) site's role in CO2 binding and stabilizing reaction intermediates. This work underscores guest‐modulated electron transfer in PCPs for tailoring catalytic properties by introducing a redox‐active metal in a multivariate approach. [ABSTRACT FROM AUTHOR]

Harnessing the energy generated from the evaporation of water has received considerable research attention in materials science; however, challenges such as poor conversion efficiency and low current output persist. Herein, an innovative synergistic material system based on titanium dioxide nanotubes coated with polypyrrole (PPy@TiO2NTs) is introduced for the simultaneous production of electricity and clean water from solar energy and seawater. The tubular structure of PPy@TiO2NT and the molecular interactions between TiO2 and PPy produce enhanced charge transfer, thereby providing the advantages of the hydrovoltaic effect, solar‐driven water evaporation (SWE), and photocatalysis. Consequently, PPy@TiO2NT‐loaded melamine foam can produce tens or more than a hundred microamperes of current in water of various salinities, which is an order of magnitude improvement over previously reported hydrovoltaic evaporation systems. In addition, under 1 sun irradiation, the system achieved an SWE rate of 2.13 kg m−2 h−1 and a methylene blue removal rate of more than 90% within 2 h. The proposed material system, featuring high electrical output and outstanding dual‐mechanism water treatment capabilities, shows high potential for synergistically harnessing solar energy and seawater, as well as for environmental management. [ABSTRACT FROM AUTHOR]