Single Atom Ag Bonding Between PF3T Nanocluster and TiO2 Leads the Ultra-Stable Visible-Light-Driven Photocatalytic H2 Production.

Atomic Ag cluster bonding is employed to reinforce the interface between PF3T nano-cluster and TiO2 nanoparticle. With an optimized Ag loading (Ag/TiO2 = 0.5 wt%), the Ag atoms will uniformly disperse on TiO2 thus generating a high density of intermediate states in the band gap to form the electron channel between the terthiophene group of PF3T and the TiO2 in the hybrid composite (denoted as T@Ag05-P). The former expands the photon absorption band width and the latter facilitates the core-hole splitting by injecting the photon excited electron (from the excitons in PF3T) into the conduction band (CB) of TiO2. These characteristics enable the high efficiency of H2 production to 16 580 µmol h-1 g-1 and photocatalysis stability without degradation under visible light exposure for 96 h. Compared to that of hybrid material without Ag bonding (TiO2@PF3T), the H2 production yield and stability are improved by 4.1 and 18.2-fold which shows the best performance among existing materials in similar component combination and interfacial reinforcement. The unique bonding method offers a new prospect to accelerate the development of photocatalytic hydrogen production technologies.

A General Photoactive H-Bonding EDA Complex Model Drives the Selective Hydrothiolation and Hydroxysulfenylation of Carbonyl Activated Alkenes.

Excitation of photoactive electron donor-acceptor (EDA) complexes to generate radical is a promising approach in radical chemistry. In this study, we introduce a new model of H-bonding EDA complexes for the selective hydrothiolation and hydroxysulfenylation of carbonyl-activated alkenes with diverse thiols under visible light conditions. The reliability of this H-bonding EDA complex model has been confirmed by meticulous experimental and theoretical calculations. Mechanistic investigations have revealed the significant influence of the solvent in determining whether the excitation of photoactive H-bonding EDA complex leads to charge transfer (CT) or energy-charge transfer (En-CT), thereby controlling Markovnikov and anti-Markovnikov selectivity. Notably, the Quantum Theory of Atoms in Molecules (QTAIM) analysis clearly shows that the excited state of the C＝O---H-S EDA complex involves closed-shell partially covalent interactions.

Dual-Atom P-Co-Dy Charge-Transfer Bridge on Black Phosphorus for Enhanced Photocatalytic CO2 Reduction.

The synergistic effect of rare earth single-atoms and transition metal single-atoms may enable us to achieve some unprecedented performance and characteristics. Here, Co-Dy dual-atoms on black phosphorus with a P-Co-Dy charge-transfer bridge are designed and fabricated as the active center for the CO2 photoreduction reaction. The synergistic effect of Co-Dy on the performance of black phosphorus is studied by combining X-ray absorption spectroscopy, ultrafast spectral analysis, and in situ technology with DFT calculations. The results show that the Co and Dy bimetallic active site can promote charge transfer by the charge transfer bridge from P to Dy, and then to Co, thereby improving the photocatalytic activity of black phosphorus. The performance of catalysts excited at different wavelength light indicates that the 4G11/2/2I15/2/4F9/2→6H15/2 and 4F9/2→6H13/2 emissions of Dy can be absorbed by black phosphorus to improve the utilization of sunlight. The in situ DRIFTS and density functional theory (DFT) calculations are used to investigate the CO2 photoreduction pathway. This work provides an depth insight into the mechanism of dual-atom catalysts with enhanced photocatalytic performance, which helps to design novel atomic photocatalysts with excellent activity for CO2 reduction reactions.

Recent Developments on the Synthesis of Oxygen- and Sulfur-containing Heterocycles and their Derivatives under Visible Light Induced Reactions.

Visible-light-mediated reactions have recently emerged as a powerful strategy for the synthesis of diverse organic molecules under mild reaction conditions. Usually, the reactions are performed at room temperature and thus sensitive functional groups remain unaffected. Thus, this protocol has received intense interest from academia as well as industries. The heterocycles, in general, are of much interest because of their biological activities and application in therapeutics. The Oxygen- and Sulfur-containing heterocyclic compounds have recently attracted attention as these compounds showed promising activities as anti-cancer drugs, antibiotics, antifungal and anti-inflammatory agents among other applications. The synthesis of this class of compounds by efficient and greener routes has become an important target. This review highlights the various procedures for the synthesis of these compounds and their derivatives under visible light-induced reactions. The green aspects and mechanism of each procedure have been discussed.

Tuning the Mechanical Properties of 3D-printed Objects by Mixing Chain Transfer Agents in Norrish Type I Photoinitiated RAFT Polymerization.

Photoinduced 3D printing via photocontrolled reversible-deactivation radical polymerization (photoRDRP) techniques has emerged as a robust technique for creating polymeric materials. However, methods for precisely adjusting the mechanical properties of these materials remain limited. In this study, we present a facile approach for adjusting the mechanical properties of 3D-printed objects by adjusting the polymer dispersity within a Norrish type I photoinitiated reversible addition-fragmentation chain transfer (NTI-RAFT) polymerization-based 3D printing process. We investigated the effects of varying the concentrations and molar ratios of trithiocarbonate (BTPA) and xanthate (EXEP) on the mechanical properties of the printed materials. Our findings demonstrate that increased concentrations of RAFT agents or higher proportions of the more active BTPA lead to a decrease in Young's modulus and glass transition temperatures, along with an increase in elongation at break, which can be attributed to the enhanced homogeneity of the polymer network. Using a commercial LCD printer, the NTI-RAFT-based 3D printing system effectively produced materials with tailored mechanical properties, highlighting its potential for practical applications.

Enhancing visible light photocatalytic activity of holmium doped g-C3N4 and DFT theoretical insights.

In the search of novel photocatalysts to increase the effect of visible light in photocatalysis, g-C3N4 (CN) has become a shining star. Rare earth metals have been used as dopant material to reinforce the photocatalytic activity of CN due to their unique electron configuration recently. In this present study, the pure and different amounts of Ho-doped g-C3N4 (HoCN) photocatalysts were successfully synthesized using urea as a precursor by the one-pot method. Morphological, structural, optical, and vibrational properties of the synthesized photocatalysts were characterized by SEM, EDX, XRD, TGA, XPS, FTIR, PL, TRPL, Raman, DRS, and BET analyses. In addition, theoretical calculations using density functional theory (DFT) were meticulously carried out to delve the changes in the structural and electronic structure of CN with holmium doping. According to calculations, the chemical potential, electrophilicity, and chemical softness are higher for HoCN, while HOMO-LUMO gap, dipole moment, and the chemical hardness are lower for the pure one. Thus, holmium doping becomes desirable with low chemical hardness which indicates more effectivity and smaller HOMO-LUMO gap designate high chemical reactivity. To determine the photocatalytic efficiency of the pure and doped CN photocatalysts, the degradation of methylene blue (MB) was monitored under visible light. The results indicate that holmium doping has improved the photocatalytic activities of CN samples. Most strikingly, this improvement is noticeable for the 0.2 mmol doped CN sample that showed two times better photocatalytic activity than the pure one.

C─H Functionalization of Heteroarenes via Electron Donor-Acceptor Complex Photoactivation.

C─H Functionalization of heteroarenes stands as a potent instrument in organic synthesis, and with the incorporation of visible light, it emerged as a transformative game-changer. In this domain, electron donor-acceptor (EDA) complex, formed through the pairing of an electron-rich substrate with an electron-accepting molecule, has garnered substantial consideration in recent years due to the related avoidance of the requirement of photocatalyst as well as oxidant. EDA complexes can undergo photoactivation under mild conditions and exhibit high functional group tolerance, making them potentially suitable for the functionalization of biologically relevant heteroarenes. This review article provides an overview of recent advancements in the field of C─H functionalization of heteroarenes via EDA complex photoactivation with literature coverage up to April, 2024.

Visible light-induced photocatalytic degradation of tetrabromobisphenol A on platinized tungsten oxide.

In this study, we investigated the degradation of the flame retardant tetrabromobisphenol A (TBBPA) using platinized tungsten oxide (Pt/WO3), synthesized via a simple photodeposition method, under visible light. The results of degradation experiments show a significant enhancement in TBBPA degradation upon surface platinization of WO3, with the degradation rate increasing by 13.4 times compared to bare WO3. The presence of Pt on the WO3 surface stores conduction band electrons, which facilitates the two-electron reduction of oxygen and enhances the production of valence band holes (hVB+) and hydroxyl radicals (●OH). Both hVB+ and ●OH are significantly involved in the degradation of TBBPA in the visible light-irradiated Pt/WO3 system. This was verified through fluorescence spectroscopy employing coumarin as a chemical probe and oxidizing species-quenching experiments. The analysis of degradation products and their toxicity assessment demonstrate that the toxicity of TBBPA-contaminated water is significantly reduced after Pt/WO3 photocatalysis. The degradation rate of TBBPA increased with increasing Pt/WO3 dosage, reached an optimum at a Pt content of 0.5 wt%, but decreased with increasing TBBPA concentration. The decrease in degradation efficiency of Pt/WO3 was minor, both in the presence of various anions and after repeated use. This study proposes that Pt/WO3 is a viable photocatalyst for the degradation of TBBPA in water under visible light.

A Dual-Active Covalent Triazine Framework Film for Efficient Visible-Light-Driven Hydrogen Peroxide Production.

Photocatalytic hydrogen peroxide production from water and oxygen offers a clean and sustainable alternative to the conventional energy-intensive anthraquinone oxidation method. Compared to powdered covalent triazine frameworks (CTFs), the film morphology of CTFs provides better connectivity in 2D, yielding several advantages: more efficient connections between active sites, reduced electron-hole pair recombination, increased resistance to superoxide radical induced corrosion, and decreased light scattering. Leveraging these benefits, it has incorporated dual active sites for both the oxygen reduction reaction (ORR) and the water oxidation reaction (WOR) into a CTF film system. This dual-active CTF film demonstrated an exceptional hydrogen peroxide production rate of 19 460 µmol h⁻¹ m⁻2 after 1 h and 17 830 µmol h⁻¹ m⁻2 after 5 h under visible light irradiation (≥420 nm) without the need for sacrificial agents.

Photoactivation of Millimeters Thick Liquid Crystal Elastomers with Broadband Visible Light Using Donor-Acceptor Stenhouse Adducts.

Light-responsive liquid crystal elastomers (LCEs) are stimuli-responsive materials that facilitate the conversion of light energy into a mechanical response. In this work, a novel polysiloxane-based LCE with donor-acceptor Stenhouse adduct (DASA) side-chains is synthesized using a late-stage functionalization strategy. It is demonstrated that this approach does not compromise the molecular alignment observed in the traditional Finkelmann method. This easy, single-batch process provides a robust platform to access well-aligned, light-responsive LCE films with thickness ranging from 400 µm to a 14-layer stack that is 5 mm thick. Upon irradiation with low-intensity broadband visible light (100-200 mW cm-2), these systems undergo 2D planar actuation and complete bleaching. Conversely, exposure to higher-intensity visible light induces bending followed by contraction (300 mW cm-2). These processes are repeatable over several cycles. Finally, it is demonstrated how light intensity and the resulting heat generation influences the photothermal stationary state equilibrium of DASA, thereby controlling its photoresponsive properties. This work establishes the groundwork for advancement of LCE-based actuators beyond thin film and UV-light reliant systems.

Photodegrading rhodamine B dye with cobalt ferrite-graphitic carbon nitride (CoFe2O4/g-C3N4) composite.

The present research utilizes a sol-gel approach to create a CoFe2O4/g-C3N4 nanocomposite (NC) and explored several analytical methods to evaluate physical, chemical and optical based characteristics via XRD, FTIR, UV-vis, SEM/EDS and XPS for the prepared pure CoFe2O4, g-C3N4, and CoFe2O4/g-C3N4 NC. The XRD results show that the prepared g-C3N4, CoFe2O4, exhibits hexagonal and cubic phases respectively, whereas the g-C3N4/CoFe2O4 NC exhibit mixing of two phases. The energy band gaps for pure g-C3N4, CoFe2O4 and g-C3N4/CoFe2O4 NC values are viz., 2.75, 1.3, and 2.4 eV. As photocatalysts, synthesized materials were utilized for the decomposition of Rhodamine-B (RhB) dye. Finally, the CoFe2O4/g-C3N4 NC showed good performance of photocatalysis for RhB dye disintegration under the stimulus of visible light. According to the induced visible light, the rate at which the photocatalytic degradation occurs for the CoFe2O4/g-C3N4 NC was found to be 57% in 120 min and this is greater when compared with pure catalysts like CoFe2O4 (28%) and g-C3N4 (10%). These outcomes suggest that the prepared NC have efficiently worked during the photocatalytic process compared with its pure materials.

Cobalt-based Polymerized Porphyrinic Network for Visible-light-driven CO2 Reduction.

Visible-light-driven conversion of carbon dioxide to valuable compounds and fuels is an important but challenging task due to the inherent stability of the CO2 molecules. Herein, we report a series of cobalt-based polymerized porphyrinic network (PPN) photocatalysts for CO2 reduction with high activity. The introduction of organic groups results in the addition of more conjugated electrons to the networks, thereby altering the molecular orbital levels within the networks. This integration of functional groups effectively adjusts the levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO). The PPN(Co)-NO2 exhibits outstanding performance, with a CO evolution rate of 12 268 µmol/g/h and 85.8% selectivity, surpassing most similar photocatalyst systems. The performance of PPN(Co)-NO2 is also excellent in terms of apparent quantum yield (AQY) for CO production (5.7% at 420 nm). Density functional theory (DFT) calculations, time-resolved photoluminescence (TRPL), and electrochemical tests reveal that the introduction of methyl and nitro groups leads to a narrower energy gap, facilitating a faster charge transfer. The coupling reaction in this study enables the formation of stable C-C bonds, enhancing the structural regulation, active site diversity, and stability of the catalysts for photocatalytic CO2 reduction. This work offers a facile strategy to develop reliable catalysts for efficient CO2 conversion.

Visible light irradiation enhanced sulfidated zero-valent iron/peroxymonosulfate process for organic pollutant degradation.

This study developed a novel process named sulfidated zero-valent iron/peroxymonosulfate/visible light irradiation (S-mZVI/PMS/vis) for enhanced organic pollutant degradation. The S-mZVI/PMS/vis process exhibited remarkable catalytic activity, achieving a 99.6% rhodamine B (RhB) removal within 10 min. The degradation rate constant of RhB by the S-mZVI/PMS/vis process was found to be 6.49 and 79.84 times higher than that by the S-mZVI/PMS and PMS/vis processes, respectively. Furthermore, the S-mZVI/PMS/vis process worked efficiently across a wide pH range (3.0-9.0), and the result of five-cycle experiments demonstrated the excellent reusability and stability of S-mZVI. Radical quenching tests and electron paramagnetic resonance analysis indicated that ·O2-, 1O2, and h+ significantly contributed to the degradation of RhB through the S-mZVI/PMS/vis process. The visible light irradiation increased the Fe2+ concentration, improved the Fe3+/Fe2+ cycle, and consequently enhanced the PMS decomposition, reactive species production, and RhB degradation. This work offers a promising strategy to highly efficiently activate PMS for organic pollutants elimination from aqueous solutions.

An important step towards the comprehensive sun protection: Blue-light exposure inhibits DNA repair in reconstituted human skin and a broadband sunscreen avoids this inhibition.

The field of sun protection is quickly changing and the research article by Douki et al., published in the current issue of Photochemistry and Photobiology, reported key experimental data that will certainly help the development of better sun care products. Mutagenic photoproducts (CPDs, cyclobutane pyrimidine dimers and 6-4PPs, pyrimidine-6-4-pyrimidone photoproducts) were formed in the reconstructed human epidermis (RHE) by UVB (312 nm) irradiation, and their concentrations were detected by HPLC-MS/MS as a function of time after the UVB treatment. RHE had been previously exposed or not (control) to blue light (427 nm). Both CPDs and 6-4PPs were shown to last longer in blue-light irradiated RHE, proving the inhibition of the DNA repair by blue light exposure. This is a highly relevant information because sunscreens allow people to enjoy longer periods under the sun and consequently, to endure very high doses of blue light. The work also reported results obtained with RHEs previously treated with a sunscreen formulation containing a broadband filter that offers blue-light protection. Interestingly, authors observed that the DNA repair was not significantly inhibited in RHE previously treated with the sunscreen offering broadband protection. Readers will find a scientifically sound proof of the importance of blue-light protection in sun care products.

Environmentally degradable carbon dots for inhibiting P. globosa growth and reducing hemolytic toxin.

Red tides not only destroy marine ecosystems but also pose a great threat to human health. The traditional anti-red tide materials are difficult to degrade effectively in the natural environment and there may be risks of environmental leakage and secondary pollution. Furthermore, they cannot reduce the toxicity of toxins released by algae. It is very important to prepare degradable materials that can effectively control red tide and reduce their toxins in the future. Herein, degradable CDs (De-CDs) with biocompatibility and non-toxicity is successfully prepared using the one-step electrolytic method. De-CDs can effectively inhibit P. globosa (algae associated with red tide) growth. More importantly, the De-CDs not only can attenuate the toxicity of toxins released by P. globosa, but also can be degraded under visible-light irradiation in the seawater and avoids environmental leakage. The successful preparation of De-CDs provides a new idea for degradable materials with anti-red tide algae in the future.

Recent progresses in synthesis and modification of g-C3N4 for improving visible-light-driven photocatalytic degradation of antibiotics.

Graphitic carbon nitride (g-C3N4) is a widely studied visible-light-active photocatalyst for low cost, non-toxicity, and facile synthesis. Nonetheless, its photocatalytic efficiency is below par, due to fast recombination of charge carriers, low surface area, and insufficient visible light absorption. Thus, the research on the modification of g-C3N4 targeting at enhanced photocatalytic performance has attracted extensive interest. A considerable amount of review articles have been published on the modification of g-C3N4 for applications. However, limited effort has been specially contributed to providing an overview and comparison on available modification strategies for improved photocatalytic activity of g-C3N4-based catalysts in antibiotics removal. There has been no attempt on the comparison of photocatalytic performances in antibiotics removal between modified g-C3N4 and other known catalysts. To address these, our study reviewed strategies that have been reported to modify g-C3N4, including metal/non-metal doping, defect tuning, structural engineering, heterostructure formation, etc. as well as compared their performances for antibiotics removal. The heterostructure formation was the most widely studied and promising route to modify g-C3N4 with superior activity. As compared to other known photocatalysts, the heterojunction g-C3N4 showed competitive performances in degradation of selected antibiotics. Related mechanisms were discussed, and finally, we revealed current challenges in practical application.

Enhancing Photocatalytic Activities for Sustainable Hydrogen Evolution on Structurally Matched CuInS2/ZnIn2S4 Heterojunctions.

Effective charge separation and migration pose a critical challenge in the field of solar-driven hydrogen production. In this work, a Z-scheme structured CuInS2/ZnIn2S4 heterojunction was successfully fabricated through a two-step hydrothermal synthesis method to significantly enhance the efficiency of solar-to-hydrogen energy conversion. Structural characterization revealed that the lattice-matched CuInS2/ZnIn2S4 heterojunction exhibits an enlarged interfacial contact area, which facilitates the transfer and separation of photogenerated charges. Microscopic analysis indicated that the CuInS2/ZnIn2S4 composite material has a tightly interwoven interface and a morphology resembling small sugar cubes. Photoelectrochemical spectroscopy analysis demonstrated that the heterojunction structure effectively enhances visible light absorption and charge separation efficiency, leading to an improvement in photocatalytic activity. Hydrogen production experimental data indicated that the CuInS2/ZnIn2S4 heterojunction photocatalyst prepared with a CuInS2 content of 20 wt% exhibits the highest hydrogen evolution rate, reaching 284.9 µmol·g-1·h-1. Moreover, this photocatalyst maintains robust photocatalytic stability even after three consecutive usage cycles. This study demonstrated that the Z-scheme CuInS2/ZnIn2S4 heterojunction photocatalyst exhibits enhanced hydrogen evolution efficiency, offering an effective structural design for harnessing solar energy to obtain hydrogen fuel. Therefore, this heterojunction photocatalyst is a promising candidate for practical applications in solar hydrogen production.

Fe-Doped g-C3N4/Bi2MoO6 Heterostructured Composition with Improved Visible Photocatalytic Activity for Rhodamine B Degradation.

The binary heterostructured semiconducting visible light photocatalyst of the iron-doped graphitic carbon nitride/bismuth molybdate (Fe-g-C3N4/Bi2MoO6) composite was prepared by coupling with Fe-doped g-C3N4 and Bi2MoO6 particles. In the present study, a comparison of structural characteristics, optical properties, and photocatalytic degradation efficiency and activity between Fe-doped g-C3N4 particles, Bi2MoO6 particles, and Fe-g-C3N4/Bi2MoO6 composite was investigated. The results of X-ray diffraction (XRD) examination indicate that the hydrothermal Bi2MoO6 particles have a single orthorhombic phase and Fourier transform infrared (FTIR) spectroscopy analysis confirms the formation of Fe-doped g-C3N4. The optical bandgaps of the Fe-doped g-C3N4 and Bi2MoO6 particles are 2.74 and 2.73 eV, respectively, as estimated from the Taut plots obtained from UV-Vis diffuse reflectance spectroscopy (DRS) spectra. This characteristic indicates that the two semiconductor materials are suitable for absorbing visible light. The transmission electron microscopy (TEM) micrograph reveals the formation of the heterojunction Fe-g-C3N4/Bi2MoO6 composite. The results of photocatalytic degradation revealed that the developed Fe-g-C3N4/Bi2MoO6 composite photocatalyst exhibited significantly better photodegradation performance than the other two single semiconductor photocatalysts. This property can be attributed to the heterostructured nanostructure, which could effectively prevent the recombination of photogenerated carriers (electron-hole pairs) and enhance photocatalytic activity. Furthermore, cycling test showed that the Fe-g-C3N4/Bi2MoO6 heterostructured photocatalyst exhibited good reproducibility and stability for organic dye photodegradation.

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C-O bonds in organic transformations.

Alkyl and acyl radicals play a critical role in the advancement of chemical synthesis. The generation of acyl and alkyl radicals by activation of C-O bonds using visible-light photoredox catalysis offers a mild and environmentally benign approach to useful chemical transformations. Alcohols, carboxylic acids, anhydrides, xanthates, oxalates, N-phthalimides, and thiocarbonates are some examples of alkyl and acyl precursors that can produce reactive radicals by homolysis of the C-O bond. These radicals can then go through a variety of transformations that are beneficial for the construction of synthetic materials that are otherwise difficult to access. This study summarizes current developments in the use of organic photocatalysts, transition-metal photoredox catalysts, and metallaphotocatalysts to produce acyl and alkyl radicals driven by visible light.

Transition-metal-catalyst-free electroreductive alkene hydroarylation with aryl halides under visible-light irradiation.

The radical hydroarylation of alkenes is an efficient strategy for accessing linear alkylarenes with high regioselectivity. Herein, we report the electroreductive hydroarylation of electron-deficient alkenes and styrene derivatives using (hetero)aryl halides under mild reaction conditions. Notably, the present hydroarylation proceeded with high efficiency under transition-metal-catalyst-free conditions. The key to success is the use of 1,3-dicyanobenzene as a redox mediator and visible-light irradiation, which effectively suppresses the formation of simple reduction, i.e., hydrodehalogenation, products to afford the desired products in good to high yields. Mechanistic investigations proposed that a reductive radical-polar crossover pathway is likely to be involved in this transformation.