Effects of surface fluoride modification on TiO2 for the photocatalytic oxidation of toluene.

In the present study, we investigated the influence of surface fluorine (F) on TiO2 for the photocatalytic oxidation (PCO) of toluene. TiO2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation.

Construction of bismuth based MOF for efficient removal of sodium diclofenac via adsorption and photocatalysis.

The mass production and widespread use of Pharmaceuticals and Personal Care Products (PPCPs) have posed a serious threat to the water environment and public health. In this work, a green metal-based Metal Organic Framework (MOF) Bi-NH2-BDC was prepared and characterized, and the adsorption characteristics of Bi-NH2-BDC were investigated with typical PPCPs-diclofenac sodium (DCF). It was found that DCF mainly covered the adsorbent surface as a single molecular layer, the adsorption reaction was a spontaneous, entropy-increasing exothermic process and the adsorption mechanisms between Bi-NH2-BDC and DCF were hydrogen bonding, π-π interactions and electrostatic interactions. In addition, Bi-NH2-BDC also had considerable photocatalytic properties, and its application in adsorbent desorption treatment effectively solved the problem of secondary pollution, achieving a green and sustainable adsorption desorption cycle.

Efficient chlorination reaction of Pt/RuO2/g-C3N4 under visible light irradiation for simultaneous removal of ammonia and bacteria from mariculture wastewater.

The removal of ammonia nitrogen (NH4+-N) and bacteria from aquaculture wastewater holds paramount ecological and production significance. In this study, Pt/RuO2/g-C3N4 photocatalysts were prepared by depositing Pt and RuO2 particles onto g-C3N4. The physicochemical properties of photocatalysts were explored by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis diffuse reflectance spectrometer (UV-vis DRS). The photocatalysts were then applied to the removal of both NH4+-N and bacteria from simulated mariculture wastewater. The results clarified that the removals of both NH4+-N and bacteria were in the sequence of g-C3N4 < RuO2/g-C3N4 < Pt/g-C3N4 < Pt/RuO2/g-C3N4. This magnificent photocatalytic ability of Pt/RuO2/g-C3N4 can be interpreted by the transfer of holes from g-C3N4 to RuO2 to facilitate the in situ generation of HClO from Cl- in wastewater, while Pt extracts photogenerated electrons for H2 formation to enhance the reaction. The removal of NH4+-N and disinfection effect were more pronounced in simulated seawater than in pure water. The removal efficiency of NH4+-N increases with an increase in pH of wastewater, while the bactericidal effect was more significant under a lower pH in a pH range of 6-9. In actual seawater aquaculture wastewater, Pt/RuO2/g-C3N4 still exhibits effective removal efficiency of NH4+-N and bactericidal performance under sunlight. This study provides an alternative avenue for removement of NH4+-N and bacteria from saline waters under sunlight.

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

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

Enhancing the photocatalytic efficiency by the molecular modification effect derived from pollutant adsorption on highly crystalline BiOBr.

The adsorption of pollutants can not only promote the direct surface reaction, but also modify the catalyst itself to improve its photoelectric characteristics, which is rarely studied for water treatment with inorganic photocatalyst. A highly crystalline BiOBr (c-BiOBr) was synthesized by a two-step preparation process. Owing to the calcination, the highly crystalline enhanced the interface interaction between pollutant and c-BiOBr. The complex of organic pollutant and [Bi2O2]2+ could promote the active electron transfer from the adsorbed pollutant to c-BiOBr for the direct pollutant degradation by holes (h+). Moreover, the pollutant adsorption actually modified c-BiOBr and promoted more unpaired electrons, which would coupling with the photoexcitation to promote generate more O2•-. The molecular modification effect derived from pollutant adsorption significantly improved the removal of pollutants. This work strongly deepens the understanding of the molecular modification effect from the pollutant adsorption and develops a novel and efficient approach for water treatment.

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

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

In Situ Construction of SnS2@SnO2 Heterostructure for Photo-Assisted Electrocatalysis of Oxygen Evolution Reaction.

Photo-assisted electrocatalysis has arisen as a promising approach for hydrogen generation by incorporating photocatalysts into electrocatalysts. 2D SnS2 is a photocatalyst that absorbs visible light. However, the rapid recombination of photo-generated electron-hole pairs significantly reduces the overall photocatalytic efficiency of SnS2, limiting its practical application. Thus, this study prepares an in situ heterojunction SnS2@SnO2 using a one-step hydrothermal method. The degradation efficiency of methyl orange (MO) using SnS2@SnO2 is measured, achieving a degradation rate of 92.75% within 1 h, which is 1.9 times higher than that of pure SnS2. Additionally, FeNiS/SnS2@SnO2 is synthesized and exhibited significant improvements in the photo-assisted oxygen evolution reaction (OER). It achieves an overpotential of 260 mV and a Tafel slope of 65.1 mV dec-1 at 10 mA cm-2, showing reductions of 11.8% and 31.8%, respectively, compared to FeNiS alone. These enhancements highlight the strong photo-response capability of SnS2@SnO2. Under the internal electric field of SnS2@SnO2, the photogenerated electrons in the conduction band of SnS2 quickly move toward SnO2, facilitating efficient photocatalytic reactions. FeNiS, with a lower Fermi energy level (EF), facilitates electron transfer from SnS2@SnO2 and enhances OER performance by efficiently participating in the reaction. This study paves a new path for 2D photocatalyst materials.

Light-Driven Site-Selective Glycosylation of Native Carbohydrates.

Carbohydrates constitute the largest source of biomass on Earth, but their synthetic modification is highly challenging due to their high content of oxygen functionalities. The site- and stereoselective modification of native sugars is a definitive goal of glycochemistry research. Recent efforts to bypass the need for protecting groups, leveraging selective activation through photochemical mechanisms for site-selective C-C bond formation from native sugars, are likely to largely impact all glycochemistry-related areas. Davis, Koh, and co-workers have recently presented their use of photocatalysis to develop a "cap and glycosylate" approach for the site- and stereoselective C-glycosylation of native sugars. The modernization of a direct radical functionalization of in situ formed thioglycoside using photocatalysis was used in the synthetic manipulation of unprotected carbohydrates. This allowed reaching complex saccharides, and post-translational modification of proteins.

Bright Nanocomposites based on Quantum Dot-Initiated Photocatalysis.

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light-emitting and solar energy conversion fields. However, the most widely-used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high-brightness nanocomposites with near-unity PL quantum yield (QY), through a novel QDs-catalyzed (-initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo-sensitizers/catalysts (always with cocatalysts) and hence non-emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as 'overall reaction' catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction-dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Solar Selective Photooxidation of Veratryl Alcohol by Suppression of Reactive Oxygen Species Through Band Modulation in the BiOI/Bi4Ti3O12 Heterojunction.

Lignin valorization through heterogeneous photocatalysis is a promising pathway for obtaining value-added products, including chemical building blocks, biofuels, etc. However, several challenges still demand attention and resolution in this field. One of the key parameters in the heterogeneous photocatalytic process is the synthesis of efficient photocatalysts that can accomplish efficient and selective reactions. Selective conversion of lignin can be achieved by using heterojunction photocatalysts which can efficiently separate charge carriers' and promote selective reactions by band structure modulation. This work details a straightforward approach for synthesizing heterojunction photocatalysts based on Bi4Ti3O12 and BiOI involving the hydrothermal and co-precipitation methods. Additionally, the synthesized composites were employed in the selective oxidation of veratryl alcohol, a lignin-derived model compound, to produce high-value-added veratraldehyde. The experimental results showed that the BiOI/Bi4Ti3O12 heterojunction (12.5 mol % BiOI) showed superior activity with a veratraldehyde yield of 5.4 and 27.2 times higher than those of Bi4Ti3O12 and BiOI, respectively. The mechanistic studies revealed that the improved activity and selectivity were due to the enhanced charge carriers' separation and the suppression of reactive oxygen species formation through modulation of band structure. This study allows a green approach to lignin-derived biomass valorization to obtain high-value chemicals.

Vinylene-linked Donor-π-Acceptor Metal-Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction.

Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal-covalent organic frameworks (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 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.

Peroxymonosulfate-assisted photocatalysis system enhanced magnetic Fe3O4@P-C3N4 treatment of tetracycline wastewater: Multi-pathways mediated electrons migration to generate reactive species.

Photocatalytic wastewater purification is essential for environmental remediation, but rapid carrier recombination and limited oxidative capacity hinder progress. This study proposes an innovative strategy by integrating homogeneous and heterogeneous electron acceptors into a g-C3N4-based photocatalytic system, significantly enhancing the multipath utilization of photogenerated electrons. A novel Fe3O4@P-C3N4 was developed to activate an advanced peroxymonosulfate-assisted photocatalysis (PAP) system, achieving complete degradation and significant mineralization of tetracycline (TC) in real water environments, outperforming others reported in the last five years. Phytic acid, as a key precursor, modifies the hollow tubular morphology and introduces phosphorus (P) heteroatoms as electronic trapping centers, enhancing the visible light response and carrier separation, thereby promoting the Fe2+/Fe3+ cycle and the formation of reactive species. Density functional theory (DFT) calculations pinpointed TC's vulnerable sites and synergically identified reactive species, revealing almost non-toxic degradation processes. Moreover, the recyclable magnetic Fe3O4@P-C3N4/PAP system demonstrates practical application potential and leaching stability in cyclic and continuous testing. This study offers unique insights into the strategic design of photocatalysts and catalytic environments, potentially advancing practical wastewater remediation.

Selective Photocatalytic C-H oxidation of 5-methylcytosine in DNA.

Selective C-H activation on complex biological macromolecules is a key goal in the field of organic chemistry. It requires thermodynamically challenging chemical transformations to be delivered in mild, aqueous conditions. 5-Methylcytosine (5mC) is a fundamentally important epigenetic modification in DNA that has major implications for biology and has emerged as a vital biomarker. Selective functionalisation of 5mC would enable new chemical approaches to tag, detect and map DNA methylation to enhance the study and exploitation of this epigenetic feature. We demonstrate the first example of direct and selective chemical oxidation of 5mC to 5-formylcytosine (5fC) in DNA, employing a photocatalytic system. This transformation was used to selectively tag 5mC. We also provide proof-of-concept for deploying this chemistry for single-base resolution sequencing of 5mC and genetic bases adenine (A), cytosine (C), guanine (G), thymine (T) in DNA on a next-generation sequencing system. This work exemplifies how photocatalysis has the potential to transform the analysis of DNA.

Green-light Hydrosilylation Photocatalysis with Platinum(II) Metalla-N-Heterocyclic Carbene Complexes.

Platinum(II) metalla-N-heterocyclic carbene complexes featuring pyridyl heterocyclic moiety demonstrate remarkable catalytic efficiency in alkyne hydrosilylation under green light irradiation. The photocatalytic properties of complexes are rationalised by the photo-induced charge transfer occurring in extended condensed system identified with the help of various experimental (UV/vis and emission spectroscopy, cyclic voltammetry) and theoretical methods (DFT/TD-DFT, IFCT analysis).

Meeting the Industrial Challenges of CO2 Photocatalytic Reduction: Moving From Molybdenum Disulfides to Oxysulfides Based Materials?

Reducing CO2 emissions is one of the greatest challenges of the century. Among the means employed to tackle CO2 emissions, the photocatalytic conversion of CO2 is an appealing way to valorize CO2 since it uses the sun energy, which is abundant. However, nowadays, the best photocatalytic systems still report too low efficiencies, and use expensive materials, so they cannot be readily industrialized for use at large scale. In this report, we first highlight general industrial and process challenges (including operating conditions). Then, focusing on MoS2/TiO2 heterojunction systems, we analyze advantages and limitations of such systems and open perspectives on Mo oxysulfides supported on TiO2 discussing their potential to reach higher efficiency for CO2 photoconversion.

Exploring the photocatalytic cleavage pathway of the ß-5 linkage lignin model compound on carbon nitride.

As a globally abundant source of biomass, lignocellulosic biomass has been the centre of  attention as a potential resource for green energy generation and  value-added chemical production. A key component of lignocellulosic biomass, lignin, which is comprised of aromatic monomers, is a potential feedstock for value added chemical production. The cleavage processes of the linkages between monomers to obtain high value products, however, requires significant investigation as it is a complex, non-facile process. This study focuses on the photocatalytic valorization of a ß-5 lignin model compound, a key linkage in the lignin structure. It was found that a greater yield of aromatic products were obtained from the photocatalytic conversion of ß-5 lignin model compound using carbon nitride (CN) when compared to Evonik P25 titanium dioxide (TiO2). Products of the ß-5 model compound photoconversion were determined and C-C bond cleavage was observed. It was also determined that the solvent participated in the reactions with the introduction of a cyano group to one of the products. Radical quenching experiments revealed that superoxide radicals participated in the CN photocatalytic conversion. These results reveal for the first time the products and possible mechanism of the photocatalytic transformation of ß-5 model compounds using  CN photocatalysis.

Indium-iron oxide nanosized solid solutions as photocatalysts for the degradation of pollutants under visible radiation.

A series of solid solutions of indium and iron oxides with different In/Fe ratios (InxFeyO3, with x + y = 2) were synthesized in the form of nanoparticles with the purpose of generating semiconductors with an intermediate band gap width compared to those of In2O3 and Fe2O3. XRD analysis proved the formation of the desired InxFeyO3 solid solutions for Fe content in the range 5-25% mol. UV-Vis absorption analysis showed that the substitution of In with Fe in the crystalline structure led to the anticipated gradual decrease of the band gaps energy values compared to In2O3. The obtained materials were tested as photocatalysts for the degradation of model organic pollutants (phenol and methylene blue) in water. Among the InxFeyO3 solid solutions, In1.7Fe0.3O3 displayed the highest photocatalytic activity in the degradation of the selected probe molecules under UV and visible radiation. Remarkably, In1.7Fe0.3O3 showed a significantly enhanced activity under visible light compared to monometallic indium oxide and iron oxide. This demonstrates that our strategy consisting in engineering the band gap by tuning the composition of InxFeyO3 solid solutions was successful in improving the photocatalytic performance under visible light. Additionally, In1.7Fe0.3O3 fully retained its photocatalytic activity upon reuse in four consecutive cycles.

Cocatalyst Embedded Ce-BDC-CeO2 S-Scheme Heterojunction Hollowed-Out Octahedrons With Rich Defects for Efficient CO2 Photoreduction.

Constructing heterojunction photocatalysts with optimized architecture and components is an effective strategy for enhancing CO2 photoreduction by promoting photogenerated carrier separation, visible light absorption, and CO2 adsorption. Herein, defect-rich photocatalysts (Ni2P@Ce-BDC-CeO2 HOOs) with S-scheme heterojunction and hollowed-out octahedral architecture are prepared by decomposing Ce-BDC octahedrons embedded with Ni2P nanoparticles and subsequent lactic acid etching for CO2 photoreduction. The hollowed-out octahedral architecture with multistage pores (micropores, mesopores, and macropores) and oxygen vacancy defects are simultaneously produced during the preparation process. The S-scheme heterojunction boosts the quick transfer and separation of photoinduced charges. The formed hollowed-out multi-stage pore structure is favorable for the adsorption and diffusion of CO2 molecules and gaseous products. As expected, the optimized photocatalyst exhibits excellent performance, producing CO with a yield of 61.6 µmol h-1 g-1, which is four times higher than that of the original Ce-BDC octahedrons. The X-ray photoelectron spectroscopy, scanning Kelvin probe, and electron spin resonance spectroscopy characterizations confirm the S-schematic charge-transfer route. The key intermediate species during the CO2 photoreduction process are detected by in situ Fourier transform infrared spectroscopy to support the proposed mechanism for CO2 photoreduction. This work presents a synthetic strategy for excellent catalysts with potential prospects in photocatalytic applications.

Ultrathin Porous Carbon Nitride Anchored with Pt Nanoclusters for Synergistic Enhancement of Hydrogen Production in Alkaline Photocatalytic Polyester Reforming.

Photocatalytic reforming (PR) of polyester waste, fueled by renewable sources like solar energy, offers a sustainable method for producing clean H2 and valuable by-products under mild conditions. The design of high-performance photocatalyst plays a pivotal role in determining the efficacy of an alkaline polyester PR system, influencing H2 generation activity and selectivity. Here, ultrathin porous carbon nitride nanosheets (UP-CN) loaded with Pt nanoclusters (Pt NCs, average diameter of 1.7 nm) with uniform Pt NCs distribution are introduced. The resulting Pt NCs/UP-CN catalyst can accelerate charge and mass transfer while providing additional active sites, achieving superior H2 generation rates of 11.69 mmol gcat -1 h-1 and 2923 mmol gPt -1 h-1 under AM 1.5 light, which nine times higher than that of Pt nanoparticles-bulk graphitic carbon nitride composite (1.29 mmol gcat -1 h-1 and 258 mmol gPt -1 h-1) as counterpart. This performance also surpasses that of previously reported carbon nitride-based and TiO2-based photocatalysts. Moreover, the density functional theory calculations reveal a significant reduction in the energy barrier for the water dissociation step (H2O + * → *H + OH) at the interface between UP-CN and anchored Pt NCs, showcasing the synergistic effect between Pt NCs and UP-CN. This catalytic system also exhibits universality across various polyester plastics.

Phosphonate-substituted Pyrazinoporphyrin - a General Photocatalyst for Efficient Sulfoxidation.

An exceptional efficiency of pyrazine-annelated porphyrin as a general photocatalyst for the oxidation of organic sulfides is demonstrated. It is shown that phosphonate-substituted pyrazinoporphyrin 2H-1 brings together sufficient photostability and high efficiency in the aerobic photooxidation of a series of various sulfides. The influence of the reaction conditions onto the efficiency of homogeneous sulfide photooxidation in the presence of the PS was investigated and strong dependence on the solvent system was observed. The use of methanol is required for the photocatalytic sulfoxidation and the ratio of the alcohol/other solvent can significantly affect the conversion and selectivity of the reaction. The application of the prepared photosensitizer (PS) in 0.001 mol% loading allowed achieving complete conversion (97-100%, turnover number up to 100000, turnover frequency up to 6250 h-1) of substrates bearing substituents of different nature, namely aromatic and aliphatic sulfides with donor or acceptor substituents and substituents prone to oxidation, as well as cyclic sulfides. The selectivity of the of the corresponding sulfoxides formation of 96-100% was revealed. Finally, a gram-scale synthesis of several sulfoxides was successfully performed with the PS under investigation, providing desired products in 66-96% yield with over 98% purity.