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.

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.

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.

High-Performance Photocatalytic Hydrogen Generation Using Robust Dianchoring Photosensitizers.

A novel series of donor-donor-π-acceptor (D-D-π-A) 9,9'-dihexylfluorene-based dianchoring organic dyes, each featuring distinct bridging electron-donating moieties, have been synthesized and characterized. Their performances in photocatalytic hydrogen evolution (PHE) were evaluated, taking into account of their photophysical and electrochemical attributes. Remarkably, (Z)-3-(5-(4-((4-(5-((E)-2-carboxy-2-cyanovinyl)thiophen-2-yl)phenyl)(9,9-dihexyl-9H-fluoren-2-yl)amino)phenyl)thiophen-2-yl)-2-cyanoacrylic acid achieved an active and robust H2 generation system with a turnover number (TON) of up to 17 400 in 126 h, with a production of 1090 µmol (26.3 mL) of hydrogen. The initial turnover frequency (TOFi), initial activity (activityi), and initial apparent quantum yield (AQYi) were 808 h-1, 505 mmol g-1 h-1, and 8.65%, respectively, under visible light irradiation in water. This photosensitizer is considered one of the most effective and durable systems for photocatalytic hydrogen production that attached to molecular Pt-TiO2, as stated out in the literature using organic dyes under visible light, when compared the TOF and TON values. The experimental results demonstrated that the dianchoring dyes with bridging units could significantly enhance PHE performance, maintaining justifiable durability over prolonged irradiation.

Efficient electron transport at the perovskite nanodots interface facilitates CO2 photoreduction.

How to achieve controllable preparation of heterostructure and in-situ optimize the interface and internal electron transfer by a fast and economic synthesis method has become a big challenge in the practical application of photocatalysis. Herein, an island-shaped SrTiO3 (STO) perovskite nanodots and TiO2 (T) compounded S-scheme SrTiO3/TiO2 (ST) heterostructure was successfully developed. During the millisecond reaction process, the decomposed Sr2+ penetrated into the TiO2 lattice causing the lattice expansion and inducing local atomic rearrangements, resulting in the generation of STO phase. Owing to the synergy of the efficient electron transport at the perovskite nanodots interface and the stronger reduction capacity, the performance of the optimized ST1 sample is greatly improved to 86.90 µmol g-1 for CO2-to-CO and 21.31 µmol g-1 for CO2-to-CH4. The utilization of electrons reached up to 119.74 µmol g-1 h-1, which was 3.13 times higher than that of T. Detailed characterizations and density functional theory (DFT) calculations proof that the formation of intermediates HCOO- and CO32- is the key to the performance improvement critically. Overall, this work originally reports a feasible strategy for flame synthesis of S-scheme heterostructure photocatalyst.

Alkali metal cation adsorption-induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production.

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25 mM after 1 h in a 0.25 M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+ < Na+ < K+ < Rb+ < Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.

Construction of S-scheme g-C3N4/PbTiO3 heterojunction and its highly efficient photocatalytic degradation of organic pollutants under simulated sunlight.

This study successfully synthesized a composite photocatalyst g-C3N4/PbTiO3 through hydrothermal and calcination methods using PbTiO3 and g-C3N4. The catalyst was characterized by XRD, FTIR, Raman, XPS, SEM, TEM, UV-vis DRS, PL, and other techniques. The results indicate that the composite photocatalyst exhibits efficient electron transfer, enhanced light absorption, effective separation and utilization of photogenerated electron-hole pairs, demonstrating superior photocatalytic activity. Under simulated sunlight, the removal efficiency of methyl blue (MB) with an initial concentration of 10 mg/L reaches 93.0% after 120 min. After five cycles, the degradation efficiency of MB is 79.2%, still maintaining 85% of the initial catalytic activity. The pH values in the range of 4.0-7.0, inorganic anions, and water quality have a minimal impact on the photocatalytic degradation of MB. Additionally, the composite photocatalyst exhibits strong removal capabilities for other pollutants, such as tetracycline. Therefore, the prepared catalyst demonstrates good feasibility for practical applications. Free radical quenching experiments indicate that hydroxyl radicals (·OH) are the primary active groups in the photocatalytic degradation of MB. Based on this, a photocatalytic mechanism involving a S-scheme heterojunction has been proposed. This study provides new insights into preparing PbTiO3 composite semiconductors and constructing novel S-scheme heterojunctions.

Oxygen-doped Porous Ultrathin Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Evolution and Rhodamine B Degradation.

Graphite phase carbon nitride (g-C3N4) is a highly promising metal-free photocatalyst. However, its applicability is restricted by low activity, due to weak quantum efficiency and small specific surface area. Exfoliating bulk crystals into porous thin-layer nanosheets and introducing element doping have been shown to improve photocatalytic efficiency, but these methods are often complex, time-consuming, and costly processes. In this study, we successfully synthesized porous oxygen-doped g-C3N4 (OCN) nanosheets utilizing a straightforward method. Our findings show that OCN have much higher light absorption and visible-light photocatalytic activity than bulk g-C3N4 (BCN) and nonporous g-C3N4 (CN). The OCN photocatalyst has a remarkable hydrogen evolution reaction (HER) rate of 8.02 mmol·g-1 h-1, which is 8 times greater than BCN. Additionally, the OCN shows a high degradation rate of 97.3% for Rhodamine B (RhB). This enhanced photocatalytic activity is ascribed to the narrow band gap and superior electron transfer capacity. Our findings suggest a potential technique for generating efficient g-C3N4 photocatalysts.

Innovative On-Resin and in Solution Peptidomimetics Synthesis via Metal-Free Photocatalytic Approach.

Nowadays, peptidomimetics are widely studied, being useful tools in drug discovery and medicinal chemistry. The coupling between a carboxylic acid with an amine to form a peptide bond is the most common reaction to obtain peptides/peptidomimetics. In this work, we have investigated an innovative metal-free photoredox-catalyzed carbamoylation to form peptidomimetics thanks to the reaction between dihydropyridines functionalized with amino acids (or peptide sequences) and differently functionalized imines. As the organic photocatalyst, we used 4CzIPN, a donor-acceptor cyanoarene vastly used in photoredox catalysis. By easily modulating the amino acid (or peptide sequence), which is directly attached to the dihydropyridine, we proposed this key-reaction as new valuable method to obtain peptidomimetics, in situ building the not-natural portion of the sequence. Moreover, we successfully employed this methodology in solid phase peptide synthesis, both inserting the new photoredox-generated amino acid at the end or in the middle of the sequence. Peptides with different lengths and secondary structures were prepared, proving the success of this approach, even in sterically hindered environment. Herein, to the best of our knowledge, we describe the first photocatalytic protocol which allows the building of the peptide backbone, with the possibility of simultaneously inserting a non-coded amino acid in the sequence.

Platinum-induced nanolization and electron-deficient gold in platinum@gold cocatalyst for efficient photocatalytic hydrogen peroxide production.

Simultaneous optimization of the number and intensity of oxygen (O2) adsorption on gold (Au) cocatalyst is highly required to greatly improve their interfacial hydrogen peroxide (H2O2)-production activity. However, it is a great challenge to realize the above effective modulation of Au by traditional photodeposition route. In this study, a platinum (Pt)-induced selective photodeposition method was designed to simultaneously regulate the particle size and electronic structure of Au cocatalyst for boosting the photocatalytic H2O2-production activity of bismuth vanadate (BiVO4) via the selective deposition of Pt@Au core-shell cocatalyst. The photocatalytic results indicate that the as-prepared BiVO4/Pt0.1@Au photocatalyst achieves a considerable H2O2-production activity with a rate of 2752.13 µmol L-1 (AQE = 13.76 %), which is obviously higher than that of BiVO4/Pt (137.63 µmol L-1) and BiVO4/Au (475.33 µmol L-1). It was found that the introduction of Pt successfully induced the formation of Au nanoparticles for enhancing the number of O2 adsorption. Meanwhile, the spontaneous transfer of free electrons of Au to Pt induces the generation of electron-deficient Auδ+ sites, which spontaneously enhances the O2-adsorption intensity for facilitating the 2-electron oxygen reduction reaction (ORR), resulting in efficient H2O2 production. The present strategy may be useful for more comprehensively regulating the intensity and number of O2 adsorption on cocatalysts to facilitate artificial photosynthesis.

Simultaneous Photocatalytic CO 2 Reduction and H 2 O Oxidation under Non-sacrificial Ambient Conditions.

The utilization of CO2, H2O, and solar energy is regarded as a sustainable route for converting CO2 into chemical feedstocks, paving the way for carbon neutrality and reclamation. However, the simultaneous photocatalytic CO2 reduction and H2O oxidation under non-sacrificial ambient conditions is still a significant challenge. Researchers have carried out extensive exploration and achieved dramatic developments in this area. In this review, we first primarily elucidate the principles of two half-reactions in the photocatalytic conversion of CO2 with H2O, i.e., CO2 reduction by the photo-generated electrons and protons, and H2O oxidation by the photo-generated holes without sacrificial agents. Subsequently, the strategies to promote two half-reactions are summarized, including the vacancy/facet/morphology design, adjacent redox site construction, and Z-scheme heterojunction development. Finally, we present the advanced in situ characterizations and future perspectives in this field. This review aims to provide fresh insights into effectively simultaneous photocatalytic CO2 reduction and H2O oxidation under non-sacrificial ambient conditions.

Nanoarchitectonics of vanadium nanoparticles decorated mesoporous carbon nitride in photocatalytic systems: A study on ethylbenzene oxidation reaction.

In this work, we have described the synthesis of vanadium (V) nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (V@mpg-C3N4) and their uses in photocatalytic ethylbenzene oxidation to the respective acetophenones. The mpg-C3N4 serves as the support for the decoration of V NPs, through a simple impregnation method. Various advanced techniques, such as XRD, UV-vis spectrometry, HRTEM, HAADF-STEM, AC-STEM, elemental mapping, and BET surface area analysis, were employed for the characterization of V@mpg-C3N4. The detailed characterization studies reveal that the V@mpg-C3N4 catalyst has a medium band gap (2.78 eV), a high surface area (76.7 m2g-1), and a mesoporous nature. The V@mpg-C3N4 photocatalysts demonstrated excellent performance in the light-assisted oxidation of ethylbenzene, achieving over 99 % conversion and selectivity for acetophenone in an environmentally friendly solvent (water) using a domestic light source (50 W white light). This developed synthesis strategy will be useful for synthesizing various noble and non-noble metal-based catalysts and their applications in organic transformation and environmental remediation.

Rational Design of Highly Porous Donor-Acceptor Based Conjugated Microporous Polymer for Photocatalytic Benzylamine Coupling Reaction.

Conjugated microporous polymers (CMPs) are an important class of organic materials with several useful features like, inherent nanoscale porosity, large specific surface area and semiconducting properties, which are very demanding for various sustainable applications. Carbazole building blocks are extensively used in designing photocatalysts due to easy electron donation and hole transportation. In the current study, a new CMP material CBZ-CMP containing carbazole unit used for photocatalytic C═N coupling reaction under blue light irradiation is designed. The CBZ-CMP framework is made through the polycondensation of 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl using FeCl3 as a catalyst. The CBZ-CMP shows very high BET surface area of 1536 m2 g-1 together with unimodal porosity (ca. 1.7 nm supermicropore), nanowire-like particle morphology (16-18 nm diameter), and low band gap property. The bi-phenyl moiety functions as the electron accepting center and the carbazole unit acts as the donor center, which accounts for the low band gap energy of CBZ-CMP. This nanoporous semiconducting CBZ-CMP material for photocatalytic benzylamine coupling reaction is explored, where it shows good conversion together with high selectivity under mild reaction conditions. This study offers simple method of preparation of a D-A-D-based porous photocatalyst for sustainable synthesis of value-added organics.

Oxygen Vacancies Regulated S-Scheme Charge Transport Route in BiVO4-OVs/g-C3N4 Heterojunction for Enhanced Photocatalytic Performance.

Oxygen vacancies (OVs) are widely considered as active sites in photocatalytic reactions, yet the crucial role of OVs in S-scheme heterojunction photocatalysts requires deeper understanding. In this work, OVs at hetero-interface regulated S-scheme BiVO4-OVs/g-C3N4 photocatalysts are constructed. The Fermi-level structures of BiVO4 and g-C3N4 lead to a redistribution of charges at the heterojunction interface, inducing an internal electric field at the interface, which tends to promote the recombination of photogenerated carriers at the interface. Importantly, the introduction of OVs induces defect electronic states in the BiVO4 bandgap, creating indirect recombination energy level that serves as crucial intermediator for photogenerated carrier recombination in the S-scheme heterojunction. As a result, the photocatalytic degradation rate on Rhodamine B (RhB) and tetracyclines (TCs) for the optimal sample is 10.7 and 11.8 times higher than the bare one, the photocatalytic hydrogen production rate is also improved to 558 µmol g-1 h-1. This work shows the importance of OVs in heterostructure photocatalysis from both thermodynamic and kinetic aspects and may provide new insight into the rational design of S-scheme photocatalysts.

Photocatalytic Hydrogen Generation in Surfactant-Free, Aqueous Organic Nanoparticle Dispersions.

Hydrogen generation in electrostatically stabilized, aqueous organic nanoparticle dispersions is investigated. For this purpose, organic nanoparticle dispersions are synthesized in water by nanoprecipitation from tetrahydrofuran and stabilized by charging through strong molecular electron acceptors. The dispersions are stable for more than 10 weeks on the shelf and during the photocatalytic process, despite the continuous transfer of charges between the reactants. The hydrogen generation in the electrostatically stabilized dispersions outperforms the hydrogen generation in organic nanoparticle dispersions which contain the common stabilizer sodium dodecyl sulfate.

Formic Acid-Intensified Photoreduction of NOx on Iron Minerals Triggers Daytime HONO Formation through Active Hydrogen.

Nitrous acid (HONO) is crucial in atmospheric chemistry as a precursor to morning peak hydroxyl radicals and significantly affects urban air quality by forming secondary pollutants, yet the mechanisms of its daytime formation is not fully understood. This study investigates the role of formic acid (HCOOH), a prevalent electron and proton donor, in the transformation of nitrogen oxides (NOx) and the formation of HONO on photoactive mineral dust. Exploiting hematite (Fe2O3) as an environmental indicator, we demonstrate that HCOOH significantly promotes the photoreduction of NO2 to HONO, while suppressing nitrate accumulation. This occurs through the formation of a surface ≡Fe-OOCH complex, where sunlight activates the C-H bond to generate and transfer active hydrogen, directly converting NO2 to HONO. Additionally, HCOOH can trigger the photolysis of nitrates as predeposited on Fe2O3, further increasing HONO production. These findings show that HCOOH-mediated photochemical reactions on iron minerals may contribute to elevated atmospheric HONO levels, highlighting a crucial pathway with broad effects on atmospheric chemistry and public health.

ZnO with Different Morphologies Sensitized by Metalloporphyrins as Catalysts for H2 Production by Water Splitting under Sunlight.

In this work, zinc oxide with different morphologies and textural properties were prepared and sensitized with metalloporphyrins (MPs) aiming to improve its solar energy harvesting capability for H2 production by water splitting under sunlight (a 300 W Xe/Hg lamp). An anionic iron(III)porphyrin and a cationic manganese(III)porphyrin were immobilized on different ZnO solids predominantly by electrostatic interactions. In general, the prepared MP-free ZnO solid yielded modest catalytic results which had apparently no direct correlation with their textural properties or morphology. On the other hand, when these ZnO solids had iron or manganese porphyrin sensitizing them, their catalytic performances changed and a superior yield towards H2 production was observed in comparison to the pure ZnO solids, making evident the synergy achieved between these two components (ZnO and metalloporphyrins) for the prepared solids. It was also observed that the metalloporphyrins and the respective free-base ligand suffered redox reactions when used as homogenous catalyst in this reaction, which could influence their performances as catalysts. The same was not observed in the solids containing immobilized MP, suggesting some protective effect of the ZnO solids on the MP complexes upon immobilization probably due to interaction of the complexes with the ZnO matrix.