Visible Light Irradiation Research Articles

C-H alkylation of heterocycles via light-mediated palladium catalysis.

Methods enabling direct C-H alkylation of heterocycles are of fundamental importance in the late-stage modification of natural products, bioactive molecules, and medicinally relevant compounds. However, there is a scarcity of a general strategy for the direct C-H alkylation of a variety of heterocycles using commercially available alkyl surrogates. We report an operationally simple palladium-catalyzed direct C-H alkylation of heterocycles using alkyl halides under the visible light irradiation with good scalability and functional group tolerance. Our studies suggest that the photoinduced alkylation proceeds through cascade of events comprising, site-selective alkyl radical addition, base-assisted deprotonation, and oxidation. A combination of experiments and computations was employed for the generalization of this strategy, which was successfully translated towards the modification of natural products and pharmaceuticals.

Fe(II) Induced Porphyrin Nanoaggregates Assembled in the Liquid-Liquid Interface with Dual Enzyme-like Activity for Colorimetric Determination of Methimazole.

The liquid-liquid interface offers a confined space to control the growth of nanomaterials. In this study, Fe(II) (water phase) induced Meso-tetra (4-carboxyphenyl) porphyrin (H2TCPP) (CHCl3, organic phase) into nanoaggregates (Fe-TCPP) in the liquid-liquid interface. By tuning the ratio of DMF in organic solvents, Fe(II) induced H2TCPP into two nanoaggregates (Fe-TCPP-1 and Fe-TCPP-2) with different morphologies via coordination interaction occurring at the water-CHCl3 interface. Interestingly, the Fe-TCPP nanoaggregates possess dual enzyme-like activity (peroxidase-like and oxidase-like activity). In particular, both Fe-TCPP-1 and Fe-TCPP-2 demonstrate a peroxidase-/oxidase-like activity under visible light irradiation that is higher than that in the dark. Comparatively, Fe-TCPP-2 exhibits enhanced peroxide-like (POD) activity together with oxidase-like (OXD) activity compared with that of Fe-TCPP-1 under the corresponding similar conditions. The excellent enzyme mimic activity of Fe-TCPP nanozymes is ascribed to the generated hydroxyl radicals (·OH) and superoxide anions (O2•-). Remarkably, the catalytic activity of Fe-TCPP-2 remains more than 90% even in the higher temperature range of 35-40 °C, which is significant for biological detection under physiological conditions. Based on the outstanding dual enzyme-like activity of Fe-TCPP-2, a colorimetric sensing platform for methimazole (an antithyroid medicine) has been developed, demonstrating a linear detection range of 10-100 μM and a detection limit of 4.44 μM.

Efficient photodegradation of acid orange 7 in water using a facile ultrasound-assisted microwave-combustion synthesized Ag-ZnAl2-xFexO4 solid-solution photocatalyst

This study explores the development of Ag-ZnAl2-xFexO4 solid-solution photocatalysts for Acid Orange 7 (AO7) degradation under visible light irradiation. The microwave auto-combustion method was employed to synthesize these photocatalysts, allowing for the investigation of the influence of Fe substitution (x) on their properties and performance. Characterization techniques revealed a trade-off between Fe content, surface area, pore size, and light absorption capacity. The Ag-ZnAlFeO4 variant achieved an optimal balance, demonstrating exceptional photocatalytic activity for AO7 degradation. This optimized photocatalyst achieved a removal efficiency of 99.3 % under neutral pH conditions, highlighting its effectiveness and potential for practical applications. Interestingly, the mineralization efficiency of AO7 reached 85.2 % after 160 minutes of reaction time. Kinetic studies supported the superior performance of Ag-ZnAlFeO4, attributing its success to its favorable morphology, high surface area, strong light absorption, and minimal electron-hole pair recombination. The proposed degradation mechanism involves light absorption, generation of electron-hole pairs, and their subsequent reactions with water and oxygen molecules to degrade AO7. This work establishes Ag-ZnAl2-xFexO4, particularly Ag-ZnAlFeO4, as a promising visible-light photocatalyst for the efficient degradation of organic pollutants.

C‐H alkylation of heterocycles via light‐mediated palladium catalysis

Methods enabling direct C‐H alkylation of heterocycles are of fundamental importance in the late‐stage modification of natural products, bioactive molecules, and medicinally relevant compounds. However, there is a scarcity of a general strategy for the direct C‐H alkylation of a variety of heterocycles using commercially available alkyl surrogates. We report an operationally simple palladium‐catalyzed direct C‐H alkylation of heterocycles using alkyl halides under the visible light irradiation with good scalability and functional group tolerance. Our studies suggest that the photoinduced alkylation proceeds through cascade of events comprising, site‐selective alkyl radical addition, base‐assisted deprotonation, and oxidation. A combination of experiments and computations was employed for the generalization of this strategy, which was successfully translated towards the modification of natural products and pharmaceuticals.

Engineering Single Ni Sites on 3D Cage-like Cucurbit[n]uril Ligands for Efficient and Selective CO2 Photocatalytic Reduction.

Solar-driven CO2 selective reduction with high conversion is a challenging task yet holds immense promise for both CO2 neutralization and green fuel production. Enhancing CO2 adsorption at the catalytic centre can trigger a highly efficient CO2 capture-to-conversion process. Herein, we introduce cucurbit[n]urils (CB[n]), a new family of molecular ligands, as a key component in the creation of a 3D cage-like metal (nickel, Ni)-complex molecular co-catalyst (CB[7]-Ni) for photocatalysis. It exhibits an unprecedented CO yield rate of 72.1 µmol· h-1 with a high selectivity of 97.9% under visible light irradiation. To verify the origin of the carbon source in the products, a straightforward isotopic tracing method is designed based on tandem reactions. The catalytic process commences with photoelectron transfer from Ru(bpy)32+ to the Ni2+ site, resulting in the reduction of Ni2+ to Ni+. The locally enriched CO2 molecules in the cage ligand CB[7] undergo selective reduction by the Ni+ nearby to form CO product. This work exemplifies the inspiring potential of ligand structure engineering in advancing the development of efficient unanchored molecular co-catalysts.

Enhanced antibiotic degradation using rGO composites under visible light photocatalysis

A robust reduced graphene oxide (rGO), polyaniline (PANI) with calcium (Ca) and magnesium (Mg) bimetallic nanocomposite was successfully prepared using an in-situ chemical facial reducing method and named rGO@PANI-Ca:Mg. Various spectroscopic techniques, including XRD, SEM, TEM, XPS, and supplementary methods, were utilized to characterize the catalyst phase, microstructure, and optical attributes. The composite's photocatalytic efficiency was assessed by degrading antibiotics such as ciprofloxacin (CP) and tetracycline (TC) using calcium peroxide (CaO2) under visible light irradiation. The rGO@PANI-Ca:Mg composite demonstrates superior degradation efficiency for CP, 45 %, and for TC, 70 %, achieving a correlation coefficient R² of 0.94 and 0.991 respectively. This performance surpasses that of pristine GO, rGO, and rGO@PANI. The heightened photocatalytic activity is ascribed to forming a heterojunction, effectively mitigating electron-hole pair recombination. The incorporation of CaO2 promotes the generation of additional active reactive oxygen species (ROS), particularly OH·, ·O2−, e-, h+, as verified by radical scavenging experiments, indicating an enhancement in the degradation and a potential mechanism is also suggested. The degradation rate of TC, CP, and real wastewater (RW) is about 71 %, 45 %, and 40.98 %, respectively. The composite demonstrates stability and reusability for up to three catalytic cycles. Our experiments also showed that when bacteria were treated with a 2 mg catalyst, the minimum inhibitory concentration (MIC) was determined to be at a 10−3 dilution. This MIC value represents the lowest concentration at which the catalyst effectively inhibited bacterial growth, as evidenced by clear inhibition zones.

Layered Perovskite La2Ti2O7 Nanostructures for Photocatalytic Degradation of Congo Red Dye Pollutant

AbstractIn photocatalytic innovation, there has been a lot of interest in creating broad spectral responsive photocatalysts to get superior catalytic performance. In this study, we synthesized highly visible‐light responsive La2Ti2O7 perovskite photocatalysts by the probe ultrasonication procedure followed by high‐temperature calcination. Such materials are characterized using UV‐vis diffuse reflectance spectra, powder X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy to illustrate the optical absorption activities, crystalline properties, chemical composition, and microscopic features. La2Ti2O7 extends optical absorption towards the visible light spectrum and narrows the band gap. The photocatalytic efficacy of the resulting La2Ti2O7 nanostructures was investigated by performing photocatalytic degradation of persistent Congo red (CR) dye while subjected to visible photon illumination using three Osram 150 W tungsten halogen lamp ((λ≥400 nm), 5000 lm nominal luminous flux, 80,600 lx radiation intensity. With effective efficiency, the optimum degradation of the 10 ppm CR dye with a percentage of 95.9 was achieved after 90 min during exposure to the La2Ti2O7 perovskite with a catalyst dosage of 30 mg/100 mL at pH 6. Consequently, La2Ti2O7 nanostructures alone depicted 19.8 % adsorption efficiency for CR dye. In addition, OH⋅ and holes were important in degrading CR dye, which included many different reaction pathways. The treated solution can also demonstrate the environment's safety for accepting water. In summary, under natural visible light irradiation, the synthesized La2Ti2O7 showed enormous promise for eliminating different organic contaminants using photocatalytic methodology.

Heterogeneous visible-light photoredox catalysis with NiCl2@g-C3N4 for induced C(sp2)-H/N[sbnd]H cross-dehydrogenative coupling

A novel photoactive NiCl2@g-C3N4 catalyst system, which effectively drives C(sp2)-H/NH bond formation between quinolin-2(1H)-ones, primary and secondary aliphatic amines under blue light irradiation. The NiCl2@g-C3N4 composite with a NiCl2 loading of 0.7wt% had the highest photoactivity, and the calculated band gap energy value is 2.56 eV The nickel ion could act as an electron acceptor enhancing carrier separation and transfer efficiency, greatly enhanced the photoreaction efficiency of g-C3N4. Preliminary mechanistic studies indicate upon visible light irradiation, the photo-generated electrons and holes act as oxidants, thereby generating amine radicals in the absence of external chemical oxidants. This provides a straightforward and efficient approach for directly 3-aminating quinoxalines-2(1H)-ones. Moreover, the heterogeneous catalyst can be recycled at least six times without significant activity loss.

Covalent Organic Framework Stabilized Single CoN4Cl2 Site Boosts Photocatalytic CO2 Reduction into Tunable Syngas

AbstractSolar carbon dioxide (CO2) reduction provides an attractive alternative to producing sustainable chemicals and fuel. However, the construction of a highly active photocatalyst was challenging because of the rapid charge recombination and sluggish surface CO2 reduction. Herein, a unique Co−N4Cl2 single site was fabricated by loading Co species into the 2,2′‐bipyridine and triazine‐containing covalent organic framework (COF) for CO2 conversion into syngas under visible light irradiation. The resulting champion catalyst TPy‐COF‐Co enabled a record‐high CO production rate of 426 mmol g−1 h−1, associated with the unprecedented turnover number (TON) and turnover frequency (TOF) of 2095 and 1607 h−1, respectively. The catalyst also exhibited favorable recycling performance and widely adjustable syngas production (CO/H2 ratio: 1.8 : 1–1 : 16). A systematical investigation including operando synchrotron X‐ray absorption fine structure (XAFS) spectroscopy, in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), and theoretical calculation indicated that the triazine‐based COF framework promoted the charge transfer towards the single Co−N4Cl2 sites that greatly promoted the CO2 activation by lowering the energy barrier of *COOH generation, facilitating the CO2 transformation. This work highlights the great potential of the molecular regulation of COF‐derived single‐atom catalysts to boost CO2 photoreduction efficiency.

Hydrogen Evolution Catalysis by Cobalt Complexes of an Aza‐Bridged Bis‐1,10‐Phenanthroline Ligand Bearing Pendant Basic Sites

AbstractA novel series of molecular Co(II) complexes with aza‐bridged bis‐1,10‐phenanthroline (bpa) ligands have been synthesized and reported for the catalytic hydrogen evolution reaction (HER). Various nitrogen donor substituents are introduced at the aza‐bridge of the bis‐phenanthroline moieties render intramolecular basic sites in the complexes’ second‐coordination sphere. Modifying the pendant nitrogen donor significantly influences the catalytic HER performance. Among these, the cobalt complex with the (2‐pyridyl)methyl substituted bis‐phenanthroline ligand (L3) exhibits the most photocatalytic HER efficiency in both organic and aqueous media. Under optimized conditions with [Ru(bpy)3]2+ as a sensitizer and ascorbic acid as an electron donor, [CoII(L3)(TfO−)2] achieves an initial turnover frequency (TOF) of 1882±65 h−1 per catalyst and a turnover number (TON) of 4842±122 in a 3 hour reaction period under the irradiation of visible light. Combined experimental and theoretical evidences illustrate that phenanthroline moieties of the bpa ligands act as electron mediators during the HER catalysis, while the pendant nitrogen donor substituents mediate proton transfer. This work provides a unique example for understanding the activity‐structure relationship of homogeneous HER catalyst concerning the redox‐active properties and second coordination sphere basic sites of organic ligand platforms.

Plants-extracts mediated CuS nanoparticles: An effective antibacterial agent

Antibacterial activity of plant-mediated synthesized CuS nanoparticles against gram-positive Bacillus subtilis and gram negative Pseudomonas putida is studied in this presented work. A facile hydrothermal approach was followed to synthesize spherical shaped CuS nanoparticles using flowers extract of Tagetes patula (S1), leaves extract of Azadirachta indica (S2), and bark extract of Terminalia arjuna (S3). Crystal phase identification, average crystallites size, surface morphology, absorbance spectra and energy band gap analyses of samples were further determined using XRD, SEM, and UV-DRS spectroscopy respectively. Furthermore, under irradiation of visible light, antibacterial activity of marigold flowers mediated (S1), neem leaves mediated (S2), and arjuna bark mediated (S3) CuS samples were studied. XRD data confirmed the marigold mediated CuS sample has relatively smaller crystallites size of 10.67 nm. The estimated band gap energies for respective S1, S2, and S3 samples are 174 eV, 175 eV, and 177 eV. The antibacterial analysis of S1 sample displays its excellent antibacterial activity with the formation of relatively large inhibition zones of 29 mm and 30 mm diameters, against Bacillus subtilis and Pseudomonas putida respectively. The demonstrated antibacterial activity of biocompatible CuS nanoparticles suggests their potential use in biomedical applications.

Antibacterial and Antifungal Characteristics of Hydroxyl Apatite Composite Material Coated on Nitrogen-doped TiO2 (HA/N-TiO2)

Photocatalytic technology using nano-material HA/TiO2 has been widely applied worldwide to treat pollutants, kill airborne gram-negative and gram-positive bacteria, and candida fungi, especially indoor air. In this study, HA/N-TiO2 material was synthesized with oxidation-reduction absorption properties and photocatalytic ability in the visible-light irradiation that helps reduce costs compared to using ultraviolet light (UV). The structure and morphology of the material were evaluated using XRD, SEM methods, showing HA/N-TiO2 has a spherical crystal structure, sharp, and uniform with particle sizes ranging from 10 to 30 nm. To assessment of the antibacterial and antifungal efficiency of the material, we inoculated the culture of microorganisms on 10x10 cm tiles coated with HA/N-TiO2 solution with the coating thickness of 0.3 µm. This coating thickness resulted in optimal antibacterial efficacy. With continuous fluorescent light 20 W exposure for 1-9 hours, up to 96-100% of inoculated bacteria were eliminated. In real-scale experiments on the wall surfaces, the quantity of bacteria and mold decreased by 20% after 30 days when treated with HA/N-TiO2 solution compared to the control sample. HA/N-TiO2 material has the potential to treat bacteria and fungi on a practical scale if there is further cost-benefit analysis extensive research.

Vapor-Solid Interface Synthesis of Highly Crystalline Covalent Triazine Frameworks for Use as Efficient Photocatalysts.

Harsh synthetic conditions for crystalline covalent triazine frameworks (CTFs) and associated limitations on structural diversities impede not only further development of functional CTFs, but also practical large-scale synthesis. Herein, a mild and universal vapor-solid interface synthesis strategy is developed for highly crystalline CTFs employing trifluoromethanesulfonic acid vapor as catalysts. A series of highly ordered simple and functional CTFs (CTF-TJUs) can be facilely produced. In particular, the porphyrin-involved functional CTF (CTF-TJU-Por1) with high crystallinity is synthesized for the first time via this universal approach. The mechanism of vapor-catalyzed trimerization of nitrile monomers is thoroughly investigated through semi in situ characterizations. As a proof of concept, the photocatalytic performance of synthesized CTFs for water splitting is evaluated. CTF-TJU-133 exhibits significantly greater photocatalytic rates for hydrogen (4.35µmolh-1) and oxygen (2.18µmolh-1) evolutions during overall water splitting under visible light irradiations compared to other CTF-TJUs, representing one of the highest values among reported CTF photocatalysts. Further studies reveal that enhanced photocatalytic performance of CTF-TJU-133 results from optimized band structure, extended visible-light absorption, and high carrier separation efficiency. This study provides a promising strategy to synthesize various simple and functional CTFs, which significantly enriched diversities of CTF family for different application purposes.

Synthesis of eco-friendly CaCO3@Zn-Al MMO core-shell nanoflowers photocatalyst using bio–eggshell waste for improved photocatalytic degradation of RhB under visible light irradiation

In this study, a type-I heterojunction was synthesized based on eggshell waste doped mixed metal oxide (ES@ZnAl MMO) for the degradation of RhB dye under visible light irradiation. The ES@ZnAl MMO core-shell was synthesized using waste eggshell and layered double hydroxide (LDH) as primary precursors. After their mechanochemical assembly and thermal treatment, CaCO3 was formed in both calcite and vaterite forms, alongside mixed metal oxides derived from the LDH (ZnO and Al2O3). The formation of a heterojunction between the semiconductors results in an improved activation of sites, a decrease in bandgap energy from 5.72 to 3.44 eV, and an increase in degradation capacity. The elemental composition, morphology, structural, and optical properties of the ES@ZnAl MMO nanocomposite were analyzed using various techniques. The optimal ES@ZnAl MMO photocatalyst demonstrated superior performance, reaching over 98% of RhB dye degradation under optimal conditions, outperforming pure ZnAl LDH, ZnAl MMO, and ES. After five run cycles, the ES@ZnAl MMO heterojunction still maintained a high photocatalytic performance for RhB dye (99%). Furthermore, it displayed high performance in degrading various other pollutants, including OG, IC, MB, and 2.4-DP, with degradation efficiencies of 97%, 99%, 99%, and 87%, respectively. This economically advantageous heterojunction showed its importance in environmental remediation, presenting a promising solution for addressing diverse pollution challenges.

Low cost fabrication of continuous flow optofluidic microreactor for efficient dye degradation using graphene QDs@MOF (Ti) photocatalyst

The optofluidic microreactor, a convergence of optics and microfluidics, offers advanced functionalities that can be pivotal in the rapid assessment of nanocatalysts for tackling environmental contamination issues. This article presents an efficient approach for degrading Methylene blue (MB) dye, commonly used in the textile industry, within a cost-effective polydimethylsiloxane (PDMS) based continuous flow optofluidic microreactor. This microreactor combines graphene quantum dots (QDs) and NH2-MIL-125 (MOF(Ti)) as a highly effective photocatalyst coating within its microchannels. By directly incorporating graphene QDs@MOF(Ti) into the microchannels, the photocatalytic medium is brought into close proximity with the flowing MB dye solutions, thereby reducing the necessary interaction time and enhancing purification efficiency. Furthermore, the findings demonstrate an impressive degradation efficiency of ∼99% for MB dye at a flow rate of 50 μL min−1 under visible light irradiation, achieved in a single pass. Additionally, the microfluidic reactor exhibits prolonged stability of the photocatalyst, enabling its reuse without significant efficiency loss. In addition, a comparative analysis highlights the advantages of microreactor-based photocatalysis over traditional methods. These advancements in the features of the graphene QDs@MOF(Ti) nanocomposite substantiate their demonstrated superiority in degradation efficiency.

Reconfigurable Visible Light-Driven Liquid Crystalline Network Showing Off-Equilibrium Motions Enabled by Mesogen-Grafted Donor-Acceptor Stenhouse Adducts.

Liquid crystalline network (LCN)-based soft actuators have opened up great opportunities to fabricate emerging and intriguing smart materials, serving as potential building blocks for intelligent soft robotics. Endowing LCN actuators with complex responsive behaviors to enhance their intelligence is both challenging and highly demanded. Herein, Donor-Acceptor Stenhouse Adducts (DASAs) molecules with rod-like mesogen and the polymerizable group are judiciously designed and synthesized, which is strong-colored at linear form and de-coloration at cyclic form after visible light. In the colored state, the DASA presents a striking photothermal effect that is capable of driving the motions of LCN film. Upon visible light irradiation, the DASA becomes colorless, making the diminishing photothermal effect. The light-gated switching of the photothermal effect renders the LCN films to be reconfigurable and perform off-equilibrium motions. The varying glass transition temperature of LCN matrix endowing tunable isomerization rates of DASAs and the equilibrium balance of photo- and thermal-isomerization at different temperatures in LCN-P-DASA film mainly guiding the off-equilibrium or stable motions, providing high adjustability of the novel visible light-driven LCN actuators. The multiply modulated LCN-P-DASA film holds great potential in constructing complex visible light-driven soft actuators based on the synergetic effect and interactions of photochemical and photothermal effects.

Ni-Metalized Covalent Organic Cage as a Photocatalyst for Selective Photoreduction of CO2 to CO.

Metal complex-based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2-to-CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis.

C(sp2)-Arylsulfones Directly from Arylsulfonyl Chlorides with Boronic Acids by Photoactivation of Boosted EDA Complexes.

Directly with arylsulfonyl chlorides, a green and efficient deborylativesulfonylation of aryl(alkenyl)boronic acids has been developed to access both diarylsulfones and vinylarylsulfones in moderate to excellent yields at room temperature under visible-light irradiation. This protocol features broad C(sp2)-arylsulfone applicability, simple operation, accessibility of raw materials and ease of scale-up. The key to the success of this photoredox transformation is introducing catalytic amounts of additives, naphthalen-2-ols, thus boosting the formed electron donor-acceptor (EDA) complexes, which can dramatically improve not only the reaction efficiency but also the selectivity. This strategywas inspired and derived from specific substrates, representing a rare paradigm of how to exploit a more general reaction system. Moreover, extensive control experiments provide insights into the proposed mechanism.

Tetracycline removal via photo-Fenton processes using Fe-based metal-organic frameworks loaded with Bi2S3: Performance evaluation and insights into the charge-transfer mechanism

Combining photocatalytic technology with the Fenton system may help overcome these technologies’ limitations. Photo-Fenton catalysis is economical and eco-friendly. The Fe based heterogeneous photo-Fenton process appears to be a promising wastewater treatment technology. Herein, an Fe based metal–organic framework (MIL-101 (Fe)) was produced via hydrothermal processing. Subsequently, Bi2S3 was loaded onto the surface of MIL-101 (Fe) to form a composite catalyst. A type-II heterojunction was established between MIL-101 (Fe) and Bi2S3. The 10 % Bi2S3-loaded MIL-101 (Fe) (MBS-10) was effective in the photocatalytic degradation of tetracycline, particularly after H2O2 addition. This outcome was due to the enhanced generation of radical species through the photo-Fenton process. The MBS-10 photocatalyst promoted Fe (II)/Fe (III) cycling in the presence of H2O2 and under visible light irradiation. MBS-10 also showed a higher kinetic rate constant during the photocatalytic reaction compared to MIL-101 (Fe) and Bi2S3, suggesting enhanced activity through greater electron-hole separation. Furthermore, MBS-10 proved to be stable and reusable photocatalyst after four testing cycles. The charge-transfer mechanism was elucidated through radical scavenging experiments which demonstrated that superoxide and hydroxyl radicals are the major charge carriers. Therefore, the Bi2S3-MIL-101 (Fe) composite exhibits great potential for degrading tetracycline antibiotics.

Dual Cocatalysts on Covalent Organic Framework as Charge Transfer Mediator Facilitating Photocatalytic Water Oxidation

AbstractCovalent organic frameworks (COFs) have been regarded as promising photocatalytic materials. However, the sluggish diffusion of photoinduced charges in a single‐component COF remains the obstacles that have to be overcome. Here, we demonstrate a synthesis of a COF bearing dual cocatalysts Co3O4 and Re complex as photocatalyst for water oxidation. The dual cocatalysts are coordinated on the COF, and enable the spatial separation of photoinduced charges. The generated electrons were attracted to Re moiety, while the holes were localized on Co3O4 cocatalyst for water oxidation to produce O2 product. The synergy of dual cocatalysts of COF promote the charge separation and redox reaction. Moreover, hydroxyl radicals generated from the hydration of COF contribute to O−O bond formation, which is the key step of O2 formation. Accordingly, an excellent O2 production rate of 400 μmol g−1 h−1 under visible light irradiation was obtained. This work may pave the way to the development of highly efficient COF photocatalysts for solar energy conversion.