Organic Photocatalysis Research Articles

Synthesis of nanospindle-akaganéite and its photocatalytic degradation for methyl orange.

Iron oxyhydroxides as important catalysts and environmental mineral materials have drawn significant interest for their potential applications in the field of wastewater treatment. In this work, we investigated the influence of nonionic surfactant Brij30 or glucose (0.01 wt%) on the formation of iron precipitates in iron(III) chloride solutions for 3 days at 40, 60 and 80 °C. The results showed that the presence of glucose or Brij30 could promote the nanospindle-akaganéite formation and the akaganéite with a length of 300-500 nm obtained at 60 °C was the optimal catalyst for organic photocatalysis degradation. Further, we investigated the capacity of C60 akaganéite for degradation removal of methyl orange (MO) under the action of hydrogen peroxide (H2O2) addition and/or UV irradiation, and in the presence of different radical scavengers at pH 4.5. We also researched the effects of various levels of H2O2 and catalyst, and the reaction pH values. It was found that akaganéites could remove almost 100% of MO under 100 mg·L-1 of catalyst and H2O2 at pH 4.5. Akaganéite maintained 86% of MO removal capacity after four successive cycles. Our results can be used as a reference for the synthesis of environmentally functional material and the application in photocatalytic degradation of organic pollutant.

Thiosulfonylation of Unactivated Alkenes with Visible-Light Organic Photocatalysis

A metal-free method for the vicinal thiosulfonylation of unactivated alkenes with thiosulfonates using 9-mesityl-10-methylacridinium perchlorate as the photo-organocatalyst with visible-light irradiation has been developed. The method can be performed in dimethyl carbonate under air at room temperature and features a broad functional group compatibility. Metrics indicate the green potential of the developed versus the state-of-the-art methodologies. Mechanistic studies revealed no single electron transfer but involvement of an energy transfer from the excited photo-organocatalyst to thiosulfonate reactant, subsequently providing a sulfenyl and a sulfonyl radical via homolytic cleavage.

Frontiers in Radical Fluoromethylation by Visible‐Light Organic Photocatalysis

AbstractFluoromethyl groups, including tri‐, di‐, and mono‐fluoromethyl (CF3, CF2H, and CH2F, respectively) groups, are important structural motifs in medicinal chemistry. Radical fluoromethylation has attracted significant interest for the late‐stage functionalization of complex bioactive molecules. Recently, light energy has been used for radical reactions in synthesis of various valuable products. Strategies using organic photocatalysts (OPCs) are beneficial for synthetic radical chemistry and various aspects of “sustainable development goals (SDGs)”. Particularly, over the past several years, considerable progress has been made in the field of photoinduced radical fluoromethylation by OPCs. In this minireview, the concepts of representative reaction systems for fluoromethyl radical generation will be discussed.

Titanate nanotube confined merger of organic photocatalysis and TEMPO catalysis for highly selective aerobic oxidation of sulfides

Here, it is discovered that titanate (H2Ti3O7) nanotubes can confine the merger of erythrosin B (ErB) photocatalysis and TEMPO catalysis for highly selective aerobic oxidation of sulfides under irradiation of green light-emitting diodes (LEDs).

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

AbstractMolecular photoredox complexes from the platinum group paved the way of organic photocatalysis. However, high price and difficulties related to removal and recycling hamper application of such complexes on the larger scale. Carbon nitride semiconductor photocatalysts are deprived at large extent of such limitations. Herein, we summarize application of ionic carbon nitrides in photocatalysis. A salt‐like structure of ionic carbon nitrides comprising negatively charged poly(heptazine imide) anion and positively charged alkali metal cations gives rise to a number of unique properties and high activity in photocatalysis. The performance of ionic carbon nitrides in H2 generation is up to 100 times higher compared with the covalent graphitic carbon nitrides. Eleven photocatalytic reactions mediated by ionic carbon nitrides and their long‐lived radicals are reviewed. Economy of using carbon nitride photocatalysts in comparison with the photoredox complexes from the platinum group has been analyzed.

Perylenequinonoid-Catalyzed [4 + 1] and [4 + 2] Annulations of Azoalkenes: Photocatalytic Access to 1,2,3-Thiadiazole/1,4,5,6-Tetrahydropyridazine Derivatives

Nitrogen-containing heterocycles are especially considered "privileged" structural scaffolds for the development of new drugs. However, traditional methods of organic synthesis are mainly based on thermal cycloaddition reaction; thus, the exploration of new strategies for the rapid assembly of N-heterocycles under mild conditions is highly desirable. Here, we developed a new method that visible light along with 1 mol % cercosporin, which is one of the perylenequinonoid pigments with excellent properties of photosensitization and can be easily produced by a new isolated endophytic fungus Cercospora sp. JNU001 strain with high yield through microbial fermentation, catalyzes the synthesis of 1,2,3-thiadiazoles and 1,4,5,6-tetrahydropyridazines by a photocatalytic process with good regioselectivity and broad functional-group compatibility under mild conditions. Thus, a bridge between microbial fermentation and organic photocatalysis for the construction of nitrogen-containing heterocycles was set up in a sustainable, environmentally friendly manner.

Catalizadores magnéticos basados en Óxidos de Hierro: Síntesis, Propiedades y Aplicaciones

Esta revisión se centra en las propiedades magnéticas, estructura, síntesis y aplicación como catalizadores de las nanopartículas magnéticas de óxidos de hierro. En los últimos años son muchos los avances logrados respecto a su síntesis, control del tamaño y forma, donde se destacan métodos como la co-precipitación, microemulsión, síntesis hidrotermal y solvotermal, entre muchas otras. Pero debido a que las nanoparticulas de óxidos de hierro son fácilmente oxidables por el medio amiente y por medios ácidos, se ve la necesidad de recubrirlas o protegerlas con materiales no magnéticos que en muchos casos funcionan también como sustancias funcionalizadoras a las cuales se une la fase activa. Así, es amplio el abanico de posibilidades de sustancias y compuestos protectores, tales como óxidos inorgánicos, polímeros y metales, al igual las técnicas para su funcionalización. Las nanopartículas magnéticas una vez funcionalizadas pueden usarse como bloques de construcción para la fabricación de una gran variedad de sistemas catalíticos, y en este trabajo se revisará brevemente algunos de estos sistemas y su aplicación en diferentes procesos como reacciones de Síntesis Orgánica, fotocatálisis y eliminación de metales y otras sustancias en aguas residuales, por citar algunos ejemplos. Finalmente, se delinearán algunas tendencias y perspectivas futuras en estas áreas de investigación.

Guiding the Design of Organic Photocatalyst for PET-RAFT Polymerization: Halogenated Xanthene Dyes.

By examining structurally similar halogenated xanthene dyes, this study establishes a guiding principle for resolving structure-property- performance relationships in the photocontrolled PET-RAFT polymerization system (PET-RAFT: photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer). We investigated the effect of the halogen substituents on the photophysical and electrochemical properties of the xanthene dyes acting as photocatalysts and their resultant effect on the performance of PET-RAFT polymerization. Consideration of the structure- property-performance relationships allowed design of a new xanthene photocatalyst, where its photocatalytic activity (oxygen tolerance and polymerization rate) was successfully optimized for PET-RAFT polymerization. We expect that this study will serve as a theoretical framework in broadly guiding the design of high performance photocatalysts for organic photocatalysis.

Organocatalytic Approach to Functional Semifluorinated Polymers Driven by Visible Light.

Through the construction of an organic photocatalysis system, photoredox catalyst (PC)/additive, where PC stands for photoredox catalyst, an organocatalyzed step transfer-addition and radical-termination (O-START) polymerization irradiated by blue LED light at room temperature is realized. Different types of α,ω-diiodoperfluoroalkane A and α,ω-unconjugated diene B are copolymerized through O-START efficiently, and generate various kinds of functional semifluorinated polymers, including polyolefins and polyesters. The process is affected by several factors; solvents, additives, and feed ratio of A to B. After optimization of all these components, the polymerization efficiency is greatly improved, generating polymers with both relatively high yield and molecular weight. Considering the mild reaction condition, easy operation process, and free-of-metal-catalyst residues in the polymer product, the organocatalytic polymerization strategy provides a simple and efficient approach to functional semifluorinated polymer materials and hopefully opens up their application in high-tech fields.

Light-activated Ullmann homocoupling of aryl halides catalyzed using gold nanoparticle-functionalized potassium niobium oxides

Lamellar, or layered, potassium niobium oxide perovskites are a class of underdeveloped semiconductors in organic photocatalysis that offer the inherent advantages of larger particle size and ease of recoverability as compared to traditional semiconductor materials.

Organic photocatalysis for the radical couplings of boronic acid derivatives in batch and flow.

We report an acridium-based organic photocatalyst as an efficient replacement for iridium-based photocatalysts to oxidise boronic acid derivatives by a single electron process. Furthermore, we applied the developed catalytic system to the synthesis of four active pharmaceutical ingredients (APIs). A straightforward scale up approach using continuous flow photoreactors is also reported affording gram an hour throughput.

Two-channel photocatalytic production of H2O2 over g-C3N4 nanosheets modified with perylene imides

Hydrogen peroxide is a promising solar fuel and widely used in many industrial processes. Here we report on a new basis for clean energy storage, generating H2O2 from H2O and O2 by organic photocatalysis. In this study, we construct an all-solid-state Z-scheme heterojunction (PIx-NCN) by assembling perylene imides (PI) on g-C3N4 nanosheets (NCN), where x is a percentage weight ratio of PI to NCN. PIx-NCN exhibits significant enhancement in photocatalytic production H2O2, and the maximum enhancement was observed for PI5.0-NCN. It was shown that PI can change H2O2 generation from single-channel to two-channel. Specifically, photoexcitation of the PI moieties transfers their conduction band electrons to the valence band of NCN, resulting in enhanced charge separation. Thus, more electrons are available to reduce O2, producing more H2O2. More importantly, the holes in the valence band of PI moiety have more positive potential (2.08V) than those of NCN (1.63V), which can oxidize OH− to form OH (1.99V) and transform to H2O2 via the second channel. Therefore, for PIx-NCN, the photogenerated electrons and holes can be separated into two different phases, helping spatially isolate the oxidation and reduction reaction sites, and thus minimizing the catalytic deactivation.

Redox-Neutral Alkylation of Imines through Organic Photocatalysis

Redox-Neutral Alkylation of Imines through Organic Photocatalysis

AIE-active tetraphenylethene functionalized metal-organic framework for selective detection of nitroaromatic explosives and organic photocatalysis.

AIE-active luminogen tetraphenylethene (TPE) was incorporated into a UiO-isoreticular zirconium metal-organic framework via the strategy of mixed dicarboxylate struts, and the resulting functionalized MOF shows a strong blue-green emission and selective sensing of nitroaromatic explosives 2,4,6-trinitrophenol (TNP) and 2,4-dinitrophenol (DNP) through fluorescence quenching. Moreover, the luminescent MOF exhibits efficient photocatalytic activity for aerobic cross-dehydrogenative coupling reactions mediated by visible light.

Correction: Conjugated microporous polycarbazole containing tris(2-phenylpyridine)iridium(iii) complexes: phosphorescence, porosity, and heterogeneous organic photocatalysis

Correction for ‘Conjugated microporous polycarbazole containing tris(2-phenylpyridine)iridium(iii) complexes: phosphorescence, porosity, and heterogeneous organic photocatalysis’ by Long Pan, et al., Polym. Chem., 2016, DOI: 10.1039/c5py01955a.

Conjugated microporous polycarbazole containing tris(2-phenylpyridine)iridium(iii) complexes: phosphorescence, porosity, and heterogeneous organic photocatalysis

Porous polycarbazole containing tris(2-phenylpyridine)iridium(iii) complexes exhibit intense phosphorescence, moderate porosities and photocatalytic activities for the aza-Henry reaction.

ChemInform Abstract: Metal—Organic Frameworks for Artificial Photosynthesis and Photocatalysis

AbstractReview: 107 refs.

Visible-light organic photocatalysis for latent radical-initiated polymerization via 2e⁻/1H⁺ transfers: initiation with parallels to photosynthesis.

We report the latent production of free radicals from energy stored in a redox potential through a 2e–/1H+ transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e–/1H+ shuttle mechanism, as opposed to the 1e– transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the “storage” of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes.

Metal–organic frameworks for artificial photosynthesis and photocatalysis

Solar energy is an alternative, sustainable energy source for mankind. Finding a convenient way to convert sunlight energy into chemical energy is a key step towards realizing large-scale solar energy utilization. Owing to their structural regularity and synthetic tunability, metal-organic frameworks (MOFs) provide an interesting platform to hierarchically organize light-harvesting antennae and catalytic centers to achieve solar energy conversion. Such photo-driven catalytic processes not only play a critical role in the solar to chemical energy conversion scheme, but also provide a novel methodology for the synthesis of fine chemicals. In this review, we summarize the fundamental principles of energy transfer and photocatalysis and provide an overview of the latest progress in energy transfer, light-harvesting, photocatalytic proton and CO2 reduction, and water oxidation using MOFs. The applications of MOFs in organic photocatalysis and degradation of model organic pollutants are also discussed.

Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis

Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) ligands. MOFs 1-6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m(2)/g. MOFs 1-6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1-3 containing [Cp*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h(-1). The [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO(2) reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic conditions was also demonstrated by comparing PXRD patterns before and after catalysis. This work illustrates the potential of combining molecular catalysts and MOF structures in developing highly active heterogeneous catalysts for solar energy utilization.