Photochemical Route Research Articles

Adsorption and Catalytic Reduction of Nitrogen Oxides (NO, N2O) on Disulfide Cluster Complexes of Cobalt and Iron-A Density Functional Study.

The reactivity of nitrogen oxide, NO, as a ligand in complexes with [Fe2-S2] and [Co2-S2] non-planar rhombic cores is examined by density functional theory (DFT). The cobalt-containing nitrosyl complexes are less stable than the iron complexes because the Co-S bonds in the [Co2-S2] core are weakened upon NO coordination. Various positions of NO were examined, including its binding to sulfur centers. The release of NO molecules can be monitored photochemically. The ability of NO to form a (NO)2 dimer provides a favorable route of electrochemical reduction, as protonation significantly stabilizes the dimeric species over the monomers. The quasilinear dimer ONNO, with trans-orientation of oxygen atoms, gains higher stability under protonation and reduction via proton-electron transfer. The first two reduction steps lead to an N2O intermediate, whose reduction is more energy demanding: in the two latter reaction steps the highest energy barrier for Co2S2(CO)6 is 109 kJ mol-1, and for Fe2S2(CO)6, it is 133 kJ mol-1. Again, the presence of favorable light absorption bands allows for a photochemical route to overcome these energy barriers. All elementary steps are exothermic, and the final products are molecular nitrogen and water.

Oxidative photochemical cyclisations to access spiroketals

The spiroketal moiety is an important substructure within many biological natural products. One method to access them is via the oxidative cyclisation of a pendant hydroxyl group on to a pre‐formed pyran. However applications of this methodology have been severely limited by requiring the use of toxic and powerful oxidants, such as lead (IV) tetraacetate or mercuric oxide. Herein we report a novel and high yielding photochemical route to prepare complex spiroketals using a photochemical oxidative approach with mild and non‐toxic reagents and demonstrate the methodology to the synthesis of a number of insect pheromones.

Photochemical Generation of Allenylidenes from Cyclopropanated Phenanthrenes: An Experimental and Computational Study.

To address the scarcity of generally applicable photochemical routes to allenylidenes in solution, phenanthrene-based sources have been investigated. Specifically, the syntheses of 1-vinylidene-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, 1-(2-phenylvinylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, and 1-(2-methylvinylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, photochemical precursors to propadienylidene, 3-phenylpropadienylidene, and 3-methylpropadienylidene have been carried out. Photolysis of these new precursors in olefin traps and benzene afforded the expected cyclopropane adducts of the corresponding allenylidenes. Quantum chemical calculations show that the ground state of all three carbenes is a singlet with a singlet-triplet gap of ∼29, 30, and 33 kcal/mol for propadienylidene, 3-phenylpropadienylidene, and 3-methylpropadienylidene, respectively.

Solvated Electrons: Dynamic Reductant in Visible Light Photoredox Catalysis

AbstractOpen shell species are alluring significant attention owing to their unique physiochemical properties in redox chemistry for activating remarkably stable bonds. Solvated electrons are one of them that have been extensively investigated due to their high reduction potential (Ered=−2.9 V vs SHE in CH3CN), diverse substrate activation, and promising applications. If the activating species have a larger redox potential with a longer lifetime, then the broader range of substrates will be activated. Hence, the solvated electron qualifies as a super‐reductant with these qualities. However, due to safety issues, generating solvated electrons by dissolving alkali metals in an ammoniated solvent limits its use towards complicated organic transformations. Instead photochemically generated solvated electron overcome this limitation and is identified as a user‐friendly, sustainable, and much safer alternative approach for producing solvated electrons. In this minireview, we have comprehensively highlighted the recent key methods to generate the solvated electron photochemically, characterization techniques, and its application in organic transformations with selected examples. The minireview provides new opportunities for chemists to understand the conceptual, physical, and mechanistic chemistry principle of this super reductant for exploiting a new photochemical route for the transformations that are difficult to achieve by other means.

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments.

Pharmaceutical residues in sediments are concerning as ubiquitous emerging contaminants. Pyrite is the most abundant sulfide minerals in the estuarine and coastal sediments, making it a major sink for pharmaceutical pollutants such as sulfamethoxazole (SMX). However, research on the adsorption and redox behaviors of SMX on the pyrite surface is limited. Here, we investigated the impact of the nonphotochemical process of pyrite on the fate of coexisting SMX. Remarkably, sulfur vacancies (SVs) on pyrite promoted the generation of nonradical species (hydrogen peroxide, H2O2 and singlet oxygen, 1O2), thereby exhibiting prominent SMX degradation performance under darkness. Nonradical 1O2 contributed approximately 73.1% of the total SMX degradation. The SVs with high surrounding electron density showed an advanced affinity for adsorbing O2 and then initiated redox reactions in the sediment electron-storing geobattery pyrite, resulting in the extensive generation of H2O2 through a two-electron oxygen reduction pathway. Surface Fe(III) (hydro)oxides on pyrite facilitated the decomposition of H2O2 to 1O2 generation. Distinct nonradical products were observed in all investigated estuarine and coastal samples with the concentrations of H2O2 ranging from 1.96 to 2.94 μM, while the concentrations of 1O2 ranged from 4.63 × 10-15 to 8.93 × 10-15 M. This dark-redox pathway outperformed traditional photochemical routes for pollutant degradation, broadening the possibilities for nonradical species use in estuarine and coastal sediments. Our study highlighted the SV-triggered process as a ubiquitous yet previously overlooked source of nonradical species, which offered fresh insights into geochemical processes and the dynamics of pollutants in regions of frequent redox oscillations and sulfur-rich sediments.

Visible Light-Induced Metal-free Arylation of Coumarin-3-carboxylates with Arylboronic Acids.

The present work represents a novel methodology for the selective arylation of coumarin-3-carboxylates with arylboronic acids via a photochemical route, marking the first-ever attempt for the direct alkenyl C-H arylation using rose bengal as a photocatalyst, which is a readily available and cost-effective alternative to transition metal catalysis. The reaction proceeds smoothly in MeOH/H2O solvent media in the presence of radical initiator affording the arylated products in good yields (60-80 %). The reaction parameters such as visible light, radical initiator, oxidant, anhydrous solvent, and inert atmosphere play a crucial role for the success of this methodology. The substituents present on the substrate show a significant effect on the conversion. This study provides a valuable contribution to the field of organic synthesis offering a new and efficient approach to the arylation of coumarin-3-carboxylic acid esters with a broad substrate scope and high functional group tolerance. It is a versatile method and provides a direct access to biologically relevant 4-arylcoumarin-3-carboxylates.

Kinetics of electrochemical Eu3+ to Eu2+ reduction in aqueous media

All lanthanides have a stable trivalent oxidation state, but some of them can also occur in the divalent or tetravalent state. Europium is well-known for its divalent oxidation state, which has been investigated in aqueous, organic, and molten salt media. In contrast to other lanthanides, Eu3+ can be easily reduced (Eo=−0.34 V vs. SHE) via chemical, electrochemical or photochemical routes, and Eu2+ is quite stable in a variety of electrolytes, including nitrate salts. To date, the kinetics of the Eu3+/Eu2+ reduction reaction has been investigated only by polarography and chronopotentiometry, most often in perchlorate medium. In this study, the kinetics of the Eu3+/Eu2+ couple were analysed in nitrate, chloride and perchlorate media by cyclic voltammetry and linear sweep voltammetry with a rotating disk electrode (RDE). The diffusion coefficient, charge transfer coefficient and rate constants were calculated based on the Levich and Koutecký-Levich analysis and Tafel plot to gain insight in the electrochemical process and the influence of the electrolyte type on it. Given the pre-existing characterization of this redox couple in perchlorate medium, it is selected as a reference system to both compare the kinetic parameters and to validate whether the methodology can be applied to other electrolytes. The Eu3+ reduction reaction was found to be quasi-reversible in these electrolytes and the calculated kinetic parameters are in line with the previously reported values.

Photochemical synthesis in inorganic chemistry

Abstract In the last few decades, photochemistry has great influence on all type of synthetic processes. While photochemical synthesis is emerging field in inorganic chemistry as it impart various magnificent properties to materials that are used for synthesis of nano-sized materials to giant supramolecular structures. There are many photochemical based synthetic approaches like electron, atom, energy transfer depending upon the need of product where one can switch the pathway. A variety of inorganic compounds have been synthesized like dienes, nitrides, indoles, gold nano-particles and supramolecular structures using photochemical route. Photochemical synthesis has various applications like artificial photosynthesis and fluorophores.

Catalyst-free photochemical CO2 hydrogenation to CO and CH4 conversion to C2H6

A simple photochemical route was developed that utilizes 172 nm vacuum ultraviolet (VUV) photons as driver for CO2 hydrogenation to CO and the transformation of CH4 to H2 and C2H6.

Metal- and base-free, aerobic photoredox catalysis with riboflavin to synthesize 2-substituted benzothiazoles.

Sustainable approaches for the synthesis of 2-substituted benzothiazoles are sought after for their use in organic chemistry, bioorganic chemistry, and industrial applications. Here, we described a visible light-driven photoredox catalytic cyclization of thioanilides to afford 2-substituted benzothiazoles using riboflavin as a photocatalyst, where oxygen is used as a clean oxidant and ethanol as a greener solvent. These results provide a new photochemical route for environmentally benign synthesis.

Efficient green light-based photocatalytic removal of bilirubin by a biocompatible nanocomposite of nitrogen doped graphene quantum dots/Au

Nitrogen-doped graphene quantum dots/Au (NGQDs/Au) nanocomposite was synthesized by hydrothermal method followed by a photochemical route. The gram-scale nitrogen-doped graphene quantum dot was synthesized by using hydrothermal method from urea and citric acid as a precursor. By adding HAuCl4 to the prepared sample, the nitrogen-doped graphene quantum dots/Au nanocomposite was made in a straightforward photochemical process. The synthesized composite was utilized directly as a biocompatible photocatalyst for bilirubin degradation under green light irradiation.The nanocomposite was characterized using FESEM, Raman, XRD, TEM, UV–Vis spectroscopy, and PL. The quantum yield of the nanocomposite was calculated. The role of surface plasmon resonance (SPR) of Au nanoparticles in reduction of the quantum yield and quantum yield effect on the photodegradation process was investigated. The photocatalytic degradation efficiency of bilirubin in presence of the synthesized nanocomposite was measured to be nearly 74.7 % after 100 min green light irradiation, which is 5 times more than blue light used in clinical phototherapy without any photocatalyst. The optical analysis results reveal that the doping of nitrogen in GQDs and compositing with gold could accelerate the suppression of charge carrier's recombination. The future application of biocompatible photocatalysts in jaundice treatment under the green light irradiation was also approved in this research.

A photochemical route in the synthesis and characterization of La2Ti2O7 and La2Ti2O7/AgO films and its evaluation in Congo red degradation and as antibacterial control to Staphylococcus aureus.

In this article, we propose a simple photochemical method to synthesize pure La2Ti2O7 films and La2Ti2O7 films doped with silver at 1.0, 3.0, and 5.0 mol%. After annealing the photo-deposited films at 900 °C, XRD, SEM, and XPS analyses showed the formation of a monoclinic La2Ti2O7 phase and the presence of Ag and AgO in doped samples. Photocatalytic tests for Congo red degradation demonstrated that pure La2Ti2O7 achieved 25.4% degradation, while doped samples reached a maximum of 92.7% degradation. Moreover, increasing silver doping on La2Ti2O7 films significantly reduced the growth of Staphylococcus aureus, indicating potential antibacterial properties. The enhanced photoactivity was attributed to the formation of a type I heterojunction between La2Ti2O7 and AgO, and a degradation mechanism was proposed based on Congo red degradation.

Iron-Catalyzed Oxidative Decarboxylation of Oxamic Acids: A Safe and Efficient Photochemical Route to Urethanes

AbstractThis study presents a facile method for synthesizing urethanes through the photocatalyzed oxidative decarboxylation of oxamic acids. The process involves the formation of an isocyanate in situ from an oxamic acid under blue-light irradiation (427 nm) in the presence of ferrocene as a photocatalyst, 2-picolinic acid as a ligand, and potassium bromate as an oxidant. The one-pot procedure effectively avoids the need for separation, purification, and storage of carcinogenic isocyanates, making it a safer and more practical method for obtaining target urethanes from easily accessible starting materials.

Photochemical Route for Synthesizing Atomically Precise Metal Nanoclusters from Disulfide.

Practical approaches to the synthesis of atomically precise metal nanoclusters are in high demand as they provide the structural basis for investigating nanomaterials' structure-property correlations with atomic precision. The Brust-Schiffrin method has been widely used, while the essential reductive ligands (e.g., thiols) limit the application of this method for synthesizing metal nanoclusters with specific frameworks and surface ligands. In this work, we developed a photochemical route for synthesizing atomically precise metal nanoclusters by applying disulfide, which is a widely available, stable, and environmentally friendly sulfur source. This method enables the construction of structurally diverse metal nanoclusters and especially features the synthesis of PhS-protected metal nanoclusters that were not easily achieved previously and the gram-scale synthesis. A reduction-oxidation cascade mechanism has been revealed for the photochemical route. This work is expected to open up new opportunities for metal nanocluster synthesis and will contribute to the practical applications of this kind of nanomaterial.

Icosahedral Pd Nanocrystal Catalysts with Dispersed Bi Atoms via Photochemical Route for Enhanced Formic Acid Oxidation Reaction

AbstractThe decoration of noble metal catalysts with specific main group or transition metal atoms offers an effective way to improve the catalytic performance through electronic structure regulation and active site optimization without losing the active surface area. Herein, icosahedral Pd nanocrystals catalysts with highly dispersed Bi atoms decoration have been realized by a simple photochemical reduction approach. The decoration of Bi atoms maintains the original Pd cyclic penta‐twinned structure. The deposition amount of Bi atoms, which greatly affect the catalytic performance, is fundamentally regulated by the irradiation time. Compared with pure Pd, the Pd−Bi icosahedral nanocrystals show significant improvement in electrocatalytic activity towards formic acid oxidation. Besides, the catalytic performance is correlated with the content of Bi. The optimal performance is occurred at the Bi content of 2.86%.

Metal-metal oxide synergistic catalysis: Pt nanoparticles anchored on mono-layer dispersed ZrO2 in SBA-15 for high efficiency selective hydrogenation

It is generally believed that noble metal catalysts exhibited higher activity for selective hydrogenation, while metal oxides were almost inactive. Here, we report metal-metal oxide synergistic catalysis for high efficiency selective hydrogenation by a hybrid nano-structure Pt/@-ZrO2/SBA-15 catalyst, which was fabricated by anchored Pt nanoparticles on the mono-layer dispersed ZrO2 film layer coated in SBA-15 support via a photochemical route. This Pt/@-ZrO2/SBA-15 catalyst exhibited remarkable catalytic activity in the selective hydrogenation of CO bond, NO2, and CC bond. For the selective hydrogenation of benzaldehyde, conversion >99.9% was achieved with >99% selectivity, and the turnover frequency (TOF) can be achieved up to 4822 h−1, which was much higher than that of the atomically dispersed Pd1/TiO2-EG catalyst (1002 h−1) reported in the literature, no decay in the activity was observed by several cycles. Combined the experimental and characterization results, proved that the ZrO2 was dispersed in a mono-layer in the channel of SBA-15, and the results showed that an appropriate loading of ZrO2 in this catalyst could maximize the advantage of this hybrid nano-structure to achieve the best catalytic activity. The superior activity of Pt/@-ZrO2/SBA-15 was attributed to the synergistic catalysis, strong interface electronic effect, and the unique properties of the special hybrid nano-structure. This work demonstrated synergistic catalysis of metal Pt nanoparticles and monolayer dispersion ZrO2 for high efficiency selective hydrogenation.

Photochemical Synthesis of Porous Triazine-/Heptazine-Based Carbon Nitride Homojunction for Efficient Overall Water Splitting.

Porous triazine-/heptazine-based carbon nitride (THCN) homojunction with chloride (Cl) doping was synthesized by a simple, one-step photochemical synthesis route for efficient visible-light-driven overall water splitting. The phase ratio of triazine-based carbon nitride (TCN) and heptazine-based carbon nitride (HCN), texture and morphology of the THCN isotype junction were finely tuned by varying ultraviolet irradiation time and washing solvents. After washing with acetonitrile, the resulting porous THCN nanosheets with 48 h irradiation contain 21 wt % TCN and 79 wt % HCN units and reveal a significantly improved photocatalytic performance with H2 and O2 production rates up to 7.9 and 4.2 μmol h-1 , respectively, about 3.8 times higher than that of THCN prepared by 36 h illumination. The dual-phase interaction, holey structure, and Cl dopants favor the exposure of active sites, extended visible-light harvesting, accelerated charge transfer, and enhanced photoreduction ability, thereby improving photocatalytic activity.

Bismuth-Based Multi-Component Heterostructured Nanocatalysts for Hydrogen Generation

Developing a unique catalytic system with enhanced activity is the topmost priority in the science of H2 energy to reduce costs in large-scale applications, such as automobiles and domestic sectors. Researchers are striving to design an effective catalytic system capable of significantly accelerating H2 production efficiency through green pathways, such as photochemical, electrochemical, and photoelectrochemical routes. Bi-based nanocatalysts are relatively cost-effective and environmentally benign materials which possess advanced optoelectronic properties. However, these nanocatalysts suffer back recombination reactions during photochemical and photoelectrochemical operations which impede their catalytic efficiency. However, heterojunction formation allows the separation of electron–hole pairs to avoid recombination via interfacial charge transfer. Thus, synergetic effects between the Bi-based heterostructured nanocatalysts largely improves the course of H2 generation. Here, we propose the systematic review of Bi-based heterostructured nanocatalysts, highlighting an in-depth discussion of various exceptional heterostructures, such as TiO2/BiWO6, BiWO6/Bi2S3, Bi2WO6/BiVO4, Bi2O3/Bi2WO6, ZnIn2S4/BiVO4, Bi2O3/Bi2MoO6, etc. The reviewed heterostructures exhibit excellent H2 evolution efficiency, ascribed to their higher stability, more exposed active sites, controlled morphology, and remarkable band-gap tunability. We adopted a slightly different approach for reviewing Bi-based heterostructures, compiling them according to their applicability in H2 energy and discussing challenges, prospects, and guidance to develop better and more efficient nanocatalytic systems.

Leveraging Crystalline and Amorphous States of a Metal‐Organic Complex for Transformation of the Photosalient Effect and Positive‐Negative Photochromism

AbstractUncovering differences between crystalline and amorphous states in molecular solids would both promote the understanding of their structure–property relationships, as well as inform development of multi‐functional materials based on the same compound. Herein, for the first time, we report an approach to leverage crystalline and amorphous states of a zero‐dimensional metal‐organic complex, which exhibited negative and positive photochromism, due to the competitive chemical routes between photocycloaddition and photogenerated radicals. Furthermore, different polymorphs lead to the on/off toggling of photo‐burst movement (photosalient effect), indicating the controllable light‐mechanical conversion. Three demos were further constructed to support their application in information encryption and anti‐counterfeiting. This work provides the proof‐of‐concept of a state‐ and polymorph‐dependent photochemical route, paving an effective way for the design of new dynamically responsive systems.

Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism.

Uncovering differences between crystalline and amorphous states in molecular solids would both promote the understanding of their structure-property relationships, as well as inform development of multi-functional materials based on the same compound. Herein, for the first time, we report an approach to leverage crystalline and amorphous states of a zero-dimensional metal-organic complex, which exhibited negative and positive photochromism, due to the competitive chemical routes between photocycloaddition and photogenerated radicals. Furthermore, different polymorphs lead to the on/off toggling of photo-burst movement (photosalient effect), indicating the controllable light-mechanical conversion. Three demos were further constructed to support their application in information encryption and anti-counterfeiting. This work provides the proof-of-concept of a state- and polymorph-dependent photochemical route, paving an effective way for the design of new dynamically responsive systems.