Photocatalytic Conditions Research Articles

Structure-Selection Dynamics of Cobalt Nanoparticles from Solution Synthesis and Their Impact on the Oxygen Evolution Reaction.

Resolving the three-dimensional structure of transition metal oxide nanoparticles (TMO-NPs), upon self-restructuring from solution, is crucial for tuning their structure-functionality. Yet, this remains challenging as this process entails complex structure fluctuations, which are difficult to track experimentally and, hence, hinder the knowledge-driven optimization of TMO-NPs. Herein, we combine high-energy synchrotron X-ray absorption and X-ray total scattering experiments with atomistic multiscale simulations to investigate the self-restructuring of self-assembled Co-NPs from solution under dark or photocatalytic water oxidation conditions at distinct reaction times and atomic length-scales. Using the atomic range order as a descriptor, we reveal that dissolution of a Co-salt in BO3 buffer leads to a self-optimization route forming disordered oxyborate Co3BOx-NPs unveiling a high oxygen yield due to the formation of surface oxo/hydroxo adsorbates. Those Co3BOx-NPs further self-restructure into distorted Co3O4-NPs and, lastly, into distorted CoOOH-NPs through a rate-limiting step integrating Co3+-states during the course of a representative photocatalytic assay. Self-restructuring does not proceed from amorphous-to-ordered states but through stochastic fluctuations of atomic nanoclusters of ≈10 Å domain size. Our key insight into the structure-selection dynamics of TMO-NPs from solution offers a route for tuning their structure-function relationships for wide-ranging emergent technologies.

Nickel/Photoredox Catalyzed Aryl-Alkyl Cross-Coupling with Alkyl Boronic Esters as Radical Precursors.

Nickel/photoredox dual catalyzed cross-coupling of aryl halides with alkylboron compounds is one of the effective methodologies for the construction of C(sp2)-C(sp3) bonds. Although elegant results have been achieved by using alkyl trifluoroborates as alkyl radical precursors, the generation of alkyl radicals from readily available alkyl boronic esters is still limited due to their high oxidation potential. We disclosed here that activation of alkyl boronic esters by MeOLi is highly efficient for the generation of alkyl radicals under photocatalysis conditions. The reaction featured with a wide substrate scope, high functional group tolerance, and late-stage modification of bioactive substances. In addition, the method was also successfully extended to alkyl boronic acids. Experimental and computational mechanistic studies indicated that the cross-coupling likely proceeds via a Ni(I)-catalyzed pathway.

Antagonistic Effect of Nitrate Conversion on Photocatalytic Reduction of Aqueous Pertechnetate and Perrhenate.

Sustainable photocatalysis can effectively reduce the radioactive 99TcO4- to less soluble TcO2·nH2O(s), but the reduction efficiency is highly susceptible to coexisting nitrate (NO3-). Here, we quantitatively investigate photocatalytic remediation conditions for Tc-contaminated water stimulated by the analogue perrhenate (ReO4-) in the presence of NO3-, and we elucidate the influence mechanism of NO3- by in situ characterizations. The interfering NO3- can compete with Re(VII) for the carbonyl radical (·CO2-) produced by formic acid (HCOOH) oxidation to generate nitrogen-containing products such as NH4+, NO2-, and NOx, resulting in the decrease in the Re(VII) reduction ratio. Under the conditions of 4% (volume ratio) HCOOH and pH = 3, the yield of NOx is the lowest, and the selectivity of N2 reaches 93%, which makes the overall reaction more in line with the pollution-free concept. The X-ray absorption fine structure reveals that the redox product Re(IV) mainly exists in the form of ReO2·nH2O(s) and is accompanied by a decrease with the increase in NO3- concentration. Re(VII)/Tc(VII) reduction suffers from a serious interferential effect of NO3-, whereas the higher the concentration of NO3-, the more conducive to slowing down the reoxidation of the reduction products, which is advantageous for the subsequent sequestration or separation.

“Novel Metal‐Free Porphyrin with Ionic Liquid and Sulphonic Acid Moieties for Visible Light Assisted Photocatalytic C−N Coupling of Heterocyclic Compounds with Aryl Halides”

AbstractMetal‐free Buchwald‐Hartwig type photocatalytic approach for N‐substitution of 1,2,4‐triazole at normal temperature was explored for the first‐time using novel imidazolium based Brønsted acid functionalized porphyrin (ImBAFPc). The energy band gap and Hammett acidity were determined by UV‐Vis spectrophotometer. The energy band gap, 1.06 eV supported absorption of radiation in the visible region. The N‐arylation of 1,2,4‐triazole with various Ar−X was achieved in a home‐made photoreactor by heterogeneous, recyclable ImBAFPc photocatalyst under irradiation of 5 W LED with good yields. The protocol tolerated electron donating and attracting Ar−X, including inactivated chlorobenzene, affording the arylated triazole with admirable yields. under ambient photocatalytic conditions.

Selective Functionalization of White Phosphorus with Alkyl Bromides under Photocatalytic Conditions: A Chlorine-Free Protocol to Dialkyl and Trialkyl Phosphine Oxides.

A novel and efficient method for the direct selective alkylation of white phosphorus (P4) with alkyl bromides has been developed, utilizing 4DPAIPN as the photocatalyst and Hantzsch ester as the reductant. This method facilitates the synthesis of structurally diverse dialkyl phosphine oxides in good yields, offering a streamlined alternative to the traditional stepwise approach of chlorinating P4 with Cl2 and subsequently displacing the chlorine atom. Noteworthy features of this reaction include excellent product selectivity, remarkable functional group tolerance, and a broad substrate scope. Additionally, this method is effective for the synthesis of trialkyl phosphine oxides.

Development of flexible and mesoporous CdS/ZnS/PVDF nanocomposites with remarkable organic dye degradation performance under natural sunlight

The engineering of polymer-based nanocomposites is a highly promising strategy for improving both the efficiency and stability of catalysts used in wastewater treatment. In this work, we explore the efficacy of flexible CdS/ZnS/PVDF nanocomposite films towards degradation of Malachite Green dye under low energy visible light and ambient sunlight. Films with varying weight percentage of CdS/ZnS nanofillers (0 %, 5 %, 10 %, 15 %, 20 %) were successfully prepared by solution casting method and the physiochemical properties were characterized using various techniques such as XRD, SEM, AFM, EDX, BET, UV–Vis DRS and FTIR. Pore diameter of 5.5 nm was observed, indicating that CdS/ZnS is mesoporous in nature. Under the optimum photocatalytic condition of 15 ppm dye concentration and pH 9, 15 wt% CdS/ZnS/PVDF showed the maximum photodegradation efficiency of 93.5 % in 30 min. The sample exhibited excellent reusability for five consecutive runs of the experiments which show a degradation percentage of 92.1 % in the fifth run and the scavenging study established that superoxide radicals play the major role in the photodegradation process. The experiments under natural sunlight on three separate days showed a remarkable photodegradation performance of 89 %, 93.4 % and 93.6 % highlighting the potential of CdS/ZnS/PVDF nanocomposites for sustainable wastewater treatment under natural sunlight.

N-Trifluoroethoxy Benzotriazolium Triflate: A Readily Available Reagent for Direct Radical Trifluoroethoxylation of Alkenes.

Herein, we describe the development and application of a novel benzotriazole-based reagent toward radical trifluoroethoxylation. Various alkene classes, including styrene derivatives, enol carbonates, and allyl silanes, are viable reaction partners in this transformation, yielding diverse trifluoroethoxylated products. Furthermore, this method is readily applicable for the late-stage modification of natural product and drugs molecules. Mechanistic and computational studies suggest the intermediacy of an OCH2CF3 radical generated under photocatalytic conditions.

Decarboxylative Xanthylation under Photocatalytic Conditions.

Xanthates are widely used in organic synthesis for the construction of various molecules and have numerous applications as bioactive compounds. Here, we present their preparation via a straightforward photocatalytic decarboxylative xanthylation process involving readily available oxime esters and xanthate dimers. This approach provides access to a wide variety of xanthate compounds in moderate to good yields, including xanthates derived from relevant pharmaceutical and bioactive molecules.

Visible Light Mediated Difluoroalkylation of Alkenes Using Mercaptobenzothiazole‐Derived Sulfide Reagent

AbstractA method for the reductive difluoromethylation of alkenes with 2‐difluoromethylthio(benzothiazole) under photocatalytic conditions is described. The reaction involves the generation of the difluoromethyl radical by means of trimethyltriazinane, which serves as a precursor for the strongly reducing cyclic diaminoalkyl radical.

SPR Effect Enables Flexible Electronic Environment and Activity of Cd0.7In2.2S4-30 for High-Performance Pyro-PEC Catalytic Capability.

Plasma-semiconductor systems hold significant promise in the field of photoelectrocatalysis. In this study, the pyroelectric material cadmium indium sulfide (Cd0.7In2.2S4-30) and Pt were used as catalysts, and a temperature gradient was introduced to investigate the influence of surface plasmon resonance (SPR) effect on the pyroelectric and photocatalytic performance. Interestingly, under the influence of the SPR effect, Cd0.7In2.2S4-30 demonstrates a 1.6-fold and 1.4-fold increase in current density under photocatalytic and pyro-photoelectrocatalytic conditions at 1.23 V vs RHE, respectively. Furthermore, under the protection of surface metal Pt, a notable enhancement in the charge separation efficiency and stability of the photoelectrode material is observed. The combination of outstanding performance reveals that Pt noble metal ions, influenced by the SPR effect, generate a localized electric field at the adjacent semiconductor interface, enhancing the charge transfer capability between metal nanoparticles and the semiconductor, thereby promoting electron-hole separation and improving semiconductor photocatalytic activity. Additionally, the SPR effect increases the yield of high-energy pyro-electrons on plasma metal and facilitates their effective transfer to the semiconductor, thereby promoting the generation of thermally induced electrons. This study reveals the multifaceted of SPR effects on the behaviors of semiconductors and provides an opportunity to rationally design metal-semiconductor photocatalytic materials for efficient solar energy conversion.

Preparation of Soybean Dreg-Based Biochar@TiO2 Composites and the Photocatalytic Degradation of Aflatoxin B1 Exposed to Simulated Sunlight Irradiation.

Aflatoxin B1 (AFB1) is a highly toxic carcinogen severely harmful to humans and animals. This study fabricated SDB-6-K-9@TiO2 composites via the hydrothermal synthesis method to reduce AFB1. The structural characterization results of the photocatalytic composites showed that TiO2 was successfully loaded onto SDB-6-K-9. The different photocatalytic degradation conditions, photocatalyst kinetics, recycling performance, and photocatalytic degradation mechanism were investigated. Photocatalysis with 6 mg of 4%SDB-6-K-9@TiO2 in a 100 μg/mL AFB1 solution presented a reduction of over 95%, exhibiting excellent performance, high stability, and reusability even after five cycles of photocatalytic experiments. Active species trapping experiments confirmed that holes (h+) played the most critical role. After structural analysis and identification of the photocatalytic degradation products, the photodegradation path and photocatalytic oxidation mechanism of 4%SDB-6-K-9@TiO2 were postulated. The results show a new way to improve TiO2's photocatalytic performance, providing a certain theoretical basis for the effective AFB1 reduction.

CuOx supported LaCoO3 perovskite for the photoassisted reverse water gas shift reaction at low temperature

CuOx/LaCoO3 systems have been studied for the rWGS reaction under thermal assisted photocatalytic conditions within low temperature range of 180–330 ºC. CuOx species deposited from chemical reduction method over LaCoO3 homogeneously covered the perovskite surface. The reduction pretreatment before reaction leads to the partial Co reduction and the complete reduction of Cu. A significant improvement on CO production has been attained upon Cu incorporation. In addition, upon UV–vis irradiation the CO production is also enhanced. Best results have been obtained for 5 wt% Cu. The highest synergistic effect was observed for the lowest temperature, for which catalytic contribution is negligible. Thus, a good compromise is attained at 300 ºC for which a CO production of 5.45 mmol/h·g and 92 % selectivity, showing a good synergistic effect between thermo and thermo-photocatalytic activity.

Photocatalyzed Imino-Difluoromethylation of Alkenes with Bifunctional Oxime Esters.

Herein, we report a simple and versatile difluoromethylene-imide reaction in which a series of olefins can undergo a difluoromethylenimine reaction under photocatalytic conditions through an energy transfer (EnT) process. The reaction has mild conditions and a wide range of applicability. We successfully synthesized 27 molecules containing difluoromethylene units, featuring easily accessible starting materials and operational simplicity.

Sodium Hypophosphite as a Halogen Atom Transfer (XAT) Agent under Photocatalytic Conditions.

The ability of sodium hypophosphite to generate the phosphorus-centered radical, which can activate the carbon-halogen bond via the halogen atom transfer (XAT) is described. The hydroalkylation of nonactivated alkenes with methyl bromoacetate was performed using sodium hypophosphite as reducing agent under photocatalytic conditions. The key phosphorus centered radical is formed from the hypophosphite anion by hydrogen atom abstraction.

Spin States Matter─from Fundamentals toward Synthetic Methodology Development and Drug Discovery.

ConspectusThe potent reactivity of carbenes and nitrenes has been traditionally harnessed by the employment of a transition-metal catalyst in which the reactivity of the metal carbene/nitrene intermediates can be controlled via the judicious tuning of the metal catalyst. In recent years, progress made in this research area has unveiled novel strategies to directly access free carbenes or nitrenes under visible-light-mediated conditions without the necessity of a metal catalyst for stabilization of the carbene/nitrene intermediate. Such photochemical approaches present new opportunities to leverage orthogonal reactions with classic metal-catalyzed transformations.In this Account, we describe the major contributions from our group over the past years pushing the boundaries of light-mediated carbene and nitrene transfer reactions. In the first section, the development from purely singlet carbene chemistry toward methods that allow access to triplet carbene intermediates will be dissected. We describe how the triplet spin state of reagents provides a rich array of novel synthetic methods that build on the fundamentals of spin conservation. We lay out the different strategies in accessing the triplet spin state of carbenes (i.e., via electronic stabilization, via triplet sensitization with suitable photocatalysts, or via exploitation of geometric features of these intermediates), followed by an analysis of how the triplet spin state can be employed to leverage reactions distinct to the classic singlet carbene chemistry.The second part focuses on free nitrene intermediates, whereby both photochemical and photocatalytic strategies are analyzed and compared. We initiate with a discussion of the reactivity of iminoiodinanes as nitrene precursors in the presence of a photocatalyst or under photochemical conditions and how these two approaches result in fundamentally distinct nitrogen-based intermediates. While a nitrene radical anion is formed under photocatalytic conditions, triplet nitrene is generated under photochemical conditions. We commence with an outline of the basic reactivity of nitrene transfer reactions under both conditions, with a focus on the reaction with substrates containing double bonds. Finally, the latest developments in advanced cycloaddition chemistry beyond classic aziridination reactions are examined, with a special emphasis on the relay of the triplet nitrene reactivity to enable a Pauson-Khand-like (2 + 2 + 1) cycloaddition reaction that offers convenient access to high value bioisosteres in drug discovery.The work from our group on spin-dependent reactivities offers insight into important fundamentals in synthesis, where the spin state of the reactive intermediate will dictate the reaction outcome. We hope this may inspire others to widen the scope of applications of light-mediated carbene and/or nitrene transfer reactions, and furthermore, we anticipate that these understandings may also enable the development of advanced catalytic systems featuring triplet metal carbene/nitrene intermediates.

Synthesis of Biodegradable Medical Materials Based on Grafted Acrylate Copolymers on Collagen Obtained under Photocatalysis Conditions

Synthesis of Biodegradable Medical Materials Based on Grafted Acrylate Copolymers on Collagen Obtained under Photocatalysis Conditions

A novel all-solid-state Z-scheme BiVO4/Ag/Cu2O heterojunction: Photocatalytic and photothermal synergistic catalysis of tetracycline under simulated sunlight irradiation

The possible hazards posed by tetracycline (TC) to the environment and public health have made it a critical concern. In this work, the all-solid-state Z-scheme heterojunction BiVO4/Ag/Cu2O nanocomposites (NCs) were synthesized through a hydrothermal approach for the purpose of achieving efficient degradation towards TC. BiVO4/Ag/Cu2O NCs were able to efficiently degrade TC when exposed to simulated sunlight. The results showed that the photocatalytic efficiency was significantly influenced by Cu2O and Ag nanocrystals. The presence of Ag with large light absorption capability facilitated the efficient electron (e-) transfer between BiVO4 and Cu2O nanocrystals, thereby expanding the spectral range of light absorption in BiVO4/Cu2O NCs. Under photocatalytic and photothermal synergistic conditions, BiVO4/Ag/Cu2O NCs with an optimal addition of Ag were able to degrade TC within 60 min at reaction rate constant (k) of 0.04816 min−1. It was discovered that the best-performing photocatalysts (BAC-2) achieved photothermal conversion rates as high as 27.9 %, and they could exhibit outstanding photocatalytic and photothermal efficiency even after six cycles. Furthermore, the results obtained in radical trapping experiments suggested that photogenerated holes (h+), electrons (e-), superoxide radicals (·O2-), hydroxyl radicals (·OH) and singlet oxygen (1 O2) were involved in the photocatalytic degradation of TC. In the context of practical application, the effects of different initial TC concentrations and different irradiation conditions were studied in depth. In addition, the all-solid-state Z-scheme heterojunction mechanism for degrading TC was put forward. This research endeavors to broaden the application scope of all-solid-state Z-scheme heterojunction photocatalysts, with the aim of achieving significantly improved photocatalytic degradation of antibiotic pollutants.

Exploring novel porphyrin photocatalyst for the conversion of frying oil to biodiesel: A step for globular economy

The current protocol addresses the outcomes on the photo-transesterification of frying sunflower oil (FSO) catalysed by porphyrin comprising sulphonic acid functionalized pyridinium ionic liquid (PcSAFPyIL). A novel photocatalyst was synthesized and confirmed by 1H and 13C NMR, Powder XRD, FT-IR, XPS, and fluorescence emission spectrophotometry. The energy band gap (1.85 eV) was determined by cyclic voltammetry, Hammett acidity (H0 = 0.217) by UV–visible spectrophotometer and metal free nature by powder XRD and XPS. The photocatalytic activity of PcSAFPyIL in the visible region was confirmed by reflecting intense Soret band (421 nm) and four Q bands (515, 554, 591 and 647 nm). This may be due to inherent aromatic characters and conjugation with chromophore groups at meso-position of porphyrin ring. The obtained photocatalyst was scrutinized for the photo-transesterification of FSO in a lab-made photoreactor. The ideal reaction parameters were found to be 20 mg photocatalyst quantity with 1:12 (FSO: ROH) under exposure of 2 x 5 W LED at room temperature, to afford 90 % biodiesel in 24 h. Moreover, the formation of biodiesel was confirmed by (1H, 13C) NMR, FT-IR, DEPT-135, and GC–MS. Further, stability, heterogeneous nature and the gram scale reaction PcSAFPyIL was also efficiently accomplished using the optimized photocatalytic conditions. Additionally, the physicochemical properties of the biodiesel fuel B15 (15 % blended with marketed diesel) and pure marketed diesel are consistent. Moreover, the engine performance and emission characteristics of B15 such as brake-specific fuel consumption (BSFC), break thermal efficiency (BTE) found comparable and better than commercial diesel.

Photoredox Activation of Fluorinated Organozinc Reagents: Hydrofluoroalkylation of Unactivated and Electron Deficient Alkenes.

Hydrofluoroalkylation of alkenes with organozinc reagents under photocatalytic conditions is described. The fluorinated alkyl radicals were generated from organozincs by the single electron oxidation of the carbon-zinc bond. The radical addition step is followed either by hydrogen atom transfer for unactivated olefins or by a reduction/protonation sequence for strongly accepting arylidenemalononitriles.

Amorphous NiB layer deposition and piezoelectric field assisted for efficient photocatalytic degradation of Sb2S3

The poor surface charge reaction efficiency and electrical conductivity limit the further application of Sb2S3 in photocatalytic degradation of pollutants. An amorphous NiB layer was deposited on the surface of Sb2S3 by photo-assisted electrodeposition, and the presence of the NiB layer accelerated the charge transport and catalytic reactivity, which greatly enhanced the degradation ability. The photocurrent density of NiB-Sb2S3 was about 0.12 mA/cm2, which was 6 times of that of pure Sb2S3. After increasing the applied mechanical site by ultrasonication, the photocurrent of NiB-Sb2S3 was further increased to 0.19 mA/cm2, which was almost 9.5 times that of pure Sb2S3 under photocatalytic conditions alone. The catalytic kinetic curves show that the degradation rate of RhB by NiB-Sb2S3 under piezoelectric-photocatalytic conditions is significantly increased, being 11.48 times of the degradation rate of Sb2S3 under photocatalytic conditions. The detailed experimental data indicate that the amorphous NiB layer not only changes the electronic structure of the catalyst surface, but also increases the number and activity of the catalyst active sites, and reduces the chance of electron and hole recombination after photoexcitation. The introduction of an applied piezoelectric field provided a driving force for carrier migration to the catalyst surface, which further improved the separation ability. This study provides a new strategy to further improve the photocatalytic degradation.