Light-induced Processes Research Articles

Visible light-induced continuous process for photodegradation of chlorpyrifos using g-C3N4/GO/La2O3 photocatalyst from agricultural aquatic waste

The widespread use of pesticides and the formation of by-products on the gradual decomposition of these pesticides have led to environmental pollution, which in turn has caused harm to both human and ecosystem health. Pesticides have been found in water bodies worldwide and are a cause of concern. Photocatalytic reactions have received significant attention in the past few decades for the breakdown of pesticides. Different parameters were studied, including the effects of pH, kinetics, dose, and regeneration. The UV–vis spectroscopy results suggest that the g-C3N4/GO/La2O3 nanocomposite is a superior reusable photocatalyst for the degradation of chlorpyrifos (CPF) compared to pure g-C3N4 and GO/ g-C3N4. This is demonstrated by the fact that the g-C3N4/GO/La2O3 nanocomposite outperforms both of these materials. The increased photocatalytic performance may be attributed to a balance between the band gap, morphology, crystalline quality, and surface area, all of which may be slowing down the electron-hole recombination rates. This may be due to the enhanced photocatalytic performance. In addition, the feasible processes were outlined from radical quenching studies, and the results clearly indicate that the presence of more OH radicals plays an essential role in the process of efficient photodegradation using novel g-C3N4/GO/La2O3 nanocomposites.

Exploring photoconduction mechanisms in Lead‐Free Cs3Sb2I9 single crystal thin films

The future commercial advancement of lead-halide perovskites (LHPs) faces obstacles due to the existence of harmful lead and the inadequate stability associated with these materials. To tackle this challenge, we have prepared a Cs3Sb2I9 perovskite single-crystalline thin film (Cs3Sb2I9 device) using a technique based on the restricted evaporation of solvents in space, aiming for effective photodetection. The photodetector in the current study shows a responsivity (R) of around 111 mA/W and a detectivity (D∗) of approximately 3.7 × 1012 Jones. While these performance metrics are comparable to other photodetectors, there is a need for additional optimization to match the capabilities of commercial silicon and germanium-based counterparts. The examination of ultrafast transient absorption provides insights into the essential photophysics inherent in Cs3Sb2I9. The synergy between the deformation potential and the Fröhlich effect plays a crucial role in shaping electronic dynamics. This synergy leads to the self-trapping of charge carriers, resulting in the creation of localized polarons within the Cs3Sb2I9 lattice within just some picoseconds. The restriction of carrier mobility within Cs3Sb2I9 arises from the self-capturing and confinement of small polarons (SPs). Furthermore, it was noted that SPs in a localized state could undergo absorption into an elevated state (photon energy ⁓ 1.60 eV). This process effectively facilitates the charge carriers' mobilization to a more dispersed eigenstate. Our research provides essential comprehension into the light-induced processes of lead-free halide perovskites (LFHPs), offering valuable insights for their prospective use in optoelectronics as promising future semiconducting agents.

Interpenetrated Donor-Acceptor Heterojunctions in 2D Conjugated Dibenzo[g,p]chrysene-Based Kagome Covalent Organic Frameworks.

Dibenzo[g,p]chrysene can be viewed as a constrained propeller-shaped tetraphenylethylene with reduced curvature and has been utilized to construct dual-pore kagome covalent organic frameworks (COFs) with tightly packed two-dimensional (2D) layers owing to its rigid and more planar structural characteristics. Here, we introduce 2D COFs based on the node 4,4',4″,4‴-(dibenzo[g,p]chrysene-2,7,10,15-tetraphenyl)tetraamine (DBCTPTA) featuring extended conjugation compared to the dibenzo[g,p]chrysene-3,6,11,14-tetraamine (DBCTA) node. We establish two exceptionally crystalline imine-linked 2D COFs with a hexagonal dual-pore kagome structure based on the DBCTPTA core. The newly synthesized thienothiophene (TT) and benzodithiophene (BDT)-based DBCTPTA COFs show a tight stacking behavior between adjacent layers. Furthermore, we obtained an unprecedented, interpenetrated electron-donor/acceptor host-guest system with an electron-donating BDT DBCTPTA COF synthesized in situ with the soluble fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) serving as molecular acceptor. The BDT DBCTPTA COF@PCBM film shows a much shorter amplitude-averaged PL lifetime of 7 ± 2 ps compared to 30 ± 4 ps of the BDT DBCTPTA COF film, indicating the light-induced charge transfer process. The successful in situ formation of interpenetrated donor-acceptor heterojunctions within 2D COFs offers a promising strategy for establishing D-A heterojunctions in diverse framework materials with open channel systems.

Heterostructured g-C3N4-TiO2 nanocomposites applied to p-toluic acid degradation under solar light-induced photocatalytic process

In this work, heterostructured photocatalysts were prepared with TiO2-P25 nanocrystals dispersed on two-dimensional layers of g-C3N4. Different g-C3N4:TiO2 ratios (25 %, 50 % and 75 %) were prepared using a wet method under ultrasonic exfoliation and thermal treatment under an oxidizing atmosphere. The heterojunctions were confirmed by X-ray diffraction, and electron microscopy, showing TiO2 nanocrystals anchored onto the surface of the g-C3N4 structure. The obtained heterojunctions increased light absorption from the ultraviolet to the visible spectrum and reduced the recombination of photoinduced charge carriers confirmed by photoluminescence and band gap energy (Eg) measurements. The photocatalytic performance was evaluated in the degradation of p-toluic acid (p-TA) (20 mg L–1) under UVA LED at 365 nm, a polychromatic lamp (UVA-UVB-visible) and solar radiation. The g-C3N4:TiO2 ratio of 25 % showed the best performance, reaching 95 % degradation after 180 min under solar radiation. The reuse tests showed that the mineralization capacity determined by total organic carbon (TOC) remained stable for 6 cycles, achieving 80.8 % TOC degradation. The heterojunction induced a significant alteration in the rheological behavior of the suspension, which made the g-C3N4-TiO2 easily recoverable, unlike the pure TiO2. The radical scavengers study indicated that the superoxide anion radical (O2•–) is the main oxidative species in p-TA photodegradation on g-C3N4-TiO2 photocatalyst. The greatest advantage of the g-C3N4 in the composite was the absorption of light in the visible range and facile catalyst recovery for reuse while presenting photocatalytic activity similar to TiO2.

S-Arylation of Thioic S-Acid Using Thianthrenium Salts via Photoactivation of Electron Donor-Acceptor Complex.

Thioesters make up an important class of bioactive compounds. Due to their chemoselectivity, they have been widely used in the synthesis of a wide range of complex bioactive molecules and natural products. At present, chemists have developed a variety of methods for the preparation of thioester compounds. However, these methods usually require the use of transition metal catalysis or harsh reaction conditions. The strategy of synthesizing thioester compounds via visible light-induced electron donor-acceptor (EDA) complex reactions avoids the problems associated with conventional methods through the development of photocatalysis. Here we report a sustainable method for thiocarbonylating aryl sulfonium salts via a visible light-induced EDA complex process without transition metals.

Design of an Electrochemical Cell for Continuous Wave EPR Measurements of Radical Ions.

The combination of continuous wave electron paramagnetic resonance (cw-EPR) with electrochemistry is highly attractive as it allows a clean in-situ generation and the subsequent spectroscopic characterisation of radical ions, which are important intermediates in many photocatalytic cycles as well as light-induced processes occurring in biological systems or optoelectronic devices. Although commercial setups for spectroelectrochemical EPR are available, they are often expensive and tailored to a particular spectroscopic setup. Here we present a design for a low-cost electrochemical EPR cell that can be used in combination with any commercial cw-EPR instrumentation. The cell design is compared to existing setups and the performance of the cell is evaluated by comparison of EPR spectra obtained by chemical and electrochemical oxidation of a graphene fragment.

Optimizing photocatalytic hydrogen evolution performance by rationally constructing S-scheme heterojunction to modulate the D-band center

The research in the field of photocatalysis has progressed, with the development of heterojunctions being recognized as an effective method to improve carrier separation efficiency in light-induced processes. In this particular study, CuCo2S4 particles were attached to a new cubic CdS surface to create an S-scheme heterojunction, thus successfully addressing this issue. Specifically, owing to the higher conduction band and Fermi level of CuCo2S4 compared to CdS, they serve as the foundation and driving force for the formation of an S-scheme heterojunction. Through in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, the direction of charge transfer in the composite photocatalyst under light exposure was determined, confirming the charge transfer mechanism of the S-scheme heterojunction. By effectively constructing the S-scheme heterojunction, the d-band center of the composite photocatalyst was adjusted, reducing the energy needed for electron filling in the anti-bonding energy band, promoting the transfer of photogenerated carriers, and ultimately enhancing the photocatalytic hydrogen production. performance. After optimization, the hydrogen evolution activity of the composite photocatalyst CdS-C/CuCo2S4-3 reached 5818.9 μmol g−1h−1, which is 2.6 times higher than that of cubic CdS (2272.3 μmol g−1h−1) and 327.4 times higher than that of CuCo2S4 (17.8 μmol g−1h−1), showcasing exceptional photocatalytic activity. Electron paramagnetic resonance and in situ X-ray photoelectron spectroscopy have established a theoretical basis for designing and constructing S-scheme heterojunctions, offering a viable method for adjusting the D-band center to enhance the performance of photocatalytic hydrogen evolution.

Light-Induced Dynamic Activation of Copper/Silicon Interface for Highly Selective Carbon Dioxide Reduction.

Numerous studies have shown a fact that phase transformation and/or reconstruction are likely to occur and play crucial roles in electrochemical scenarios. Nevertheless, a decisive factor behind the diverse photoelectrochemical activity and selectivity of various copper/silicon photoelectrodes is still largely debated and missing in the community, especially the possibly dynamic behaviors of metal catalyst/semiconductor interface. Herein, through in situ X-ray absorption spectroscopy and transmission electron microscope, a model system of Cu nanocrystals with well-defined facets on black p-type silicon (BSi) is unprecedentedly demonstrated to reveal the dynamic phase transformation of forming irreversible silicide at Cu nanocrystal-BSi interface during photoelectrocatalysis, which is validated to originate from the atomic interdiffusion between Cu and Si driven by light-induced dynamic activation process. Significantly, the adaptive junction at Cu-Si interface is activated by an expansion of interatomic Cu-Cu distance for CO2 electroreduction, which efficiently restricts the C-C coupling pathway but strengthens the bonding with key intermediate of *CHO for CH4 yield, resulting in a remarkable 16-fold improvement in the product ratio of CH4/C2 products and an intriguing selectivity switch. This work offers new insights into dynamic structural transformations of metal/semiconductor junction and design of highly efficient catalysts toward photosynthesis.

Orchestrating Nuclear Dynamics in a Permanganate Doped Crystal with Chirped Pump-Probe Spectroscopy.

Pump-probe spectroscopy is a powerful tool to investigate light-induced dynamical processes in molecules and solids. Targeting vibrational excitations occurring on the time scales of nuclear motions is challenging, as pulse durations shorter than a vibrational period are needed to initiate the dynamics, and complex experimental schemes are required to isolate weak signatures arising from wavepacket motion in different electronic states. Here, we demonstrate how introducing a temporal delay between the spectral components of femtosecond beams, namely a chirp resulting in the increase of their duration, can counterintuitively boost the desired signals by 2 orders of magnitude. Measuring the time-domain vibrational response of permanganate ions embedded in a KClO4 matrix, we identify an intricate dependence of the vibrational response on pulse chirps and probed wavelength that can be exploited to unveil weak signatures of the doping ions─otherwise dominated by the nonresonant matrix─or to obtain vibrational excitations pertaining only to the excited state, suppressing ground-state contributions.

Sustainable Synthesis through Catalyst-Free Photoinduced Cascaded Bond Formation.

The beginning of photochemical reactions revolutionized synthetic chemistry through sustainable practices. This review explores cutting-edge developments in leveraging light-induced processes for generating cascaded C-C and C-hetero bonds without catalysts. Significantly, catalyst-free photoinduced methodologies have garnered considerable attention, especially in the creation of varied heterocyclic frameworks for drug design and the synthesis of natural products. The article delves into underlying mechanisms, addresses limitations, and evaluates various methodologies, emphasizing the potential of photocatalyst and transition metal-free photochemical reactions to enhance sustainability. Divided into two sections, it covers recent strides in C-C and C-heteroatom and multiple C-heteroatom bond formation reactions.

Electron Imaging of Nanoscale Charge Distributions Induced by Femtosecond Light Pulses.

Surface charging is ubiquitously observable during in situ transmission electron microscopy of nonconducting specimens as a result of electron beam/sample interactions or optical stimuli and often limits the achievable image stability and spatial or spectral resolution. Here, we report on the electron-optical imaging of surface charging on a nanostructured surface following femtosecond multiphoton photoemission. By quantitatively extracting the light-induced electrostatic potential and studying the charging dynamics on relevant time scales, we gain insights into the details of the multiphoton photoemission process in the presence of an electrostatic background field. We study the interaction of the charge distribution with the high-energy electron beam and secondary electrons and propose a simple model to describe the interplay of electron- and light-induced processes. In addition, we demonstrate how to mitigate sample charging by simultaneously optically illuminating the sample.

Influence of fluorine atoms on reactive oxygen species-mediated degradation of ophthalmic fluoroquinolones. Kinetic and cytotoxicity studies

Fluoroquinolones have been attractive broad-spectrum antibiotics for ophthalmic application. However, they have shown phototoxicity as a significant side effect, which is strongly dependent on fluoroquinolone structure and some environment conditions. Beyond their photo-reactivity, an indirect light-induced process deserves to be considered. The photosensitized action of molecules present in the ocular organ, such as Riboflavin, may produce reactive oxygen species (ROS) that could degrade fluoroquinolones. As a consequence, the antibiotics may lose their therapeutic action and/or produce degradation products with harmful effects on health.In this contribution, a kinetic analysis of ROS-mediated degradation processes of ophthalmic quinolones is addressed. Further, considering the evidence towards the structure-modulated phototoxicity, we evaluated the influence of structural fluorine atoms on these processes. The non-fluorinated precursor Nalidixic Acid and the fluoroquinolones (Ciprofloxacin, Norfloxacin and Lomefloxacin) were selected for this study. Cytotoxicity experiments in Vero cells were performed in order to investigate the potential toxicity of the ROS-mediated degradation products.Our results suggest that quinolones may be degraded by ROS and these processes are regulated by the ionization state of quinolone and the presence of fluorine atoms in their structure. Both effects increase the electron donor ability of the quinolones, which favor electron transfer processes and increase their reactivity towards species with an electrophilic character. Interestingly, this fluorine-dominated effect has been recently called “fluoromaticity”.Cytotoxicity assays indicated that neither the Qs nor their ROS-mediated degradation products presented injury on Vero cells under the current experimental conditions.

Degradation of methylmercury into Hg(0) by the oxidation of iron(II) minerals

Mercury contamination is a global concern, and the degradation and detoxification of methylmercury have gained significant attention due to its neurotoxicity and biomagnification within the food chain. However, the currently known pathways of abiotic demethylation are limited to light-induced photodegradation process and little is known about light-independent abiotic demethylation of methylmercury. In this study, we reported a novel abiotic pathway for the degradation of methylmercury through the oxidation of both mineral structural iron(II) and surface-adsorbed iron(II) in the absence of light. Our findings reveal that methylmercury can be oxidatively degraded by reactive oxygen species, specifically hydroxyl and superoxide radicals, which are generated from the oxidation of iron(II) minerals under dark conditions. Surprisingly, Hg(0) trapping experiments demonstrated that inorganic Hg(II) resulting from the oxidative degradation of methylmercury was rapidly reduced to gaseous Hg(0) by iron(II) minerals. The demethylation of methylmercury, coupled with the generation of Hg(0), suggests a potential natural attenuation process for methylmercury. Our results highlight the underappreciated roles of iron(II) minerals in the abiotic degradation of methylmercury and the release of gaseous Hg(0) into the atmosphere.

Phytic Acid Customized Hydrogel Polymer Electrolyte and Prussian Blue Analogue Cathode Material for Rechargeable Zinc Metal Hydrogel Batteries.

Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this,the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085Scm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of ≈2.3V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360h with a capacity of 0.50mAhcm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of ≈1.6V and a comparable capacity output of 63mAhg-1 at 0.10Ag-1 of the current rate validating the potential application of ZHPE.

Mechanics of polymers obtained by layered photopolymerization

The photopolymerization process is a high-precision and efficient technology to obtain solid polymers starting from a photosensible liquid resin made of monomer units. This technology is widely used in Additive Manufacturing (AM) to produce objects whose size can fall within the range 10−5−100 m. The outstanding potentialities of this technology can be harnessed to tailor the structure of a polymeric material by controlling how the light-induced polymerization process is performed, typically by operating on subsequent layers forming the final object. The present research illustrates the chemical-physics phenomena involved in the photopolymerization and presents a multi-physics framework and the related governing equations. Its implementation within a computational framework is developed and several simulations demonstrating the influence of the AM printing setup on the final microstructure of the obtained polymer are presented. It is shown that photopolymerization-based AM technology allows us to finely tune the mechanical properties distribution within the material domain, enabling the material's architecture to be tailored to the application of interest.

Light-induced phase transformation to two-dimensional amorphous spinel CoAlOx nanosheets as a tandem photothermal catalyst for efficient and durable toluene oxidation

Low temperature fabrication of spinel oxides and development of efficient and durable toluene photothermal catalysts remain challenging. Herein, two-dimensional amorphous spinel CoAlOx nanosheets (CoAl-LDH-L2) have been fabricated via a light-induced phase transformation strategy using intense photooxidation. Light-induced decomposition and phase transformation process have been used to elucidate the growth mechanism. The CoAl-LDH-L2 exhibits improved toluene adsorption and photothermal conversion, with the highest photothermal catalytic toluene conversion (∼100 % at 500 ppm) at 90 °C, outperforming most previously reported catalysts. Irradiation with mild external heating significantly increases the mineralization rate (∼90 %) and improves the long-term and cycling stability (∼5% losses within 39 h) relative to that under single-light-driven conditions. In-situ DRIFT spectroscopy was also performed for revealing the “tandem photothermal catalysis” mechanism for toluene conversion. This work offers a novel strategy for developing spinel oxides as low-temperature photothermal catalyst in a green and sustainable way.

Investigating the role of corrole as an excitation energy relay in light-induced processes in closely connected N,N'-bis(biphenyl-4-yl)aniline functionalized corrole donor-acceptor dyad.

A photosynthetic antenna-reaction center model, BBA-PFCor comprised of N,N'-bis(biphenyl-4-yl)aniline (BBA) covalently functionalized to bis(pentafluoro)corrole moiety has been prepared and the contribution of the BBA as the photoinduced energy transfer antenna was investigated. UV-visible studies have shown that integrating the electron-rich BBA chromophore into the corrole core has broadened the soret band of the corrole moiety with the absorption spanning from 300 to 700 nm. Electrochemical studies, in corroboration with the computational calculations, revealed that, BBA moiety can act as an electron reservoir and, in the excited state, it would transfer the excited energy to the corrole moiety in the dyad. Steady-state fluorescence studies have demonstrated that, upon photoexcitation of the BBA moiety of BBA-PFCor at 310 nm in solvents of varied polarity, the BBA emission centered at 400 nm was observed to be quenched, with the concomitant appearance of the corrole emission from 500 to 700 nm, indicating the happening of photoinduced energy transfer (PEnT) from 1BBA* to corrole moiety. Parallel control experiments involving the excitation of the corrole moiety at 410 nm did not result in the diminishing of the corrole emission, suggesting that the quenching of the BBA emission in BBA-PFCor is majorly due to intramolecular PEnT from 1BBA* to corrole moiety leading to the formation of singlet excited corrole, that is, 1BBA*-PFCor ➔ BBA-1PFCor*. The free energy changes of PEnT, ΔGEnT, were found to be thermodynamically feasible in all the solvents used for the study. Parallel time-resolved fluorescence studies were congruent with the steady-state fluorescence results and provided further evidence for the occurrence of ultrafast PEnT from 1BBA*➔corrole in the dyad with the rates of energy transfer (kEnT) of ~108 s-1.

The transcription factor StMYB113 regulates light-induced greening by modulating steroidal glycoalkaloid biosynthesis in potatoes (Solanum tuberosum L.)

During harvesting, storage, transportation, and processing, potato (Solanum tuberosum L.) tubers undergo greening after exposure to light, leading to the accumulation of toxic glycoside alkaloids, resulting in quality deterioration and economic losses. However, the underlying mechanisms are unclear. This study compared the transcriptome and proteome differences among four potato cultivars during the light-induced greening process, identifying 3,751 unique proteins (high confidence; ≥91.7%). The levels of enzymes involved in steroidal glycoalkaloid biosynthesis varied among the cultivars. In addition, coexpression network analysis of the transcriptomic data identified the transcription factor MYB113 (Soltu.DM.10G020780.1) as a potential positive regulator of steroidal glycoalkaloid biosynthesis. The dual-luciferase assay revealed that StMYB113 could bind to the promoters of steroidal glycoalkaloid biosynthesis-related genes and activate them. The transgenic lines overexpressing Solanum tuberosum L. Myb domain protein (StMYB113) exhibited greater mRNA abundance of these genes and elevated levels of steroidal glycoalkaloids. This study provided a theoretical basis for exploring the impact of light on the synthesis of solanine in potatoes.

A Theoretical Perspective on the Photochemistry of Boron-Nitrogen Lewis Adducts.

Boron-Nitrogen (B-N) Lewis adducts form a versatile family of compounds with numerous applications in functional molecules. Despite the growing interest in this family of compounds for optoelectronic applications, little is currently known about their photophysics and photochemistry. Even the electronic absorption spectrum of ammonia borane, the textbook example of a B-N Lewis adduct, is unavailable. Given the versatility of the light-induced processes exhibited by these molecules, we propose in this work a detailed theoretical study of the photochemistry and photophysics of simple B-N Lewis adducts. We used advanced techniques in computational photochemistry to identify and characterize the possible photochemical pathways followed by ammonia borane and extended this knowledge to the substituted B-N Lewis adducts pyridine-borane and pyridine-boric acid. The photochemistry observed for this series of molecules allows us to extract qualitative rules to rationalize the light-induced behavior of more complex B-N-containing molecules.

2.2]Paracyclophane-based coumarins: effective organo-photocatalysts for light-induced desulfonylation processes.

Herein, we demonstrate for the first time that coumarins derived from [2.2]paracyclophane (pCp) can act as effective organo-photocatalysts and promote the reductive cleavage of sulfonamides under light-irradiation. In the presence of these original compounds, photodesulfonylation reactions occur under mild conditions at low catalyst loadings in the presence of Hantzsch ester. Theoretical and experimental investigations are described, which elucidate the reaction mechanism and the nature of the active species involved in the photocatalytic process. This proof-of-concept study paves the way for further application of pCps in the field of photocatalysis.