High Photoactivity Research Articles

Plasmon-Enhanced Photoelectrochemistry of Photosystem II on a Hierarchical Tin Oxide Electrode for Ultrasensitive Detection of 17β-Estradiol.

Despite its excellent efficiency in natural photosynthesis, the utilization of photosystem II (PSII)-based artificial photoelectrochemical (PEC) systems for analytical purposes is hindered due to the low enzyme loading density and ineffective electron transfer (ET) processes. Here, we present a straightforward and effective approach to prepare a PSII-based biohybrid photoanode with remarkable photoresponse, enabled by the use of a hierarchically structured inverse-opal tin oxide (IO-SnO2) electrode combined with gold nanoparticles (Au NPs). The porous, carbon-containing IO-SnO2 structure allows for a high density and photoactivity loading of PSII complexes, while also providing strong electrical coupling between the protein film and the electrode. A new electron transfer pathway mediated by Au NPs was identified at the protein-electrode interface, which efficiently shuttles the photogenerated electrons from the enzyme to the IO-SnO2 electrode. Furthermore, the PEC response of the electrode was significantly enhanced by the surface plasmon resonance (SPR) effect of Au NPs. Upon light irradiation, this PSII-based photoanode exhibited an impressively high and stable photocurrent output, which was utilized to fabricate an aptasensor for 17β-Estradiol (E2) detection. Under optimal conditions, a detection limit of 0.33 pM was obtained, along with a broad detection range from 15 pM to 30 nM. The applicability of the aptasensor was assessed by measuring E2 in water and urine samples, demonstrating its feasibility in environmental monitoring and clinical tests.

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

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

Azobenzene-Bridged Covalent Organic Frameworks Boosting Photocatalytic Hydrogen Peroxide Production from Alkaline Water: One Atom Makes a Significant Improvement.

Covalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H2O2) production. However, the construction of COFs with new active sites, high photoactivity, and wide-range light absorption for efficient H2O2 production remains challenging. Herein, we present the synthesis of a novel azobenzene-bridged 2D COF (COF-TPT-Azo) with excellent performance on photocatalytic H2O2 production under alkaline conditions. Notably, although COF-TPT-Azo differs by only one atom (-N=N- vs. -C=N-) from its corresponding imine-linked counterpart (COF-TPT-TPA), COF-TPT-Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal-free photocatalyst, COF-TPT-Azo achieves a high photocatalytic H2O2 production rate up to 1498 μmol g-1 h-1 at pH = 11, which is 7.9 times higher than that of COF-TPT-TPA. Further density functional theory (DFT) calculations reveal that the -N=N- linkages are the active sites for photocatalysis. This work provides new prospects for developing high-performance COF-based photocatalysts.

Azobenzene‐Bridged Covalent Organic Frameworks Boosting Photocatalytic Hydrogen Peroxide Production from Alkaline Water: One Atom Makes a Significant Improvement

AbstractCovalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H2O2) production. However, the construction of COFs with new active sites, high photoactivity, and wide‐range light absorption for efficient H2O2 production remains challenging. Herein, we present the synthesis of a novel azobenzene‐bridged 2D COF (COF‐TPT‐Azo) with excellent performance on photocatalytic H2O2 production under alkaline conditions. Notably, although COF‐TPT‐Azo differs by only one atom (−N=N− vs. −C=N−) from its corresponding imine‐linked counterpart (COF‐TPT‐TPA), COF‐TPT‐Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal‐free photocatalyst, COF‐TPT‐Azo achieves a high photocatalytic H2O2 production rate up to 1498 μmol g−1 h−1 at pH = 11, which is 7.9 times higher than that of COF‐TPT‐TPA. Further density functional theory (DFT) calculations reveal that the −N=N− linkages are the active sites for photocatalysis. This work provides new prospects for developing high‐performance COF‐based photocatalysts.

Investigating and correlating the photocatalytic activity of synthesised strontium titanate nanopowder with calcination temperature

In this study, SrTiO3 nanoparticles were synthesised in high yield using a simple and low-cost method, followed by calcination. The effect of the calcination temperature in the range from 700 to 1100 °C on the morphology, phase structure, crystallite size, and photocatalytic activity of SrTiO3 nanoparticles was investigated. Analysis of the morphology and structure of the synthesised samples revealed an increase in the average particle size from 70.4 to 361.72 nm as well as crystallite growth with increasing calcination temperature (from 800 to 1100 °C), likely due to the fusion of smaller crystallites into larger ones. A possible pathway for the growth mechanism of strontium titanate grains was also proposed. The SrTiO3 sample calcined at 800 °C exhibited the highest methylene blue (MB) photodegradation efficiency, achieving 100 % degradation within 30 min of irradiation. The pseudo-first-order reaction rate constant k for this sample was determined to be 0.156 min−1, which is almost 1.8 and 14.19 times higher compared to those of commercial P25 and SrTiO3, respectively. The analysis indicated that the high photoactivity of this sample was due to its high crystallinity, relatively small particle size, and optimal light absorption, which enhanced the separation and transport of the photogenerated charges and increased the number of active sites, thereby positively affecting the photocatalytic properties. Additionally, the effects of the initial dye concentration and amount of photocatalyst loaded on the photodegradation efficiency were investigated.

Cathodic shift in flatband potential of hematite based photoelectrodes: Evaluating and correlating the redshift to solar driven photocatalysis

As a promising metal oxide semi-conductor, hematite (α-Fe2O3) has interesting optical properties to be regarded as photoactive material. In this study, we evaluated the cathodic shift in onset potential (Eonset) and the negative shift in flat band potential (Efb). It was observed that the Eonset value of −0.457 V for α-Fe2O3 based electrode shifted to −0.638 V for the ternary nanocomposite (PNFC) [Pani/Ni-α-Fe2O3/CNT] based electrode. The flat band potential for α-Fe2O3 in 1 M NaOH is at −0.49 V which shifts to −0.68 V for the ternary nanocomposite (PNFC). This photoelectrochemical enhancement appears due to electron-hole pair separation. Therefore, it apparently increases the photocurrent trace for PNFC at −0.60 V to 7.04 mA cm-2, compared to the photocurrent of 4.52 mA cm-2 observed for pristine α-Fe2O3. According to the Mott-Schottky plot, the donor concentration (Nd) for the α-Fe2O3 is 4.83 × 109 cm-3, whereas for the ternary nanocomposite (PNFC) is 7.68 × 109 cm-3, respectively. As evident, the Nd value increase for the ternary nanocomposite PNFC points to the proximity of the Fermi (Ef) level below the CB edge when Ni doped α-Fe2O3 comes in contact with polyaniline (Pani). Indeed, the ternary nanocomposite PNFC with lower Eg value (1.32 eV) and higher photocurrent (7.04 mA cm-2) show higher photo-activity with percent degradation of 98.42 % for photocatalytic degradation of Sunset Yellow under visible light irradiation. The aforementioned correlations of the energetic levels of band edges with the shifting of Efb to more negative potentials provide insight into the high photo-activity observed.

Hierarchical Branched TiO2 Photo/Photoelectrocatalyst with Directed Charge Transfer for Efficient Hydrogen Production from Seawater.

The directed electron transport channel design in semiconductors, which could promote charge utilization, is attractive but rarely reported. Hierarchical branched titanium dioxide (HB-TiO2), possessing a charge cascade transfer channel, was constructed by assembling titanium-defected TiO2 nanobranches on oxygen-defected TiO2 nanobelts. The interfacial Ti/O vacancies have been detected by X-ray photoelectron and electron paramagnetic resonance spectroscopies, and the vacancies act as the "bridge" of photogenerated carrier transport. This structure maintained high photoactivity in H2 production in different mass fractions of NaCl solutions. The photocurrent density of the HB-TiO2 photoanode in natural seawater is 3.9, 2.1, and 2.6 times that of oxygen-defected TiO2 nanobelts, titanium-defected TiO2 nanobranches, and their mixture, respectively. Besides, the charge transport mechanism from the inner lattice to the TiO2 surface is proposed.

A Review of the Efficacy of Nanomaterial-Based Natural Photosensitizers to Overcome Multidrug Resistance in Cancer.

Natural photosensitizers (PS) are compounds derived from nature, with photodynamic properties. Natural PSs have a similar action to that of commercial PSs, where cancer cell death occurs by necrosis, apoptosis, and autophagy through ROS generation. Natural PSs have garnered great interest over the last few decades because of their high biocompatibility and good photoactivity. Specific wavelengths could cause phytochemicals to produce harmful ROS for photodynamic therapy (PDT). However, natural PSs have some shortcomings, such as reduced solubility and lower uptake, making them less appropriate for PDT. Nanotechnology offers an opportunity to develop suitable carriers for various natural PSs for PDT applications. Various nanoparticles have been developed to improve the outcome with enhanced solubility, optical adsorption, and tumor targeting. Multidrug resistance (MDR) is a phenomenon in which tumor cells develop resistance to a wide range of structurally and functionally unrelated drugs. Over the last decade, several researchers have extensively studied the effect of natural PS-based photodynamic treatment (PDT) on MDR cells. Though the outcomes of clinical trials for natural PSs were inconclusive, significant advancement is still required before PSs can be used as a PDT agent for treating MDR tumors. This review addresses the increasing literature on MDR tumor progression and the efficacy of PDT, emphasizing the importance of developing new nano-based natural PSs in the fight against MDR that have the required features for an MDR tumor photosensitizing regimen.

Synthesis and Evaluation of Novel meso-Tetraphenyltetrabenzoporphyrins for Photodynamic Therapy.

To discover effective photosensitizers for photodynamic therapy (PDT), a series of new meso-tetraphenyltetrabenzoporphyrin (m-Ph4TBP) derivatives were designed, prepared, and characterized. All m-Ph4TBPs own two characteristic absorption bands in the range of 450-500 and 600-700 nm and have the ability to generate singlet oxygen upon photoexcitation. Most of the m-Ph4TBPs demonstrated high photoactivity, among which compounds I4, I6, I12, and I13 induced apoptosis and also exhibited excellent photodynamic activities in vivo. Nonetheless, the liver organs of the I4 and I6-PDT groups showed clear calcifications, whereas the liver tissues of the other PDT groups showed no calcification. It was indicated that compared to phenolic m-Ph4TBPs, glycol m-Ph4TBPs exhibited superior biological safety in mice. According to comprehensive evaluations, m-Ph4TBP I12 displayed excellent photodynamic antitumor efficacy and biological safety and can be regarded as a promising antitumor drug candidate.

In-situ synthesis of sunlight-driven CuO-ZnO heterostructure photocatalyst for enhanced elimination of organic pollutants and CO2 reduction

Removing hazardous organic pollutants, such as 4-nitrophenol (4-NP) and Congo red (CR) dyes from aqueous media and CO2 from the atmospheric medium remains a significant challenge. Herein, we report a facile in-situ synthetic approach for fabricating CuO-ZnO heterostructure photocatalysts through the surfactant-assisted co-precipitation method. The catalytic results demonstrate that the Cu1O-ZnO photocatalyst exhibits excellent activity under direct sunlight irradiation, owing to the heterostructure formation between the CuO and ZnO. The Cu1O-ZnO photocatalyst showed higher reaction rate constant (k) values of 0.20 min−1 for 4-NP and 0.09 min−1 for CR compared to previous reports. Additionally, efficient CO2 reduction was also achieved over Cu1O-ZnO photocatalyst. The optical and structural characterization results indicate that the improved photocatalytic reduction and degradation observed for the Cu1O-ZnO photocatalyst can be attributed to the strong synergistic interaction between p-type CuO and n-type ZnO and the construction of the p-n heterojunction. As a result, the absorption of visible light distinctly increased and inhibited the recombination rate of the photo-created electron-hole (e−/h+). Furthermore, the Cu1O-ZnO photocatalyst exhibited remarkable durability and recyclability, retaining high photoactivity (≥ 93%) after five cycles, demonstrating its potential for real-world applications in the photocatalytic reduction and degradation reactions under direct sunlight irradiation.

TiO2 Nanoparticles with Adjustable Phase Composition Prepared by an Inverse Microemulsion Method: Physicochemical Characterization and Photocatalytic Properties.

Titania nanoparticles (NPs) find wide application in photocatalysis, photovoltaics, gas sensing, lithium batteries, etc. One of the most important synthetic challenges is maintaining control over the polymorph composition of the prepared nanomaterial. In the present work, TiO2 NPs corresponding to anatase, rutile, or an anatase/rutile/brookite mixture were obtained at 80 °C by an inverse microemulsion method in a ternary system of water/cetyltrimethylammonium bromide/1-hexanol in a weight ratio of 17:28:55. The only synthesis variables were the preparation of the aqueous component and the nature of the Ti precursor (Ti(IV) ethoxide, isopropoxide, butoxide, or chloride). The materials were characterized with X-ray diffraction, scanning/transmission electron microscopy, N2 adsorption-desorption isotherms, FTIR and Raman vibrational spectroscopies, and diffuse reflectance spectroscopy. The synthesis products differed significantly not only in phase composition, but also in crystallinity, textural properties, and adsorption properties towards water. All TiO2 NPs were active in the photocatalytic decomposition of rhodamine B, a model dye pollutant of wastewater streams. The mixed-phase anatase/rutile/brookite nanopowders obtained from alkoxy precursors showed the best photocatalytic performance, comparable to or better than the P25 reference. The exceptionally high photoactivity was attributed to the advantageous electronic effects known to accompany multiphase titania composition, namely high specific surface area and strong surface hydration. Among the single-phase materials, anatase samples showed better photoactivity than rutile ones, and this effect was associated, primarily, with the much higher specific surface area of anatase photocatalysts.

Quantitative analysis of the electromagnetic hybrid nanofluid flow within the gap of two tubes using deep learning neural networks

Purpose(1) A mathematical model for the Hybrid nanofluids flow is used as carriers for delivering drugs. (2) The flow conditions are controlled to enable drug-loaded nanofluids to flow through the smaller gap between the two tubes. (3) Hybrid nanofluids (HNFs) made from silver (Ag) and titanium dioxide (TiO2) nanoparticles are analyzed for applications of drug delivery. (Ag) and (TiO2) (NPs) are suitable candidates for cancer treatment due to their excellent biocompatibility, high photoactivity, and low toxicity. (4) The new strategy of artificial neural networks (ANN) is used which is machine-based and more prominent in validation, and comparison with other techniques.Design/methodology/approachThe two Tubes are settled in such a manner that the gap between them is uniform. The Control Volume Finite Element Method; Rk-4 and Artificial Neural Network (ANN).Findings(1) From the obtained results it is observed that the dispersion and distribution of drug-loaded nanoparticles within the body will be improved by the convective motion caused by hybrid nanofluids. The effectiveness and uniformity of drug delivery to target tissues or organs is improved based on the uniform flow and uniform gap. (2) The targeting efficiency of nanofluids is further improved with the addition of the magnetic field. (3) The size of the cylinders, and flow rate, are considered uniform to optimize the drug delivery.Research limitations/implications(1)The flow phenomena is considered laminar, one can use the same idea through a turbulent flow case. (2) The gap is considered uniform and will be interesting if someone extends the idea as non-uniform.Practical implications(1) To deliver drugs to the targeted area, a suitable mathematical model is required. (2) The analysis of hybrid nanofluids (HNFs) derived from silver (Ag) and titanium dioxide (TiO2) nanoparticles is conducted for the purpose of drug delivery. The biocompatibility, high photoactivity, and low toxicity of (Ag) and (TiO2) (NPs) make them ideal candidates for cancer treatment. (3) Machine-based artificial neural networks (ANN) have a new strategy that is more prominent in validation compared to other techniques.Social implicationsThe drug delivery model is a useful strategy for new researchers. (1) They can extend this idea using a non-uniform gap. (2) The flow is considered uniform, the new researchers can extend the idea using a turbulent case. (3) Other hybrid nanofluids flow, in the same model for other industrial usages are possible.Originality/valueAll the obtained results are new. The experimental thermophysical results are used from the existing literature and references are provided.

Sol-gel Pechini preparation of CuEr2TiO6 nanoparticles as highly efficient photocatalyst for visible light degradation of acid red 88

This study reports preparation of CuEr2TiO6 nanoparticles using Pechini sol-gel method. The characterization of nanoparticles was carried out using FESEM, EDX, XRD, PL, DRS, Raman, and FTIR. DRS analysis shows that the prepared nanoparticles can serve as an effective visible light photocatalyst. Photocatalytic activity of the prepared nanoparticles was investigated toward degradation of aqueous solution of acid red 88 (AR88) under visible light irradiation. The highest photoactivity (91.2 %) was achieved after 150 min illumination using 40 mg of the photocatalyst. Effect of some contributing factors was studied on degradation rate of AR 88, including amount of photocatalyst and H2O2 concentration. Also, in order to examine stability of the prepared nanoparticles for long-time applications, the recyclability experiments were conducted at 7 successive reaction cycles which confirm the great stability of the prepared nanoparticles. Also, radical scavenging experiments reveal that the dominant species in photocatalytic reactions are hydroxyl radicals.

LAMP-visualized photofuel cell self-powered dual-mode sensing platform for detection of transmissible gastroenteritis virus

The detection of transmissible gastroenteritis virus (TGEV) is of great significance to reduce the loss of pig industry. A LAMP-visualization/PFC self-powered dual-mode output sensor platform was constructed to detect TGEV by combining a simple and intuitive photoelectrochromic material with a highly sensitive PFC self-powered sensing platform without external power supply. The PFC sensing substrate was constructed using CdS nanoparticles modified ZnO NRs (CdS/ZnO NRs) as the photoanode, which exhibited high photoactivity, and Prussian blue (PB) as the cathode. After LAMP reaction on the optical anode, visual signals caused by PB discolorimetry can be detected semi-quantitatively, or PFC power density electrical signals collected by electrochemical workstation can be used. The output power density value is logarithm of TGEV concentration. The linear relationship was good within the detection range of 0.075 fg/μL-7.5 ng/μL, with a detection limit of 0.025 fg/μL (S/N = 3). This multi-signal output sensing platform provides more choices for quantifying TGEV detection results, and the two methods can be mutually verified, which meets the needs of different scenarios and improves the reliability of detection. It has a good effect in the actual sample detection, without the use of expensive and complex instruments, and has a broad application prospect.

Fabricating mesoporous titanium nanocomposites with high adsorption and photolysis performance by using rice husk ash as a renewable support source

Rice husk (RH) is a valuable and renewable source of bioenergy. Once RH has been burned to produce thermal energy, RH ash (RHA) remains, and this ash can be used as a sustainable resource to improve the circular economy. In this study, we used RHA as a silicon source to fabricate RH-SBA-15. Incipient wetness impregnation was then employed to directly incorporate TiO2 nanocrystals into the mesopores of the RH-SBA-15. XRD and TEM confirmed the successful integration of TiO2 into the framework of RH-SBA-15, with the hexagonal array and ordered mesostructure of RH-SBA-15 being unchanged. FTIR and XPS revealed the formation of Ti–O–Si bonds on the surface of RH-SBA-15, which enhanced the activity of TiO2. The pore volume and surface area of TiO2/RH-SBA-15 were 0.292–0.604 cm3/g and 170–366 m2/g. Photocatalytic tests were conducted to examine the catalysts used in the degradation of Reactive Blue 4 (RB4). The results indicated that TiO2/RH-SBA-15 exhibited 63% higher catalytic efficiency than that did bare TiO2. The surface adsorption of RH-SBA-15 and the high photolytic activity of TiO2 resulted in an improvement in RB4 degradation. The photoactivity increased with decreasing solution pH and calcination temperature and increasing catalyst mass. A TiO2 ratio of 25% resulted in the highest photoactivity, yielding a composite that completely eliminated RB4 within 5 h. The catalyst composites had high stability and photoactivity after four cycles. Overall, the method used in this study for fabricating mesoporous photocatalysts from recycled RHA is valuable for bio-waste disposal and wastewater purification.

Ion Pairing Enables Targeted Prodrug Activation via Red Light Photocatalysis: A Proof-of-Concept Study with Anticancer Gold Complexes.

Photocatalysis has found increasing applications in biological systems, for example, in localized prodrug activation; however, high-energy light is usually required without giving sufficient efficiency and target selectivity. In this work, we report that ion pairing between photocatalysts and prodrugs can significantly improve the photoactivation efficiency and enable tumor-targeted activation by red light. This is exemplified by a gold-based prodrug (1d) functionalized with a morpholine moiety. Such a modification causes 1d to hydrolyze in aqueous solution, forming a cationic species that tightly interacts with anionic photosensitizers including Eosin Y (EY) and Rose Bengal (RB), along with a significant bathochromic shift of absorption tailing to the far-red region. As a result, a high photoactivation efficiency of 1d by EY or RB under low-energy light was found, leading to an effective release of active gold species in living cells, as monitored by a gold-specific biosensor (GolS-mCherry). Importantly, the morpholine moiety, with pKa ∼6.9, in 1d brings in a highly pH-sensitive and preferential ionic interaction under a slightly acidic condition over the normal physiological pH, enabling tumor-targeted prodrug activation by red light irradiation in vitro and in vivo. Since a similar absorption change was found in other morpholine/amine-containing clinic drugs, photocages, and precursors of reactive labeling intermediates, it is believed that the ion-pairing strategy could be extended for targeted activation of different prodrugs and for mapping of an acidic microenvironment by low-energy light.

New ketoxime ester-amine photoinitiator based on charge transfer complex for free radical LED polymerization

Recently, visible-light polymerization has received increasing attention because of the development of LED sources and the innovation of photopolymerization technology, which is derived from different strategies to design photoinitiating systems such as the construction of D-π-A-type photoinitiators or the use of up-conversion nanoparticles. However, the association of electron donor and acceptor molecules to form a charge-transfer complex (CTC) for polymerization has rarely been reported. Hence, a ketoxime ester (PFO) with a pentafluorophenone ring as an electron-defect acceptor has been designed and synthesized as a photosensitizer. Our investigation results showed that CTCs could be formed by associating PFO with amines that contain electron-rich rings and process a better absorption property in the visible-light region than PFO. Moreover, the two kinds of free radicals with high photoactivity were generated from CTCs via photochemical transformation, such as intermolecular charge transfer and α-cleavage, which can play a role in initiating the polymerization of acrylate monomers, and the efficiency of initiating polymerization is higher than that of PFO alone under LED@395–425 nm irradiation.

Cobalt Oxide on Boron-Doped Graphitic Carbon Nitride as Bifunctional Photocatalysts for CO2 Reduction and Hydrogen Evolution.

In this work, the prepared cobalt oxide decorated boron-doped g-C3N4 (CoOx/g-C3N4) heterojunction exhibits remarkable activity in CO2 reduction (CO2RR), resulting in high yields of CH3COOH (∼383 μmol·gcatalyst-1) and CH3OH (∼371 μmol·gcatalyst-1) with 58% selectivity to C2+ under visible light. However, the same system leads to high H2 evolution (HER) by increasing the cobalt oxide content, suggesting that the selectivity and preference for the CO2RR or HER depend on oxide decoration. By comparing HER and CO2RR evolution in the same system, this work provides critical insights into the catalytic mechanism, indicating that the CoOx/g-C3N4 heterojunction formation is necessary to foster high visible light photoactivity.

Photo-Reactivity of dissolved black carbon unveiled by combination of optical spectroscopy and FT-ICR MS analysis: Effects of pyrolysis temperature

Dissolved black carbon (DBC) has high photoactivity, which plays an important role in contaminants photodegradation. However, it is unclear how pyrolysis temperatures would affect the composition and photo-reactivity of DBC at the molecular level. Herein, we combined complementary techniques to study the characteristics of DBC pyrolyzed at 200 - 500 ℃, as well as the photoproduction of reactive species and the photodegradation of tetracycline (TC). Bulk composition characterization found that condensed aromatic carbonyl compounds (ConAC) with narrow molecular weights in DBC experienced an increase from 200 to 500 °C, which enhanced the photoproduction of 3DBC*,1O2, and ·OH. Molecular-level data suggested that 3DBC* and 1O2 were both related to the same DBC compounds. Comparatively, the patterns for ·OH were less pronounced, implying its precursor was not 3DBC* and had more complexity. Plentiful CHOx species of ConAC in DBC400 and DBC500 (DBCT, where T = pyrolysis temperature) accelerated the generation of 3DBC* and 1O2, enhancing the photodegradation of TC, and mainly triplet states of quinones reacted with TC. In contrast, DBC200 and DBC300 exhibited inhibition since massive CHOx species in lignin-like reduced 3TC* to TC. Our data revealed the diverse photochemical behavior mechanisms of DBC pyrolyzed at 200 – 500 ℃ at the molecular level and the implications for aquatic contaminants photochemistry.

APPLICATION OF ACTIVATING INFLUENCES IN OBTAINING TiO2-PILLARED MONTMORILLONITE WITH IMPROVED PHOTOCATALYTIC PROPERTIES

A new approach to the obtaining of a highly efficient photocatalyst - TiO2-pillared montmorillonite – by hydrothermally activated intercalation of mechanically dispersed bentonite matrix with the polyhydroxocomplexes of titanium is proposed. The material was characterized by the X-ray diffractometry, low-temperature nitrogen adsorption-desorption, scanning electron microscopy, energy dispersive microanalysis, and zeta potential measurement. The use of short-term (up to 3 min) mechanical dispersion in a planetary mill significantly increases the capacity of cation exchange during intercalation, and the photocatalysts obtained after annealing at 500 °C are characterized by significantly higher values of specific surface area and total pore volume compared with mechanically untreated and initial montmorillonite. The average size of TiO2 crystallites is about 10 nm and the content of anatase is over 90%. Mechanical activation leads to a significant change in the ζ-potential of montmorillonite particles from a significantly negative value in the source material to almost zero, which is an additional argument for more efficient intercalation. Hydrothermal treatment leads to the appearance of coral-like formations of titania on the surface of montmorillonite, and after mechanical treatment they significantly increase in size. Adsorption and photocatalytic properties were studied in a quartz reactor using the rhodamine B dye as example. Complete photocatalytic destruction of the dye was achieved within about 100 min (initial concentration of 40 mg/l, amount of photocatalyst 1 g/l, UV lamp power 250 W). Adsorption kinetics is described by pseudo-first and pseudo-second order models. The kinetics of photocatalysis is described by the Langmuir-Hinshelwood model. The high photoactivity is explained both by the improvement of textural properties and the appearance of additional photocatalytic centers due to the defective structure of mechanically activated montmorillonite.