Probable Reaction Pathways Research Articles

Well Defined Phosphine Free Ni-Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines.

In this work, we unveil a novel synthesis of bench stable Ni (II) complexes supported by tetradentate Schiff-base ligands and the complexes were devoid of any phosphine or phosphine-based ligand. These Ni-complexes were successfully applied for the dehydrogenation of secondary alcohols for ketone and ketazine syntheses. Secondary alcohols with different functional groups were well tolerated during catalytic cycle. Moreover, we successfully extended this protocol for the synthesis of biologically significant ketones and ketazines. On the basis of various control experiments, probable reaction pathway was proposed and an acceptorless alcohol dehydrogenation mechanism was suggested.

Elucidating the Synergistic Promotional Mechanism of Water and Oxygen in the Aerobic C-C Homocoupling Reaction Catalyzed by Visible-Light-Derived Core-Shell Pd@A-CQDs Nanostructures.

Rational design and precise synthesis of biogenic noble-metal-based catalysts possessing distinctive structure and composition play a crucial role in the chemical industry, enabling sustainable construction of an inclusive range of chemical resources. In this study, we have effectively fabricated Pd@A-CQDs through a straightforward one-pot aqueous protocol assisted by visible light employing renewable biomass-derived amine-rich carbon quantum dots (A-CQDs). The remarkable visible light harnessing capability (bandgap, ca. 2.81 eV), high density (35.7 × 1018 cm-3), and long lifetime (25 ps) of photocharge carriers and amine-rich surface in A-CQDs make them ideal candidates as both reducing and stabilizing agents, thereby facilitating the in situ construction of metallic Pd(0) nanoparticles. Comprehensive physicochemical characterizations have provided compelling evidence for the spherical morphology of Pd@A-CQDs core-shell nanostructures, with ultrathin A-CQDs shells of ca. 1.9 nm and an average diameter of 14 ± 1 nm. The effectiveness of the synthesized Pd@A-CQDs catalysts was assessed in the ligand- and base-free homocoupling reaction of arylboronic acids in water at ambient temperature. The catalytic tests demonstrated the selective production of the homocoupled compound over protodeboronation products with excellent yield and high catalyst recyclability under ambient conditions. The protocol employed exhibited a high TOF (1.05 × 10-2 mol g-1 min-1) and a low E-factor, with a remarkably low palladium loading. XPS analysis confirmed the retention of the metallic nature of the palladium core within the catalysts during the reaction. The catalytic function of the palladium core in conjunction with the A-CQDs shell, along with the promotional effects provided by water and oxygen for the formation of nucleophilic tetravalent boron, was conclusively recognized by 11B NMR and O2-TPD measurements. The obtained experimental results deliver valuable insights into the probable reaction pathway for the homocoupling reaction catalyzed by the Pd@A-CQDs catalysts. Through a comprehensive and sustainable evaluation, the current methodology exhibits superior performance compared to previously documented techniques in relation to estimated circularity and adherence to good manufacturing practices (GMP).

Bimetallic Mn-Ce oxides modified α-Fe2O3 nanorods for low temperature catalytic thermal desorption of naphthalene in soil

Developing highly active catalytic thermal desorption system is of great significance to soil remediation in a sustainable manner. Herein, Mn-Ce oxides modified α-Fe2O3 nanorods were fabricated for catalytic thermal desorption of naphthalene. When N2 was injected at 500 mL/min and heated at 180 °C for 5 min, the removal rate of naphthalene in soil by Ce-Mn/α-Fe2O3 reached a maximum of 99.96 %, and the corresponding removal rate achieved 32.1 %. Such excellent catalytic performances can be attributed to the mutual conversion of oxidation valence states of MnOx, CeO2, and Fe2O3, which enhance the oxygen mobility of the catalyst surface, resulting in abundant oxygen vacancies and acidic sites. Combined with the tests of GC–MS and FT-IR, the degradation intermediates were identified and a probable reaction pathway was proposed. This study provides an economical and efficient strategy for the enhancement of catalytic thermal desorption, showing crucial practical significance for PHAs remediation in soil.

Prepared Sulfonic-Acid-Based Ionic Liquid for Catalytic Conversion of Furfuryl Alcohol to Ethyl Levulinate.

Efficient utilization of Brønsted acids has been advanced through the synthesis of a novel pyridinium propyl sulfonic acid ionic liquid catalyst, [PSna][HSO4]. Employing niacin and 1,3-propanesulfonic lactone, the synthesis aimed to achieve a catalyst that combines atom-efficiency with stability. Optimal catalytic activity was demonstrated at a temperature of 110 °C over a 2 h reaction time, resulting in a furfuryl alcohol conversion and ethyl levulinate yield of 97.79% and 96.10%, respectively. Notably, the extraction and recovery of [PSna][HSO4] exhibited commendable repeatability with up to five cycles, maintaining furfuryl alcohol conversion and ethyl levulinate yield at 93.74% and 88.17%, which highlights the catalyst's durability. Density flooding theory (DFT) calculations were employed to determine the most probable reaction pathways and identify all possible transition states and the reaction energy barriers overcome at each step of the reaction.

Photocatalytic degradation of enrofloxacin with CoAl-LDH mediated persulfate system: Efficiency evaluations and reaction pathways

Residual enrofloxacin (ENR) exposed in aqueous environments is challenging to the ecosphere. In this work, a layered double hydroxide CoAl-LDH was used to activate the common oxidizing agent persulfate (PS) for photodegradation of ENR, and the degradation pathways of ENR were scrutinized and elucidated. The results indicated that, under the optimal conditions obtained through orthogonal experiments, even though the degradation rate of ENR was as high as 97.72%, the removal of total organic carbon (TOC) from the system was only about 30%. Eleven probable reaction pathways were categorized, and thirty-one types of intermediates were identified in participating in the complex degradation process. The major products of ENR were P4 (C17H20FN3O3), P22 (C19H22FN3O4), P19 (C17H18FN3O3), which are mainly derived from the cleavage of the piperazine groups and quinolone rings. Density functional theory (DFT) calculations of the Fukui index for ENR revealed that the two N atoms in the piperazine ring were the core reactive sites in triggering the degradation chains, which were sensitive for electrophilic attack by the dominant radicals (•OH and SO4•-) generated from the composite PS-UV-CoAl-LDH system.

Trimetallic Alloy as an Electrocatalyst for Direct Low Temperature Fuel Cells: The Case of MF Oxidation on Pt3Pd3Sn2

Methyl formate (MF) has been considered an attractive hydrogen carrier alternative fuel due to its high energy density, ease of storage and transport, and low boiling point (32o C @ 1 atmosphere) liquid. However, the low number of publications on efficient anodic catalysts is impeding the development of a direct methyl formate fuel cell (DMFFC).In this study, a first-principles density functional theory (DFT) calculation was performed to study the MF electro-oxidation on the surface of the Pt3Pd3Sn2 (111) alloy. This surface was proven to be the most active in the anodic oxidation of other small organic molecules1,2. A detailed thermochemistry and kinetics study of MF oxidation was carried out to determine the active sites, most probable reaction pathway for the oxidation of CH3OCHO to CO2, and analyzed the dehydrogenation steps via direct (HCOOH pathway) and indirect (CO pathway) mechanisms.The potential required for complete oxidation of MF to CO2 is 0.66 V. The study revealed that Sn plays an essential role in the mitigation of CO poisoning through water activation and surface oxide reaction mechanisms in a bifunctional manner. Furthermore, based on our findings, Pt and Pd work synergistically to enhance the utilization of active sites for the initiation of MF oxidation and promote HCOOH oxidation, which accelerates the kinetics of the electrochemical reaction.

Molecular dynamics study on the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) catalyzed by aluminum nanoparticles with different contents

The mechanism of thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) catalyzed by nano-sized aluminum powder remains unclarified. In the present study, reactive molecular dynamics simulations using the parameterized reactive force field with low gradient correction (ReaxFF-lg) were conducted to study the microscale process of the RDX thermal decomposition catalyzed by different Al contents, and the density functional theory calculations were used to analyze the initial decomposition pathways of RDX on the Al surface. The thermal disintegration and the released energy of RDX are significantly facilitated by an increase in Al concentration at a lower level and the optimal value is around 35 wt%, while a higher concentration of Al will lead to an opposite effect. The dissociation of nitro group is the most probable initial reaction pathway for RDX decomposition on the Al surface. In addition, the evolutions of Al-containing clusters, key intermediates, and final products were analyzed, providing more information about this reaction. The findings suggest that the addition of Al nanoparticles improves the properties of RDX-based explosives, but the optimal amount of Al is critical for achieving the desired effects. The detailed analysis of the reaction mechanism and intermediate products provides valuable insights into the underlying mechanisms of the Al/RDX system.

Chlorinated Cubane-1,4-dicarboxylic Acids.

Herein, we report radical chlorination of cubane-1,4-dicarboxylic acid leading preferentially to one monochlorinated cubane dicarboxylate (ca. 70%) that is accompanied by four dichlorinated derivatives (ca. 20% in total). The exact positions of the chlorine atoms have been confirmed by X-ray diffraction of the corresponding single crystals. The acidity constants of all dicarboxylic acids in water were determined by capillary electrophoresis (3.17 ± 0.04 and 4.09 ± 0.05 for monochlorinated and ca. 2.71 ± 0.05 and 3.75 ± 0.05 for dichlorinated cubanes). All chlorinated derivatives as well as the parent diacid showed high thermal stability (decomposition above 250 °C) as documented by differential scanning calorimetry. The probable reaction pathways leading to individual isomers were proposed, and the energies of individual transition states and intermediates were obtained using density functional theory calculations (B3LYP-D3BJ/6-311+G(d,p)). The relative strain energies for all newly prepared derivatives as well as for hypothetical hexahalogenated (fluorinated, chlorinated, brominated, and iodinated) derivatives of cubane-1,4-dicarboxylic acids were predicted using wavefunction theory methods. The hexafluorinated derivative was identified as the most strained compound (57.5 kcal/mol), and the relative strain decreased as the size of halogen atoms increased (23.7 for hexachloro, 16.7 for hexabromo, and 4.0 kcal/mol for the hexaiodo derivative).

Using the composite material of GO and g-C3N4 nanosheets as substrate to in-situ grow Co3O4 nanosheets for efficient Hg0 removal

Chemisorption is an effective method to remove Hg0 from coal-fired flue gas. During this process, Hg0 will convert to Hg2+ and be solidified on sorbent surface. The number of adsorption sites and the electron transfer between Hg0 and sorbents play an important role in the removal process. In the present work, GO with a rapid electron transfer was compounded with NS-g-C3N4 to improve the electron donating ability of NS-g-C3N4. After that, Co3O4 nanosheets were grown in-situ in the interlayer space of GO and NS-g-C3N4 composites. A series of sorbents were successfully synthesized by changing GO concentration. SEM and TEM results show that the corresponding Co3O4/GCN (GCN denote the GO and NS-g-C3N4 composites) sorbent has better Co3O4 nanosheet dispersibility when GO concentration is 5 mg/mL. This results in a large amount of chemisorbed oxygen, which is favor to the oxidation of Hg0 to HgO. In addition, XPS results show that the interaction between Co3O4 and GCN give a rapid electrons transfer from GCN to Co3O4, thus improving the activation of gaseous oxygen. Therefore, Co3O4/GCN-5 has excellent Hg0 removal efficiency of about 95 % at 200 °C and high stability under different flue gas conditions. A probable reaction path way was deduced by the results of XPS and Hg0 adsorption–desorption experiment.

In Situ-Generated CuI Catalytic System for Oxidative N-Formylation of N-Heterocycles and Acyclic Amines with Methanol.

The development of a sustainable and simple catalytic system for N-formylation of N-heterocycles with methanol by direct coupling remains a challenge, owing to many competing side reactions, given the sensitivity of N-heterocycles to many catalytic oxidation or dehydrogenation systems. This work concerns the development of an in situ-generated CuI catalytic system for oxidative N-formylation of N-heterocycles with methanol that is based on the case study of a more typical 1,2,3,4-tetrahydroquinoline as substrate. Aside from N-heterocycles, some acyclic amines are also transformed into the corresponding N-formamides in moderate yields. Furthermore, a probable reaction mechanism and reaction pathway are proposed and extension of work based on some findings leads to a demonstration that the formed ⋅O2 - and ⋅OOH radicals in the catalytic system is related to the formation of undesired tar-like products.

Photochemical charge accumulation in a heteroleptic copper(i)-anthraquinone molecular dyad via proton-coupled electron transfer.

Developing efficient photocatalysts that perform multi electron redox reactions is critical to achieving solar energy conversion. One can reach this goal by developing systems which mimic natural photosynthesis and exploit strategies such as proton-coupled electron transfer (PCET) to achieve photochemical charge accumulation. We report herein a heteroleptic Cu(i)bis(phenanthroline) complex, Cu-AnQ, featuring a fused phenazine-anthraquinone moiety that photochemically accumulates two electrons in the anthraquinone unit via PCET. Full spectroscopic and electrochemical analyses allowed us to identify the reduced species and revealed that up to three electrons can be accumulated in the phenazine-anthraquinone ring system under electrochemical conditions. Continuous photolysis of Cu-AnQ in the presence of sacrificial electron donor produced doubly reduced monoprotonated photoproduct confirmed unambiguously by X-ray crystallography. Formation of this photoproduct indicates that a PCET process occurred during illumination and two electrons were accumulated in the system. The role of the heteroleptic Cu(i)bis(phenanthroline) moiety participating in the photochemical charge accumulation as a light absorber was evidenced by comparing the photolysis of Cu-AnQ and the free AnQ ligand with less reductive triethylamine as a sacrificial electron donor, in which photogenerated doubly reduced species was observed with Cu-AnQ, but not with the free ligand. The thermodynamic properties of Cu-AnQ were examined by DFT which mapped the probable reaction pathway for photochemical charge accumulation and the capacity for solar energy stored in the process. This study presents a unique system built on earth-abundant transition metal complex to store electrons, and tune the storage of solar energy by the degree of protonation of the electron acceptor.

In-situ growth of Co/Zn bimetallic MOF on GO surface to prepare GO supporting Co@C single-atom catalyst for Hg0 oxidation

Oxidation of Hg0 to Hg2+ is an efficient way to remove Hg0 from flue gas. Chemisorbed oxygen as the main active site plays an important role in Hg0 oxidation process. Single-atom catalyst has an excellent ability of transforming gaseous oxygen into chemisorbed oxygen. In the present work, graphene oxide (GO) was used as support to in-situ grow Co/Zn bimetallic MOF on GO surface. After pyrolysis, a GO supported Co@C single-atom catalyst was obtained. SEM and TEM results show that GO supporting gives a high dispersion for calcined MOF particles. HAADF-STEM results prove that most of the Co atoms in calcined MOF particles stay as single-atom status. EXAFS indicated that the Co atoms in the catalyst was coordinated with N, and the coordination was dominated by CoN2. CoN2 can capture and activate gaseous oxygen forming more chemisorbed oxygen. Thanks to the high dispersion of calcined MOF and higher chemisorbed oxygen concentration, the Hg0 oxidation efficiency of the obtained catalyst (Co2.5-SAs@NC/GO-1) can reach above 90 % in the temperature range of 120–180 °C with 0.075 g loading amount at the GHSV of 180, 000 h−1. The probable reaction pathway was analyzed by an adsorption–desorption experiment and XPS over the used and regenerated Co2.5-SAs@NC/GO-1.

Diastereo- and regioselective petasis aryl and allyl boration of ninhydrins towards synthesis of functionalized indene-diones and dihydrobenzoindeno-oxazin-ones.

Petasis aryl and allyl borations were accomplished using substituted ninhydrins, boronic acids or 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 1,2-aminophenols in Hexafluoroisopropanol (HFIP) without any catalysts to synthesize different aryl and allyl derivatives of ninhydrins. The nature of substitution in the boronic acids and 1,2-amino phenols was the key factor in determining the diastereo-regioselectivity and the type of product distributions. The products were isolated and characterized by HMBC, HSQC, 1H, 13C NMR experiments and X-ray single crystallographic analysis. A probable reaction pathway involves in situ formation of acyclic and cyclic ninhydrin-amino alcohol adducts, with the positioned hydroxyl group determining the stereo-regioselective outcome via tetracoordinated boron intermediates. A metal free diastereo- and regioselective Petasis aryl and allyl boration of ninhydrins.

TMEDA-Catalyzed Regioselective Decarboalkoxy C-N Bond Formation: A Unified Direct Access to Indolo[2,1-a]isoquinoline and Dibenzopyrrocoline Alkaloids.

An unprecedented TMEDA-catalyzed, regioselective, decarboethoxy direct C-N coupling protocol towards the synthesis of dibenzopyrrocolines 17 a-i and 5,6-dihydroindolo[2,1-a]isoquinoline 15 a-f/18 a-c alkaloids via the identification of N,N,N',N'-tetramethylethylenediamine (TMEDA) as a homogeneous catalyst is reported. The transition-metal-free, TMEDA-catalytic novel protocol is operationally simple and showed a wide range of functional group tolerance and substrate compatibility. The gram-scale application and synthesis of naturally occurring Cryptaustoline (dibenzopyrrocoline) alkaloid, further highlights the importance and versatile nature of the developed protocol. This finding also offers a TMEDA-catalyzed direct synthesis of dibenzopyrrocolines and substituted 5,6-dihydroindolo[2,1-a]isoquinoline compounds in a one-pot. The probable reaction pathway involves the free-radical sequential approach via a single electron transfer (SET) mechanism.

Mechanistic insights on the radical scavenging activity of oat avenanthramides

AbstractAvenanthramides, the phenolic antioxidants exclusively found in oats (Avena sativa L.), have long been recognized for their immense health benefits owing to their antioxidant potential. Herein, hydroperoxyl radical (•OOH) scavenging activity of oat avenanthramides is investigated in detail, using density functional theory for the first time. Three probable mechanisms: (a) hydrogen atom transfer (HAT), (b) single electron transfer followed by proton transfer, and (c) sequential proton loss electron transfer (SPLET), are considered towards evaluating the antioxidant potential of avenanthramides (A–C) in the gas phase as well as in both polar and non‐polar media. Based on the computed data, HAT is found to be the thermodynamically preferred mechanism for antioxidant activity in the gas phase. In the polar medium, SPLET represents the most probable reaction pathway. Our thermodynamic and kinetic data computed at the B3LYP level predict avenanthramide C, characterized by an ortho‐dihydroxy functionality on the aromatic ring, as the most potent radical scavenger among the three variants, in agreement with the available experimental reports.

Synthesis, photophysical properties and catalytic activity of Ƙ3-SCS pincer palladium (II) complex of N,N'-di-tert-butylbenzene-1,3-dicarbothioamide supported by DFT analysis

The title complex [PdCl(L)] (1), is obtained from the reaction of SCS pincer ligand HL (where, HL = N,N'-di-tert-butylbenzene-1,3-dicarbothioamide) with lithium tetrachloropalladate (II) in methanol. The compound 1 is characterized by elemental analysis, FTIR, 1H, and 13C NMR spectroscopy, UV–Vis spectroscopy, and X-ray crystallographic techniques. At room temperature, 1 emits luminescence light of wavelength 460 nm in the solid state upon excitation by UV light of wavelength 280 nm. The average emission lifetime indicates that, both the ligand and complex emission is fluorescence in nature and involves mainly ligand centers π-π* deexcitation. It also shows good catalytic activity towards Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions of aryl bromides with tert-butyl acrylate and p-tolylboronic acid respectively. For both type of reactions, >99% conversion of the substrates is found to occur for electronically activated p-nitro bromobenzene using 1 mol % of 1. Further, modern DFT calculations are performed to decipher the mechanistic insight on the preferable pathways of the Mizoroki-Heck cross-coupling reaction. Stepwise free energy of reactions for various probable reaction pathways suggest that the catalytic route has profound preference for Pd(0)-Pd(II) over Pd(II)-Pd(IV) pathway.

Singlet Oxygen Oxidation of the Radical Cations of 8-Oxo-2'-deoxyguanosine and Its 9-Methyl Analogue: Dynamics, Potential Energy Surface, and Products Mediated by C5-O2 -Addition.

8-Oxo-2'-deoxyguanosine (OG) is the most common DNA lesion. Notably, OG becomes more susceptible to oxidative damage than the undamaged nucleoside, forming mutagenic products in vivo. Herein the reactions of singlet O2 with the radical cations of 8-oxo-2'-deoxyguanosine (OG.+ ) and 9-methyl-8-oxoguanine (9MOG.+ ) were investigated using ion-molecule scattering mass spectrometry, from which barrierless, exothermic O2 -addition products were detected for both reaction systems. Corroborated by static reaction potential energy surface constructed using multi-reference CASPT2 theory and molecular dynamics simulated in the presence of the reactants' kinetic and internal energies, the C5-terminal O2 -addition was pinpointed as the most probable reaction pathway. By elucidating the reaction mechanism, kinetics and dynamics, and reaction products and energetics, this work constitutes the first report unraveling the synergetic damage of OG by ionizing radiation and singlet O2 .

Quantum chemical study of gas-phase reactions of isoprene with OH radicals producing highly oxidised second-generation products.

The formation of secondary organic aerosols caused by atmospheric oxidation of isoprene is harmful to human health and the climate; thus, isoprene oxidation is further mandatory to obtain less harmful or harmless highly oxidised products. In this numerical investigation, 2-hydroperoxy-2-methylbut-3-en-1-ol (ISOPOOH) was considered the model compound to investigate the formation of three RO2 radicals (C5H11O4, C5H11O6 and C5H11O5) and two saturated highly oxidised products (C5H12O6 and C5H10O6). The complete reaction network and its thermodynamics and kinetics were analysed to obtain the most probable and feasible reaction pathways. Four different levels of theories (HF, B3LYP, M06-2X and ωB97XD with basis set of 6-31+g(d,p)) were employed to explore a global minimum of ISOPOOH. All theories provided approximately close energetics; however, because of the novelty of the functional and parameterisation of the basis set, the ωB97XD functional was selected to examine the reaction mechanism. C5H12O6 was formed as the second-generation highly oxidised product during ISOPOOH oxidation.

CO2 reduction by single copper atom supported on g-C3N4 with asymmetrical active sites

Electrochemical reduction of CO2 requires catalysts beyond Cu with high activity and selectivity to produce C2 products. Different from many single-atom catalysts that show high performance in obtaining C1 products, Cu supported on carbon nitride (Cu-C3N4) has shown a unique capability to generate C2 products by providing asymmetrical active sites. Herein, we study 17 possible pathways and reaction mechanisms of CO2 reduction toward ethylene – a featured C2 product, on Cu-C3N4. The possible reaction intermediates along with different reaction pathways on three active sites of Cu-C3N4 (Cu, C, and N) were obtained by density functional theory (DFT) computations. The most probable reaction pathway toward C2H4 production is 1.08 eV at open circuit conditions, which is benefited by the synergistic effect of both Cu and C active sites. Comparing with other pathways utilizing Cu/N and C/N active sites, the carbon atom provides a perfect settling centre for the first CO2 after reduction by Cu and leaves Cu vacant for the second CO2 reduction. Our study provides reaction mechanism insights for C2 production on Cu-C3N4 and sheds light on designing electrocatalysts with dual active sites.

Photocatalytic degradation of 3-methyl-4-nitrophenol over Ag/AgCl-decorated/[MOYI]-coated/ZnO nanostructures: Material characterization, photocatalytic performance, and in-vivo toxicity assessment of the photoproducts

In this work, a facile ionic liquid-mediated method was utilized to fabricate an efficient photocatalyst for environmental remediation. The eco-friendly aspect of the treatment was explored through an in-vivo toxicity bioassay. ZnO particles, prepared by a combined solid state-pyrolysis method, were coated by 1-methyl-3-(oxiran-2ylmethyl)-1H-imidazolium-3-chloride ([MOYI]Cl) ionic liquid. Then, Ag/AgCl species were grown on the surface to make a heterojunction system leading to efficient charge separation and light absorption extension to the visible domain. The products were characterized by XRD, FTIR, SEM, EDX, DRS, BET, and PL analysis. Photocatalytic performance of the nanostructures was evaluated by the degradation of 3-methyl-4-nitrophenol (from the semivolatile organic compounds, SVOCs, family) solutions under visible light. According to the results, the photocatalyst was able to completely degrade the pollutant and decrease the amount of COD from 210 to 32 mg/L within 90 min of the photoreaction. Reusability studies revealed that the degradation efficiency slightly decreased to 92% after five repetitive experiments. In order to investigate the eco-friendly aspect of the treatment procedure, an in-vivo bioassay was conducted to evaluate the acute toxicity of the contaminant solution, before and after the photochemical reaction, in terms of physical, biochemical and hematological markers of the laboratory rats. LC-MS analysis was applied to identify the chemical structure of the reaction products and propose the most probable reaction pathway. The results showed that the photocatalytic treatment over the prepared materials is an eco-friendly and reliable method to effectively transform such toxic contaminants into non-toxic or less harmful compounds.