Search

Fluorinated alcohols as solvents strongly influence and direct chemical reaction through donation of strong hydrogen bonds while being weak acceptors. We used 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as the activating solvent for a nitric acid and FeCl3-catalyzed aerobic oxidation of secondary alcohols to ketones. Reaction proceeded selectively with excellent yields with no reaction on the primary alcohol group. Oxidation of benzyl alcohols proceeds selectively to aldehydes with only HNO3 as the catalyst, while reaction on tertiary alcohols proceeds through dehydration and dimerization. A mechanistic study showed in situ formation of NOCl that converts alcohol into alkyl nitrite, which in the presence of Fe3+ ions and fluorinated alcohol decomposes into ketone. The study indicates that iron(III) acts also as the single-electron transfer catalyst in regeneration of NOCl reactive species.

The results of experimental investigation of the interphase distribution of iron(III) in an environmentally friendly aqueous two-phase system based on polypropylene glycol with a molecular weight of 425 and sodium chloride have been presented. The mechanism of extraction has been determined, and the quantitative characteristics of the extraction of iron(III) using the system under study have been found.

We analyzed the products of alkylphenol (ortho-, meta-, and para-cresols and 4-isopropylphenol) oxidation by iron(III) chloride in aqueous solutions by HPLC with electrospray ionization and mass-spectrometric detection in the negative ion mode. It was found that the main products formed by the nucleophilic addition of the initial alkylphenols to reactive intermediates, quinone methides. The resulting adducts can be further oxidized, which, after several oxidation–addition cycles, leads to the appearance of a series of compounds with molecular weights belonging to sequences of values of 108, 214, 320, 426, 536, 638, … for cresols and 136, 270, 404, 538, 672, … for 4-isopropylphenol. Such processes are similar to the oxidation of alkylphenols by air oxygen in aqueous solutions and to their electrochemical oxidation yielding dimeric and oligomeric products.

Three-component coupling of 2-naphthol, aldehydes, and urea has been accomplished in the presence of FeCl3 under microwave irradiation and solvent-free conditions to afford the corresponding synthesis of 1-phenyl-1, 2-dihydro-3H-naphtho[1,2-e][1,3]oxazin-3-onederivatives in excellent yields. It is a promising catalyst for the microwave-assisted reaction providing high product yield in a short period.

A highly efficient method has been developed for the synthesis of diphenylmethyl (DPM) esters from 2-diphenylmethoxypyridine. Various carboxylic acids readily reacted with 2-diphenylmethoxypyridine...

The radial distribution functions of iron(III) chloride aqueous solutions in a wide range of concentrations under ambient conditions have been calculated from the experimental data obtained earlier by X-ray diffraction method. Various models of the structural organization of the systems investigated have been developed. By calculating the theoretical functions for each model and comparing them with the experimental functions, optimal variants have been identified. Quantitative characteristics of the nearest environment structure of Fe3+ and Cl− ions, such as coordination numbers, interparticle distances and varieties of ion pairs, have been determined. It has been found that in a saturated solution of iron(III) chloride the cation coordinates four water molecules at an average distance of 0.210 nm and two chloride ions. As the concentration decreases, the number of solvent molecules in the first coordination sphere of the cation increases to six, and contact ionic associates turn into solvent-separated ion pairs. The Fe3+ ion also forms a second coordination sphere at an average distance of 0.408 nm, the number of H2O molecules in which increases with dilution.

A novel facile synthetic method for producing diphenylmethyl (DPM) ethers from 2-diphenylmethoxypyridine was developed. A variety of DPM ethers was successfully achieved with high yield via treatment of alcohols with 2-diphenylmethoxypyridine in the presence of catalytic FeCl3. The procedure is a practical and efficient synthetic procedure to protect various alcohols, and it can be applied to prepare bioactive compounds.

Fabrication of hybrid system coupling inorganic semiconductor photosensitizer with molecular catalyst provides a promising approach to achieve highly efficient CO2 reduction into solar fuels, as the semiconductor nanomaterials can meet the prerequisites of visible-light photoresponse and high charge-separation efficiency for achieving high photocatalytic efficiency. In this work, CdS/Bi2S3 heterostructures have been prepared via an ion-exchange reaction and employed as the photosensitizer to couple with tetra(4-carboxyphenyl)porphyrin iron(III) chloride (FeTCPP) molecular catalyst for photoreduction of CO2 into CO and H2 under visible-light irradiation. The sulfur vacancy in CdS surface can be reduced by the formation of CdS/Bi2S3 heterostructure. The content of Bi2S3 can be modulated via tailoring the ion-exchange reaction time. The resulting effect on the performace of CO2 photoreduction has been investigated in detail. Benefiting from the enhanced separation and utilization of charge carriers, CdS/Bi2S3-0.5 h/FeTCPP hybrid catalyst exhibits 8.2 times CO yield (1.93 mmol/g/h) and 1.7 times H2 yield (6.08 mmol/g/h) of CdS/FeTCPP hybrid catalyst. More important, the results of energy level alignment, electron spin resonance and photocatalysis indicate that electron-transfer direction can be changed once the CdS/Bi2S3 heterostructure is coupled with FeTCPP. In the CdS/Bi2S3 heterostructure, electrons transfer mainly from the conduction band of CdS to Bi2S3, while it is mainly from the conduction band of CdS to FeTCPP in the CdS/Bi2S3/FeTCPP hybrid.

In this study, the Fe-containing tailings (Fe-TO) ore was reutilized and enriched with FeCl3 as a heterogeneous catalyst for the Fenton process to degrade the organic dyes from aqueous solution. The determinants of the heterogeneous catalytic Fenton system which included iron modification ratio, solution pH, catalyst dosage, H2O2 dosage and initial concentration of organic dyes were systematically investigated. The modification ratio of 15% (w/w of iron), pH of 3, MFe-TO15 dosage of 0.5 g L−1 and H2O2 dosage of 840 mg L−1 were chosen as the best operational conditions for Fenton oxidation of organic dyes. The decolorization efficiency of both MB and RhB by MFe-TO15/H2O2 was higher than that of Fe-TO/H2O2 by about two times. The kinetic study showed the degradation of organic dyes well fitted the pseudo-first-order kinetic model with apparent constant rate values (Kd) following the same sequence as the degradation efficiency of organic dyes. The degradation mechanism of dyes could be attributed to adsorption due to the good-development in textural properties of the iron modified catalyst (MFe-TO) with an increase in BET surface area, pore volume and pore diameter of, respectively, 2, 5 and 5 times and leaching iron through homogeneous Fenton reaction. However, the oxidation process occurring on the MFe-TO15's surface by heterogeneous Fenton reaction which enhanced decomposition of H2O2 for continuous generation of hydroxyl radicals was the main mechanism. The key role of *OH radical in oxidation of organic dyes was further ascertained by the remarkable drop in the decolorization of both organic dyes when the various radical-scavengers, including tert-butanol and chloride were supplemented into Fenton systems. A good stability of the catalyst was obtained through leaching test with low leaching iron ratio. The applied modified catalyst remained stable through three consecutive runs. From these findings, it can be concluded that the modified material can be applied as a feasible, inexpensive and highly effective catalyst for removal of persistent organic compounds from wastewater.

We report here our results on the application of ynamides as substrates in the reactions with diorganyl dichalcogenides and iron(III) chloride to give selectively three different types of compounds: E-α-chloro-β-(organoselenyl)enamides, 4-(organochalcogenyl)oxazolones, and vinyl tosylates. The results reveal that the selectivity in the formation of products was obtained by controlling the functional groups directly bonded to the nitrogen atom of the ynamides. Thus, α-chloro-β-(organoselenyl) enamide derivatives were exclusively obtained when the TsN- and MsN-ynamides were treated with a mixture of diorganyl diselenides (1.0 equiv) and FeCl3 (3.0 equiv) in dichloroethane (DCE, 3 mL), at room temperature. The 4-(organochalcogenyl)oxazolones were selectively obtained with ynamides having an ester group, directly bonded to the nitrogen atom, upon treatment with a solution of FeCl3 (1.5 equiv) and diorganyl dichalcogenides (1.0 equiv) in dichloromethane (3 mL) at room temperature. Finally, vinyl tosylates were obtained from ynamides having an ester group, directly bonded to the nitrogen atom, by reaction with p-toluenesulfonic acid. We also studied the application of the prepared compounds as substrates for Suzuki and Sonogashira cross-coupling reactions.

Provedeno je testiranje membranskih elektroda napravljenih od mješavine željezovog(III) fosfata i srebrovog sulfida uz dodatak teflona koji je odgovoran za kompaktnost. Opisano je testiranje dvije prethodno napravljene membrane u otopini željezovog(III) klorida, te ispitivanje odziva na željezove(III) katione potenciometrijskom metodom, kojoj je prednost jednostavnost i niska cijena. Testiranje se provodi u kiselom području pri pH=1. Osnovni cilj bio je testirati membrane zadanih sastava i donošenje zaključka o mogućnosti praktične primjene takvih membrana. Odziv na željezove(III) katione ispituje se kod membrana sljedećeg sastava: • Membrana 1 : FePO 4 : Ag 2 S : PTFE = 1 : 2 : 3 • Membrana 2 : FePO 4 : Ag 2 S : PTFE = 1 : 3 : 4 Membrane su ispitane na odziv na željezove(III) katione u elektrokemijskoj ćeliji koristeći otopinu željezovog(III) klorida metodom slijednog razrjeđivanja puferom sumporne kiseline pH vrijednosti 1. Dobivene vrijednosti odziva zatim su grafički obrađene. The testing has been carried out of membrane electrodes made of mixture of ferric phosphate and silver sulfide with the addition of polytetrafluoroethylene which is responsible for compactness. Testing of two pre-made membranes in the solution of iron(III) chloride, and testing the response to iron(III) cations by potenciometric method, which has advantage of simplicity and low cost. Testings are carried out in the acidic region at pH=1. The main goal was to test membrane electrodes of the given composition and to reach a conclusion on the practical application of such membranes. The response to iron(III) cations is tested for membranes of the following composition: • Membrane 1 : FePO 4 : Ag 2 S : PTFE = 1 : 2 : 3 • Membrane 2 : FePO 4 : Ag 2 S : PTFE = 1 : 3 : 4 The membranes were tested for response to ferric cations in electrochemical cell using a solution of ferric chloride by sequental dilution method with sulfuric acid pufer.The resulting response values were graphically analyzed.

A highly efficient iron(iii) chloride-promoted cyclization between α,β-alkynic tosylhydrazones and diselenides to form a 4-(arylselanyl)-1H-pyrazole skeleton is studied. This reaction forms C-N and C-Se bonds in one step by utilizing inexpensive iron(iii) chloride instead of expensive transition metal additives. This strategy features easily synthesized substrates, mild reaction conditions and high tolerance to functional groups.

Amide functional groups are prominent in a broad range of organic compounds with diverse beneficial applications. In this work, we report the synthesis of these functional groups via an iron(iii) chloride-catalyzed direct amidation of esters. The reactions are conducted under solvent-free conditions and found to be compatible with a range of amine and ester substrates generating the desired amides in short reaction times and good to excellent yields at a catalyst loading of 15 mol%.

The effectiveness of the modification of wheat straw biochar using FeCl3 and HCl, alone or combined, on ammonium adsorption was evaluated using kinetic and isotherm models. The adsorption mechanisms were studied by comparative analysis of the surface properties of the biochars before and after ammonium adsorption. The results indicate that the modification methods enhanced the ammonium adsorption capacity by at least 14%, due to the increased OH and OCO functional groups and specific surface area, and increased Fe3+/Fe2+ redox coupling serving as an electron shuttle. It can be concluded that chemical modification of wheat straw biochars using FeCl3 and HCl increased the effectiveness of biochars for the treatment of ammonium-contaminated wastewater.

A simple and straightforward protocol has been accomplished for synthesis of pyrazolo[3,4-b]pyridines by reacting 5-amino-1-phenyl-3-(trifluoromethyl)-1H-pyrazole-4-carbaldehyde (1) and β-enaminoketones (2) promoted by Iron(III)chloride. This protocol was also able to produce quinolines (5) by the reaction of O-nitrobenzaldehydes and β-enaminoketones. Simple reaction conditions, high compatibility and excellent yields are the advantages of this protocol.

The coordination chemistry of FeCl3 is distinctly different to that of the other 3d metal halides. It has a distinct preference for O-donor ligands. Although it primarily forms six-coordinate compl...

The hybrid coupling between inorganic semiconductor and molecular catalyst can provide a promising approach for the construction of highly efficient and selective photocatalytic CO2 reduction systems. This hybrid system can take full advantage of the strong light harvesting capability of semiconductor and high selectivity of molecular catalyst. The interaction linker bridging the semiconductor and molecular catalyst plays an important role in supplying efficient electron transfer channels. In this study, both CdS with and without ethylenediamine functionalization (i.e., CdS-EF and CdS) have been successfully synthesized and further respectively coupled with tetra(4-carboxyphenyl)porphyrin iron(III) chloride (FeTCPP) for CO2 photoreduction. It is found that CdS-EF exhibits inferior photocatalytic activity to CdS, while CdS-EF/FeTCPP hybrid photocatalyst shows much higher activity than CdS/FeTCPP. This is because hydrogen bonding exists between the amino groups in CdS-EF and carboxyl groups in FeTCPP, which can act as electron transfer channels from CdS to FeTCPP in the obtained hybrid system.

In this work there were studied various methods for concentrating the algae biomass, and mechanisms of concentration processes of the microalgae cells. Presented are papers devoted to usage of various coagulants and flocculants (iron (III) chlorides and sulphates, titanium tetrachloride, slaked lime, potassium chloride, potassium permanganat, aluminum potassium sulphates, Flopam FO 4550 SH). In the experimental part there is studied the usage of FeCl3*6H2O coagulant in the amount of 4, 6, 8, 10, 20, 30 mg/l of microalga Chlorella Sorokiniana suspension. Microstructure investigations have shown that at addition of ferrous chloride of concentration more than 20 mg/l, the cell death is more than 50%. Concentrations from 4 to 10 mg/l achieve low degree of precipitation (not more than 18%). Aiming at increasing degree of precipitation we investigated usage of two-component system coagulant-flocculant. Usage of two-component system results in a significant increase of precipitation degree of microalga Chlorella Sorokiniana: at addition of chitosan the degree reaches 53%, at addition of PAA it is 79%. It was determined the volume of the thickened biomass sludge. It shows that usage of chitosan results in more tightened biomass layer, which occupies minimal volume (V = 140 ml). The following three-component mixture is an optimum variant for high-efficient precipitation of biomass: coagulant FeCl3 in the amount of 6 mg/l; flocculants as a mixture of chitosan 2% and PAA 1% in the amount of 10 ml/l. Addition of chitosan solution as a flocculant results in decrease of pH value, which is caused by usage of acetic acid for preparation of chitosan solution. Microstucture analysis of the precipitated biomass shows that at coloration of Chlorella Sorokiniana cells by methylene blue, the amount of dead (colored) cells is not less than 5%. Consequently, the precipitated biomass might be used for obtaining of valuable components.

Mussel-inspired polydopamine (PDA) coatings have received widespread concern due to the advantages of eco-friendliness, adhesion nature, and film-forming feasibility. However, self-polymerization of dopamine assisted by air-oxidation under alkaline condition is time-consuming, and the ensuing uneven PDA coatings restrict their applications. In this study, we proposed a rapid PDA deposition triggered by a facile system of iron (III) chloride/hydrogen peroxide (FeCl3/H2O2) under acidic condition. The oxygen-radical species generated by FeCl3/H2O2 largely promote covalent polymerization and deposition rate of dopamine. This not only considerably shortens the deposition time of PDA, but also improves the stability of PDA coatings, combined with the chelation of Fe ions in PDA matrices. SEM, AFM, XPS, zeta potential and water contact angle analyses confirmed the formation of a hydrophilic, smooth, and negatively charged PDA layer onto several membrane substrates. Herein, PDA-coated hydrolyzed polyacrylonitrile membranes yield a remarkable NF performance with superior dye retentions (direct red 23: 98.6%, Congo red: 99.0%, reactive blue 2: 98.2%) and a high water permeability (17.5 L m−2 h−1 bar−1). Furthermore, a low salt rejection (NaCl: 5.6%) of PDA-modified membranes demonstrates their great potential in fractionation of dye/salt mixtures. Meanwhile, the PDA-modified membranes show an excellent organic fouling resistance and a long-term stability. This facile, environmental-friendly method provides a rapid PDA deposition onto various substrates for a wide range of applications, including filtration membranes.

The suitability of methanesulfonic acid as a copper lixiviant with ferric chloride as an oxidant was studied by analysing the leaching kinetics and by characterising solid residues from leach tests on a chalcopyrite-rich ore sample. The effects of temperature, initial acidity, ferric-ion concentration and particle size were determined. The leach kinetics were dependent on the temperature and particle size, whereas the acid and ferric concentrations had a minimal impact on the leaching rate within the ranges studied. Although a sulfur layer formed on the solid residue, the reaction mechanism could be modeled with the shrinking-core model with surface chemical-reaction control, which implies that lixiviant flow through the sulfur layer did not control the reaction rate. The apparent activation energy was 101 kJ mol−1 as calculated by the Arrhenius and 'time-to-a-given-fraction' methods. The activation parameters of the reaction were an enthalpy (ΔH++) of 99.4 kJ mol−1, and an entropy (ΔS++) of −197 J mol−1 K−1 as calculated by using transition state theory and the Eyring equation.

A facile synthesis of 2,3-disubstituted carbazoles through electrocyclization of 2,3-divinylindoles using FeCl3 in DMF at reflux is reported. The methodology was found to be applicable for smooth transformation of 3-aryl-2-vinylindole as well as 2-styrylbiphenyl into the respective benzo[c]carbazole and phenanthrene.

Transition metal-nitrogen-carbon (MNC) based non-platinum metal catalysts obtained by pyrolysis of a transition metal, carbon and nitrogen sources were viewed as an inexpensive substitute for the platinum-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Due to the pyrolysis step involved in synthesizing MNC catalysts, the exact active site structure responsible for ORR was not conclusively identified thereby limiting the efforts of scientists in identifying effective synthetic routes to achieve highly active MNC catalysts with required active site structure and site density. To alleviate the lack of clarity on the active site structure of MNC catalysts, as a substitute, copper, and cobalt-based metal-organic frameworks and complexes were synthesized recently and shown to be ORR active. In this study, we have synthesized an Iron(III) chloride-benzotriazole ( [ FeCl 3 ( btaH ) 2 ] ) adduct and demonstrated its ORR activity in alkaline medium, which primarily reduces oxygen by 4-electron reduction pathway. Single crystal XRD characterization revealed the crystal structure of [ FeCl 3 ( btaH ) 2 ] unambiguously. The ORR onset potential, Tafel slopes, and methanol tolerance ability of [ FeCl 3 ( btaH ) 2 ] were compared against commercial 20 wt% Pt/C. [ FeCl 3 ( btaH ) 2 ] adduct shows complete methanol tolerance and ORR onset potential of 0.89 V vs. RHE, which is highest among the unpyrolyzed metal-organic frameworks/complexes.

The paper presents the investigation on the estimated efficiency of iron (III) chloride solutions in the decontamination process of radioactive soils with 90 Sr, according to kinetic and thermodynamic characteristics of the desorption process. The specific 90 Sr radioactivity of soil samples was (3.9±0.3)·104 Bq·g. The adsorption isotherms of Sr 2+ and Fe 3+ are described with the Langmuir equation. The values of Gibbs energy G0298 = -4.65 kJ·mol -1 and equilibrium ion exchange constant Keq = 6,5 confirm the hypothesis of strontium removal from soils with iron (III) cations. The effectiveness of the method is substantiated by experimental and calculated results of this study samples of radioactive soils are deactivated in 90% after 9.5 hours, whereas the kinetic constant is 6.77·10 s -1 . The suggested method of soil cleanup with 0.2 M Fe 3+ solutions is optimal and complies with the environmental requirements.

Herein, we describe the development of a synthetic strategy towards chiral 3-pyrrolines based on the design principle of iron(III)-catalyzed carbonyl-olefin metathesis. This approach takes advantage of commercially available amino acids as chiral pool reagents and FeCl(3) as a Lewis acid catalyst. Our strategy is characterized by its operational simplicity, mild reaction conditions and functional group tolerance. Investigations show that an electron-deficient nitrogen protecting group overcomes limitations arising from competitive binding of the Lewis acid catalyst to unfavorable Lewis basic sites, which ultimately enables catalytic turnover.

Photocatalytic reduction of CO 2 into value-added chemicals is particularly attractive as it could produce renewable energy and capture greenhouse gas. Photoreduction of CO 2 can be realized over molecular and inorganic catalysts. The former usually exhibit high activity, but low stability and often inactive under visible-light irradiation; the latter has low activity, but good stability. Here we use g-C 3 N 4 nanosheets as the photosensitizer to integrate with Fe tetra(4-carboxylphenyl)porphyrin chloride (FeTCPP) molecular catalyst. Besides π-π stacking between tri- s -triazine unit and porphyrin, the carboxyl group modified Fe porphyrin is used for the first time in CO 2 photoreduction so as to form hydrogen bonding with the rich amino groups in g-C 3 N 4 nanosheets. g-C 3 N 4 /FeTCPP heterogeneous catalysts are prepared via a facile self-assembly approach, in which light harvest is separated from catalysis spatially and temporally. The obtained g-C 3 N 4 /FeTCPP heterogeneous catalysts exhibit high activity for CO 2 reduction under visible-light irradiation, with CO yield of 6.52 mmol g −1 in 6 h and selectivity up to 98%. Fluorescence data indicate that the electrons can efficiently transfer from the g-C 3 N 4 nanosheets to FeTCPP. The mechanism for CO 2 reduction over the g-C 3 N 4 /FeTCPP heterogeneous catalysts is proposed based on the results of quasi in-situ ESR and UV–vis measurements. This work may pave a facile approach for fabricating the high-efficient photocatalysts for CO 2 reduction, as well as better understanding the related mechanism.

Construction of solid solution semiconductors has attracted much attention in photocatalysis by virtue of their tunable elemental composition and band structure. The integration of semiconductor sensitizers with molecular catalysts provides a promising way to fabricate highly efficient, selective and stable systems for CO2 photoreduction. Here ZnxCd1-xS (ZCS) solid solutions with a well-defined floccule-like morphology composed of nanoribbons are synthesized and used as the photosensitizer to couple with tetra(4-carboxyphenyl)porphyrin iron(iii) chloride (FeTCPP) for CO2 reduction. The effects of changes in surface atoms of the ZCS solid solution on the performance of CO2 photoreduction are investigated. Regardless of the presence of FeTCPP, our results show that the introduction of Zn into CdS can affect the activity and selectivity of CO2 photoreduction, as well as the stability of the obtained photocatalysts. More importantly, the presence of Zn can build efficient electron transfer channels from ZCS to FeTCPP and, thus, greatly facilitate the interfacial charge transfer. Benefitting from the efficient charge separation and electron transfer, ZCS-1/FeTCPP (Zn0.14Cd0.84S/FeTCPP) exhibits the highest activity for CO2 reduction under visible-light irradiation, with a CO yield of 1.28 μmol and a selectivity up to 93% after 4 h.

Glycosyl chlorides have historically been activated using harsh conditions and/or toxic stoichiometric promoters. More recently, the Ye and the Jacobsen groups showed that glycosyl chlorides can be activated under organocatalytic conditions. However, those reactions are slow, require specialized catalysts and high temperatures, but still provide only moderate yields. Presented herein is a simple method for the activation of glycosyl chlorides using abundant and inexpensive ferric chloride in catalytic amounts. Our preliminary results indicate that both benzylated and benzoylated glycosyl chlorides can be activated with 20 mol% of FeCl(3)

The reaction between diphenylmethanols and substituted benzenes is useful to yield triarylmethane derivatives which are important skeletons in various functional materials and biologically relevant substances. The Reactions were carried out under microwave irradiation as environmentally-friendly method. In cyclohexane, the reaction was accelerated under microwave irradiation as compared to under conventional heating. Also, when more than 0.8 equivalents of iron(III) chloride were used, the acceleration was observed. Notably, when iron(III) chloride and arenes were combined, the temperature of the reaction solution rose to 40°C. It is considered that a chemical species was formed upon coordination of iron(III) chloride to the diphenylmethanols or arenes.