Reaction Of Bismuth Research Articles

Anionic Chemistry Modulation Enabled Environmental Self‐Charging Aqueous Zinc Batteries: The Case of Carbonate Ions

Anionic chemistry modulation represents a promising avenue to enhance the electrochemical performance and unlock versatile applications in cutting‐edge energy storage devices. Herein, we propose a methodology that involves anionic chemistry of carbonate anions to tailor the electrochemical oxidation‐reduction reactions of bismuth (Bi) electrodes, where the conversion energy barrier for Bi (0) to Bi (III) has been significantly reduced, endowing anionic full batteries with enhanced electrochemical kinetics and chemical self‐charging property. The elaborately designed batteries with an air‐switch demonstrate rapid self‐recharging capabilities, recovering over 80% of the electrochemical full charging capacity within a remarkably short timeframe of 1 hour and achieving a cumulative self‐charging capacity of 5 Ah g‐1. The aqueous self‐charging battery strategy induced by carbonate anion, as proposed in this study, holds the potential for extending to various anionic systems, including seawater‐based Cl− ion batteries. This work offers a universal framework for advancing next‐generation multi‐functional power sources.

Exploring Bismuth (III) Sulpha Drugs Schiff Base Coordination Complexes: Design, Synthesis, Structural, Spectroscopic Characterization, and Biological Evaluations

The present study aimed to prepare and then evaluate the tetra and coordinated Bismuth (III) complexes [BiCl2 (L)] (LH = N, O donor Schiff base employed by the condensation of 1-acetyl-2-naphthol and 2-acetyl-1-naphthol using sulpha drugs as ligand) were derived by the reaction of bismuth (III) trichloride and sodium salt of an N, O donor Schiff base ligand and characterized. The authenticity of all the synthesized ligands and their Bi (III) complexes had been identified by microanalysis, various spectroscopic techniques like FT-IR, 1H NMR, and elemental analysis. The spectral evidence of the complexes has revealed the bidentate complexing nature of the Schiff base through phenolic oxygen and azomethine nitrogen atoms. The Schiff base ligand and Bismuth (III) complexes were assessed for antimicrobial activity. Assessment of antimicrobial activity against Gram-negative & Gram-positive bacteria and fungi has demonstrated that the complex (III) was more active than the Schiff base.

Monomeric octahedral bismuth(III) benzaldehyde-N1-alkyl thiosemicarbazones: Synthesis, characterization and biological properties

Due to their chemical and biological properties, the interest in thiosemicarbazones and their metal complexes is increasing day by day. In this study, the effect of the substituents at the N1 atoms of the thiosemicarbazones and the effect of halogen atoms on the type and biological properties of bismuth(III) complexes is investigated. The reactions of bismuth(III) halide with a series of benzaldehyde-N1-alkyl-thiosemicarbazones in 1:3 M ratio yield bismuth(III) halide complexes: {BiBr3(η1-S-Hbztsc)3} (1), {BiCl3(η1-S-Hbzmtsc)3} (2), {BiBr3(η1-S-Hbzmtsc)3} (3), {[BiCl3(η1-S-Hbzetsc)3].CH3OH} (4) and {BiBr3(η1-S-Hbzetsc)3} (5). Complexes 1–5 were characterized by a number of different spectroscopic methods. The crystal structures of complexes 1–5 and the free ligand benzaldehyde-N-methyl-thiosemicarbazone were determined by X-ray diffraction. Complexes 1–5 were tested for their in vitro cytotoxic activity against human breast adenocarcinoma (MCF-7) cell line. Complexes 1–5 showed low cytotoxic activity. The antibacterial activities of 1–5 and their free ligands against four strains bacteria of Staphylococcus epidermidis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli have been examined. The results indicated that bismuth(III) complexes 1–5 are most active against E. coli and, among them, complex 4 exhibits the highest activity. Lipoxygenase (LOX) inhibitory activity of the bismuth(III) halide complexes 1–5 and the free ligands has been detected experimentally. The IC50 values indicate that bismuth(III) halide complexes 1–5 have a higher enzyme inhibition potential than free ligands and cisplatin.

Bismuth(III) Iodide Complexes with 1-Ethyl-4-Dimethylaminopyridinium: Structure, Thermal Stability, and Optical Properties

Polynuclear bismuth(III) iodide complexes with 1-ethyl-4-dimethylaminopyridinium (1-EtDMAP)4[Bi8I28] (1) and (1-EtDMAP)BiI4 (2) have been obtained by the reactions of bismuth(III) iodide with an organic iodide salt cations in organic solvents and characterized by X-ray diffraction. The optical properties and thermal stability of the obtained compounds have been studied.

Spectrophotometric determination of bismuth (III) via pyrocatecol violet dye as chromogenic reagent

Direct, rapid, simple, precise and an accurate spectrophotometric method for the estimation of bismuth (III) ion was proposed. The reaction of bismuth (III) ion with pyrocatecol violet in aqueous solution in the presence of cetyl trimethyl ammonium bromide) CTAB)to form at pH 3.4 a colored complex which was showing maximum absorption at 648 nm. The linearity of the proposed method was obeyed Beer's law over the concentration range of 5-200 µg /25 ml i.e (0.2-8.0) ppm. The molar absorptivity factor found to be 1.72×104 l/mol.cm and, Sandall's sensitivity index was 0.01215 µg/cm. The proposed method was successfully applied for the determination of bismuth (III) in water and pharmaceutical preperation (Tablet).

Synthesis, structure and density functional theory calculations of a novel photoluminescent trisarylborane-bismuth(III) complex.

A novel trisarylborane-Bi(III) complex, tris(4-(dimesitylboryl)phenyl)bismuthine [Bi(PhBMes2 )3 ], in which (Ph=phenyl, and Mes=mesityl), was synthesized via the reaction of bismuth (III) chloride (BiCl3 ) with three equivalents of lithiated (4-bromophenyl)- dimesitylborane [BrPhBMes2 ]. The new trisarylbismuthine was characterized by elemental analysis, ultraviolet-visible (UV-vis) spectroscopy, and NMR (1 H and 13 C) spectroscopy. The molecular structure of Bi(PhBMes2 )3 in the solid state was determined using single-crystal X-ray diffraction analysis, which showed short intermolecular C-H···H-C contact. The complex is a fluorescent emitter (λmax =395nm) at room temperature and a phosphorescent emitter (λmax =423nm) at 77K, which displayed a long lifetime of 495ms. The UV-vis transitions were investigated using density function theory (DFT) and time-dependent (TD)-DFT calculations. Natural bond orbital analysis showed that the bismuth (III) center was mainly Lewis acidic in nature.

The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis, Crystal Structures, and Chemical Bonding

The intermetalloid clusters [M2Bi12]4+ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.

Bismuth(III) Complex of the [S4]•- Radical Anion: Dimer Formation via Pancake Bonds.

Reaction of bismuth(II) compounds with sulfur gives mixtures of [Bi(NONR)]2(μ2-Sn) (NONR = [O(SiMe2NR)2]2-). Examples for n = 1 and 3 have been crystallographically verified for R = 2,6-iPr2C6H3 (Dipp) and R = tBu, and the pentasulfide (n = 5) for R = Dipp. The corresponding product from reaction with the new Bi(II) radical Bi(NONAr‡)• (Ar‡ = C6H2(CHPh2)2-tBu-2,6,4) exists as the dimer [Bi(NONAr‡)(S4)]2, with π*(SOMO)-π*(SOMO) interactions linking the sulfur chains through trans-antarafacial pancake bonds.

Application of β-correction spectrophotometry for determination and speciation of bismuth (III) & (V) species in various water samples, soil, hair and drug formulations

A simple strategy has been developed for determination and speciation of bismuth(III) & (V) coupled dual wave β-correction spectrophotometry. The principle of the study was based on the reaction of bismuth(III) with reagent 1-(o-arsonophenylazo)-2-napthol-3,6-disulphuric acid (Thorin-I) to form a deep red orange colored complex species. The absorbance intensity was recorded at λmax=540nm. The method exhibits a wide linear range (0.25–20.0μgmL−1) and Ringbom's plots in the range 1.6–10.0μgmL−1 for bismuth(III) ions, respectively. The lower limit of detection (LOD) and quantification (LOQ) obtained were 0.045 and 0.15μgmL−1, respectively. Bismuth(V) was determined after reduction to bismuth(III) with Mn2+ in acidic solution. Trace level speciation studies were performed with satisfactorily recovery percentages for bismuth species. The method was applied for analysis of total bismuth in tap water, well water, marine water, hair sample, pharmaceutical formulations (cream) and in certified reference material (IAEA Soil-7). The results were compared successfully in terms of F and t-test with the reference method inductively coupled plasma-mass spectrometry(ICP-OES) and no significant difference was noticed at 95% confidence (P=0.05). The developed method has a unique advantage to be quantitatively applied to a variety of samples due to rapid response, short analytical time and ability to be detected by naked eye with good reproducibility. The LOD offered has a value lower than that recommended by World Health Organization (WHO) and compared successfully with some reported spectrochemical and electrochemical methods.

Bi13S18I2: (Re)discovery of a Subvalent Bismuth Compound Featuring [Bi2]4+ Dimers Grown in Sulfur/Iodine Flux Mixtures

Reactions of bismuth in sulfur/iodine flux mixtures were explored at various temperatures and iodine concentrations. The observed products include Bi2S3, BiSI, and Bi13S18I2. The latter compound, formerly reported as “Bi19I3S27” grows as well formed needles from the flux. This enabled extensive crystallographic studies by single crystal XRD and powder synchrotron XRD. These data allow a more accurate assignment of the disordered bismuth sites in the structure, indicating formation of subvalent Bi24+ dimers; this results in a stoichiometry of Bi13S18I2. Thermal decomposition studies and Raman spectroscopy support this structural model, and electronic structure calculations and optical reflectance studies indicate this compound is an indirect band gap semiconductor with band gap of 0.3 eV.

Study of activation energy and thermodynamic parameters of bismuth sulfide by thermogravimetric analysis

Bismuth sulfide chalcogenide was successfully synthesized inside the ampoule by conventional high temperature solid state solvothermal reaction of bismuth and sulfur. It was prepared by adjusting stoichiometric amount of the bismuth and sulfur heated in evacuated sealed quartz ampoule at 850°C for 12h, which is easy to be maintained and controlled. The key step was only adjusting the sulfur content. Synthesized powder was characterized by Energy dispersive Analysis by Energy Dispersive X-ray Spectroscopy (EDXS) and Thermo Gravimetric Analysis (TGA) in an air atmosphere. TGA curves were used to study the decomposition step of the isolated compounds. Activation energy (Eα) for decomposition has been calculated using Broido method. The thermodynamic parameters such as change in enthalpy (ΔH), change in entropy (S) and Gibb's free energy (ΔG) are estimated. TGA analysis shows a remarkable thermal stability with addition of sulfur content.

Multivariate optimisation of a rapid and simple automated method for bismuth determination in well water samples exploiting long path length spectrophotometry

ABSTRACTAn automated spectrophotometric system is proposed for the determination of bismuth in well water samples, using multi-syringe flow injection analysis (MSFIA) and exploiting a liquid waveguide capillary cell (LWCC). This method is based on the colorimetric reaction of bismuth and methylthymol blue (MTB) in the presence of polyvinylpyrrolidone (PVP) in acid medium (0.1 mol L−1 HNO3). The Bi(III)–MTB complex was measured at 600 nm. The method was optimised by multivariate techniques. Some figures of merit of the proposed system are worth being highlighted, such as its wide linear working range (between 4.9 and 600 μg L−1), its low detection limit (1.5 μg L−1 of bismuth) and its high intra-day precision and inter-day precision (0.7% (n = 12) and 1.4% (n = 5), respectively, both expressed as RSD). Moreover, a high injection frequency of 30 h−1 is achieved, as the proposed analyser is a powerful tool for fast Bi(III) determination. The method developed was successfully validated by analysing reference samples (pharmaceutical samples) by comparing the results with those obtained by ICP-OES and it was satisfactorily applied to well water samples. Besides, the present system is miniaturised allowing in situ measurements in control processes and field analysis.

Sonochemical Synthesis of Bismuth(III) Nano Coordination Compound and Direct Synthesis of Bi2O3 Nanoparticles from a Bismuth(III) Nano Coordination Compound Precursor

A new coordination Compound [Bi(L)(NO3)2(ONO2)(CH3OH)] (1) [L: C5H4NCH=NNHCONC5H4] has been synthesized by the reaction of Bismuth(III) bromide with the ligand pyridine-2-carbaldehyde isoniazid and characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. Single crystal X-ray diffraction reveals that the compound 1 is mononuclear complex, contains Bismuth(III) in a distorted tricapped trigonal prismatic geometry environment of NNO donors of Schiff base ligand, five oxygen atoms of Nitrate molecules and one oxygen atom of methanol molecule. We also synthesized a nano form of the compound 1 by the sonochemical method and characterized it by elemental analysis, scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy. The δ-Bi2O3 nano-particle was obtained by calcinations of the nano compound 1 at 500 oC under air atmosphere and was characterized by SEM and XRD.

Facile synthesis of flower-like Bi12O17Cl2/β-Bi2O3 composites with enhanced visible light photocatalytic performance for the degradation of 4-tert-butylphenol

Novel three-dimensional flower-like Bi12O17Cl2/β-Bi2O3 composites are prepared using a facile solvothermal-calcining process and their photocatalytic performances for the degradation of 4-tert-butylphenol (PTBP, a representative alkylphenol) are evaluated under visible light irradiation. The formation of such composites is assumed to involve the reduction of Bi(III) to nano-metallic bismuth via a solvothermal process, followed by the reaction of bismuth with oxygen and bismuth oxide chloride hydroxide during the calcination in air. The XRD, XPS, EDS mapping, HRTEM, UV–vis DRS, and photocurrent measurement results indicate that heterojunctions are formed between Bi12O17Cl2 and β-Bi2O3 with broad contact interfaces. The as-synthesized Bi12O17Cl2/β-Bi2O3 hybrid materials possess favorable band structures, heterojunction structures, relatively high specific surface areas, and hierarchical micro/nano-structures, resulting in superior photocatalytic and mineralization efficiencies for the decomposition of PTBP under visible light irradiation. The optimum photocatalytic activity of a Bi12O17Cl2/β-Bi2O3 sample is approximately 3, 12, 51, and 107 times higher than the activities of single β-Bi2O3, Bi12O17Cl2, nitrogen-doped TiO2, and BiOCl, respectively. In addition, the photogenerated reactive species are identified based on free radicals trapping experiments and EPR analysis, which reveals that the photodegradation of PTPB over Bi12O17Cl2/β-Bi2O3 under visible light is dominated by direct hole and superoxide radical oxidation rather than oxidized by hydroxyl radical.

Supramolecular assemblies of two piperazine metal-organic bismuth(III) derivatives: a new precursor for the preparation of bismuth(III) oxide bromide nano-structures

Two BiBr3 supramolecular complexes, [Bi(2-bpmp)Br2.06Cl0.94] (1) and [Bi(4-H2bpmp)Br4.29Cl0.71]·H2O (2) {2-bpmp = N,N′-bis(2-pyridylmethyl)piperazine and 4-bpmp = N,N′-bis(4-pyridylmethyl)piperazine}, were prepared by reaction of bismuth(III) chloride and potassium bromide with two nitrogen donor ligands under thermal gradient conditions using the branched tube method. Compounds 1 and 2 were structurally characterized by single-crystal X-ray diffraction. In monomeric 1, bismuth is coordinated by two pyridyl and piperazine nitrogens of 2-bpmp, and by three halides. Compound 2 is also monomeric but is bonded to only one pyridyl nitrogen. In both compounds, extensive hydrogen-bonding interactions lead to supramolecular networks; in 2, the hydrogen bonds are augmented by π–π stacking interactions. Thermal stabilities of both compounds were studied by thermal gravimetric and differential thermal analyses. Thermal decomposition of nanosized 1 and 2 in air produced BiOBr nanoparticles.

Spectrophotometric Determination of Bismuth(III) with Arsenazo(III) Reagent in Water samples and Veterinary Preparation

A simple , sensitive and accurate spectrophotometric method for the trace determination of bismuth (III) has been developed .This method is based on the reaction of bismuth (III) with arsenazo(III) in acid solution (pH=1.9) to form a blue water soluble complex which exhibits maximum absorption at 612nm .Beer's law is obeyed over the concentration range of 2-85 ?g bismuth (III) in a final volume of 20 mL( i.e. 0.1 – 4.25?g.mL-1) with a correlation coefficient of (0.9981) and molar absorptivity 1.9×104 L.mol-1.cm-1 . The limit of detection (LOD) and the limit of quantification (LOQ) are 0.0633 and 0.0847 ?g.mL-1 , respectively . Under optimum conditions,the stoichiometry of the reaction between bismuth (III) and arsenazo(III) reagent was found to be 1:2. The recoveries were obtained in the range of 98.9 - 100.0% and a relative standard deviation of ±0.59 to ±2.73% depending on the concentration level of bismuth. The effect of interferences by a number of common cations and anions in the presence of composite mixture has been studied .The proposed method has been applied successfully for determination of bismuth in water samples and veterinary preparation .

Spectrophotometric Determination of Bismuth(III) with Arsenazo(III) Reagent in Water samples and Veterinary Preparation

A simple , sensitive and accurate spectrophotometric method for the trace determination of bismuth (III) has been developed .This method is based on the reaction of bismuth (III) with arsenazo(III) in acid solution (pH=1.9) to form a blue water soluble complex which exhibits maximum absorption at 612nm .Beer's law is obeyed over the concentration range of 2-85 ?g bismuth (III) in a final volume of 20 mL( i.e. 0.1 – 4.25?g.mL-1) with a correlation coefficient of (0.9981) and molar absorptivity 1.9×104 L.mol-1.cm-1 . The limit of detection (LOD) and the limit of quantification (LOQ) are 0.0633 and 0.0847 ?g.mL-1 , respectively . Under optimum conditions,the stoichiometry of the reaction between bismuth (III) and arsenazo(III) reagent was found to be 1:2. The recoveries were obtained in the range of 98.9 - 100.0% and a relative standard deviation of ±0.59 to ±2.73% depending on the concentration level of bismuth. The effect of interferences by a number of common cations and anions in the presence of composite mixture has been studied .The proposed method has been applied successfully for determination of bismuth in water samples and veterinary preparation .

Spectrophotometric Determination of Bismuth with Alizarine Red S and Cetylpyridinium Chloride - Application to Water Samples, Urine and Veterinary Preparation

A simple, accurate, sensitive and reliable method for spectrophotometric determination of Bismuth(III) is developed. The method is based on the reaction of bismuth (III) with alizarine red S (ARS) and cetylpyridinium chloride (CPC) in the presence of Triton X-100 at pH 3 to form a pink, water soluble ternary complex which shows a maximum absorption at 507 nm with a molar absorptivity of 1.4 x104 L.mol-1cm-1. The calibration curve is linear in the concentration range 5– 150 μg of bismuth (III) in a final volume of 20mL (i.e. 0.25-7.5 μg mL-1) with a determination coefficient of (R2) (0.9974). The limit of detection (LOD) and the limit of quantification (LOQ) are 0.0671 and 0.2235 g.mL-1, respectively. Under optimum conditions, the stoichiometry of the reaction between bismuth (III), alizarine red S and cetylpyridinium chloride is found to be 1:3:6, respectively. The recoveries are obtained in the range of 98.8- 102.1% and a relative standard deviation (RSD) of ± 0.93 to ±3.07% depending on the concentration level. The proposed method has been applied successfully to the determination of bismuth (III) in various samples such as, natural waters, urine and veterinary preparation

Improved Spectrophotometric Determination of Bismuth (III) with Bromopyrogallol Red in Mixed Surfactants-Application to Waters and Veterinary Preparation

A simple and sensitive spectrophotometric method for the determination of trace amounts of bismuth is established. The method is based on the reaction of bismuth with bromopyrogallol red at pH 3 in the presence of a mixture of cetylpyridinium chloride and triton X-100 surfactants to form a blue coloured complex which shows maximum absorbance at 644 nm. A plot of absorbance with bismuth concentration gives a straight line indicating that Beer,s law has been obeyed over the range 3-150 µg/25 ml, i.e., 0.12-6 ppm with a molar absorptivity of 3.3×104 l.mol-1.cm-1 and Sandell,s sensitivity index of 0.006 µg.cm-2. The interfering effect of a number of common captions and anions in the presence of comosite mixture (NaF and tartaric acid) and ascorbic acid as masking agents has been studied. The effect of common excipients has also been examined. The method has been applied successfully to the determination of bismuth in water samples and a veterinary preparation.

Spectrophotometric study of competitive complexation equilibria involving overlapped spectral responding species: Determination of the stability constant of bismuth-pyrophosphate complex

Abstract Spectrophotometric study of competitive complex formation equilibria involving overlapped spectral responding species applying a simple and versatile algorithm was carried out. The algorithm involves multivariable regression for calculation of equilibrium concentrations from multiwavelength data and mass action law for the stability constant calculation. The used regression functions are part of common statistical software. Stability constants and complex stoichiometry of competing equilibria were simultaneously determined. The species concentration profiles at several spectral overlapping and α-coefficient of competing reaction were obtained. Non-absorbing bismuth — pyrophosphate (PPh) system was studied as a competitive reaction of bismuth — 4-(2-Pyridylazo) resorcinol (PAR) complex. The formation of Bi-PPh complex with 1:1 stoichiometry was proved in the studied concentration region (CBi = 1×10−5 mol L−1; CPPh = 5×10−6 − 1×10−4 mol L−1). The stability constant of the complex at pH 1 and µ = 1.0 have been determined: logβ = 4.2±0.2.