New amino group functionalized porous carbon for strong chelation ability towards toxic heavy metals

Herein, ethylenediamine functionalized porous carbon (PC-ED/1.5) was synthesized, then characterized by various methods and finally used as a functional material for Cu(ii) and Pb(ii) ion removal from water. XPS revealed the presence of numerous functionalities within the surface of PC including –NH and C–N–C groups. Furthermore, S_BET, RS, XRD and FTIR analyses confirmed the changes implemented on the PC surface. Thereafter, a systematic study was implemented to analyze the interactions of the PC-ED/1.5 surface with Cu(ii) and Pb(ii) heavy metal ions. Hence, adsorption experiments showed that the PC-ED/1.5 exhibits maximum adsorption capacities of 123.45 mg g⁻¹ and 140.84 mg g⁻¹ for Cu(ii) and Pb(ii), respectively. Moreover, in situ electrostatic interactions occurring between the divalent cation and the PC-ED/1.5 functional groups was investigated. The mechanism involves chelation processes, electrostatic interactions and mechanical trapping of the metal ions in the adsorbent pores. Interestingly, a synergistic effect of the pores and surface active sites was observed. Finally, by using alginate bio-polymer we prepared membrane films of PC-ED/1.5 which showed long-term stability, regeneration capabilities and high mass recovery.

Herein, ethylenediamine functionalized porous carbon (PC-ED/1.5) was synthesized, then characterized by various methods and finally used as a functional material for Cu(ii) and Pb(ii) ion removal from water.     

An electrochemical sensor based on a MOF/ZnO composite for the highly sensitive detection of Cu(ii) in river water samples

Cu(ii) ions are one of the most common forms of copper present in water and can cause bioaccumulation and toxicity in the human body; therefore, sensitive and selective detection methods are required. Herein, a copper ion sensor based on a UiO-66-NH₂/ZnO composite material is proposed. The UiO-66-NH₂/ZnO nanocomposite was prepared by an ultrasonic mixing method. The morphology and structure of the nanocomposite were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The sensitivity to Cu(ii) is 6.46 μA μM⁻¹ and the detection limit is 0.01435 μM. The composite material is rich in –OH and –NH₂ groups, which are active sites for Cu(ii) adsorption. The UiO-66-NH₂/ZnO-modified electrode has good repeatability and anti-interference ability. The sensor was successfully used for the determination of Cu(ii) in an actual water sample.

Cu(ii) ions are one of the most common forms of copper present in water and can cause bioaccumulation and toxicity in the human body; therefore, sensitive and selective detection methods are required.     

Mimicking 2,2′:6′,2′′:6′′,2′′′-quaterpyridine complexes for the light-driven hydrogen evolution reaction: synthesis,structural, thermal and physicochemical characterizations

The synthetic difficulties associated with quaterpyridine (qtpy) complexes have limited their use in the formation of various metallosupramolecular architectures in spite of their diverse structural and physicochemical properties. Providing a new facile synthetic route to the synthesis of functionalised qtpy mimics, we herein report the synthesis of three novel –NH₂ functionalized qtpy-like complexes 12–14 with the general formula M(C₁₆H₁₄N₁₂)(NO₃)₂ (M = Co(ii), Ni(ii) and Cu(ii)) in high yield and purity. Characterization of these complexes has been done by single crystal X-ray diffraction (SCXRD), thermogravimetric analysis, UV-Vis, infrared, mass spectrometry and cyclic voltammetry. As indicated by SCXRD, in all the synthesized complexes, the metal ions show a strongly distorted octahedral coordination geometry and typical hydrogen bonding networks involving DAT groups. In addition, complexes 12–14 have been analyzed as potential photocatalysts for hydrogen evolution reaction (HER) displaying good turnover numbers (TONs). Hydrogen produced from these photocatalysts can serve as the possible alternative for fossil fuels. To the best of our knowledge, this is the only study showcasing –NH₂ functionalized qtpy-like complexes of Co(ii), Ni(ii) and Cu(ii) and employing them as photocatalysts for HER. Thus, a single proposed strategy solves two purposes-one related to synthesis while second is related to our environment.

Facile synthesis of three novel –NH₂ functionalized qtpy-like complexes, their characterizations and study of their photocatalytic properties for hydrogen evolution reaction.     

Assorted functionality-appended UiO-66-NH2 for highly efficient uranium(vi) sorption at acidic/neutral/basic pH

A series of functionalized metal organic frameworks (MOFs) were synthesized by the post-synthetic modification (PSM) of Zr(iv)-containing UiO-66-NH₂ MOFs using covalent grafting with various functional groups utilizing pendant –NH₂ moieties. The tethering of amide (with/without pendant carboxylic acid), iminopyridine, phoshinic amide and sulphur-containing functionalities produced a library of eight different UiO-66-NH₂ derivatives. The functionalized MOFs were characterized by FT-IR spectroscopy, NMR, PXRD, TGA, SEM-EDX and BET surface area analysis. Uranyl ion extraction with the functionalized MOFs was investigated in acidic/neutral/basic conditions (pH 1 to 9). This work presents a comprehensive study of different functionalized MOFs to investigate the effects of various analytical parameters, including pH, contact time, and desorption process. The MOFs as solid phase extractants (SPEs) provide a direct comparison of the sorption efficiencies of different functional groups on a common solid support. A phosphorous-functionalized material, UiO-66-PO-Ph, with enhanced thermal stability (∼500 °C) exhibits the best sorption capacity (∼96%) in an acidic medium (pH 3). The parent MOF UiO-66-NH₂ (92%) and iminopyridine-functionalized UiO-66-IMP (90%) showed excellent sorption in neutral conditions (pH 7). Amide-containing MOFs UiO-66-AM1 (40%), UiO-66-AMMal (31%) and UiO-66-AMGlu (70%), sulfur-based MOFs UiO-66-SMA (65%) and UiO-66-SSA (27%), and phosphorous-functionalized UiO-66-PO-OPh (50%) displayed maximum sorption in basic conditions (pH 8). The kinetics studies revealed rapid uranium sorption in about 2 h due to the effective binding of uranyl ions with the anchored functional groups of MOFs; quantitative elution of uranyl ions from the MOF framework was carried out with 0.1/0.01 M HNO₃. The MOFs also exhibit moderate recyclability for uranium sorption and can be regenerated by an acidic solution. The functionalized MOFs alter the stability in acidic/basic media; thus, UiO-66-NH₂ is a versatile MOF material employed as an SPE for the extraction of radionuclides from aqueous media. This work also provides a platform for the development of new functionalized MOF materials for the efficient sorption of uranium as well as moderate recyclability for its removal, and the potential applications include the removal of uranium from aqueous waste streams.

Eight assorted functionalities were anchored on UiO-66-NH₂via PSM strategy displaying MOFs with similar framework but variable uranyl binding affinities. The excellent sorption capacity of UiO-66-PO-Ph makes it efficient uranium sorbent material.     

Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes

The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH₃)(OH)₂) and hemiacetal (RCH(OH)(OCH₃)) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic ¹H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the ¹H vicinities were done with 2D ¹H–¹³C HETCOR, ¹H–¹H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of ¹³C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group.

The complex chemical functionalization of the aldehyde group was elucidated in copper and cobalt complexes for 4- and 3-pyridinecarboxaldehyde ligands.     

Photoaccelerated energy transfer catalysis of the Suzuki–Miyaura coupling through ligand regulation on Ir(iii)–Pd(ii) bimetallic complexes

Three bimetallic Ir(iii)–Pd(ii) complexes [Ir(ppy)₂(bpm)PdCl₂](PF₆) (ppy = 2-phenylpyridine, 1), [Ir(dfppy)₂(bpm)PdCl₂](PF₆) (dfppy = (4,6-difluorophenyl)pyridine, 2), and [Ir(pq)₂(bpm)PdCl₂](PF₆) (pq = 2-phenylquinoline, 3) were synthesized by using 2,2′-bipyrimidine (bpm) as a bridging ligand. The influences of the cyclometalated ligand at the Ir(iii) center on the photophysical and electrochemical properties as well as photocatalytic activity for the Suzuki–Miyaura coupling reaction under mild conditions were evaluated. The results revealed that complex 3 enables dramatically accelerating the Suzuki–Miyaura coupling reaction under visible light irradiation at room temperature, due to the effective absorption of visible light and appropriate locus of the excited chromophore. Mechanism studies showed that the chromophore [Ir(pq)₂(bpm)] fragment absorbs visible light to produce the triplet excited state centering on the bridging ligand which boosts the formation of electron rich Pd(ii) units and facilitates the oxidative addition step of the catalytic cycle. Simultaneously, the excited chromophore undergoes energy transfer efficiently to the Pd(ii) reaction site to form the excited Pd(ii) species, resulting in enhancement of Pd(ii) reduction steps of the Suzuki–Miyaura coupling reaction and increasing the reactivity of the catalyst. This provides a new strategy for designing photocatalysts for coupling reaction through altering the cyclometalated ligand to modulate the photophysical properties and the cooperation between two metal units.

A series bimetallic catalysts were synthesized. Relationship between the structure of catalysts and catalytic reactivities were studied and improvement of the catalytic efficiency for Suzuki–Miyaura coupling was accomplished by regulating their chromophores.     

Alkaline earth metal ion coordination increases the radical scavenging efficiency of kaempferol

Flavonoids are used as natural additives and antioxidants in foods, and after coordination to metal ions, as drug candidates, depending on the flavonoid structure. The rate of radical scavenging of the ubiquitous plant flavonoid kaempferol (3,5,7,4′-tetrahydroxyflavone, Kaem) was found to be significantly enhanced by coordination of Mg(ii), Ca(ii), Sr(ii), and Ba(ii) ions, whereas the radical scavenging rate of apigenin (5,7,4′-trihydroxyflavone, Api) was almost unaffected by alkaline earth metal (AEM) ions, as studied for short-lived β-carotene radical cations (β-Car˙⁺) formed by laser flash photolysis in chloroform/ethanol (7 : 3) and for the semi-stable 2,2-diphenyl-1-picrylhydrazyl radical, DPPH˙, in ethanol at 25 °C. A 1 : 1 Mg(ii)–Kaem complex was found to be in equilibrium with a 1 : 2 Mg(ii)–Kaem₂ complex, while for Ca(ii), Sr(ii) and Ba(ii), only 1 : 2 AEM(ii)–Kaem complexes were detected, where all complexes showed 3-hydroxyl and 4-carbonyl coordination and stability constants of higher than 10⁹ L² mol⁻². The 1 : 2 Ca(ii)–Kaem₂ complex had the highest second order rate constant for both β-Car˙⁺ (5 × 10⁸ L mol⁻¹ s⁻¹) and DPPH˙ radical (3 × 10⁵ L mol⁻¹ s⁻¹) scavenging, which can be attributed to the optimal combination of the stronger electron withdrawing capability of the (n − 1)d orbital in the heavier AEM ions and their spatially asymmetrical structures in 1 : 2 AEM–Kaem complexes with metal ion coordination of the least steric hindrance of two perpendicular flavone backbones as ligands in the Ca(ii) complex, as shown by density functional theory calculations.

Radical scavenging activity of kaempferol is notably enhanced by Ca(ii) binding.     

Cd(ii) removal by Fe(ii) surface chemically modified layered double hydroxide–graphene oxide: performance and mechanism

Cd(ii) adsorption onto Fe(ii) modified Layered double hydroxide–graphene oxide (LDH–GO@Fe(ii)) was investigated using batch experiments. With the modification of Fe(ii), LDH–GO maintained its structure, while Fe(ii) species formed non-crystalline iron oxide clusters on the surface of the LDH/GO. A kinetics study indicated that adsorption obeyed a pseudo-second-order rate law. The equilibrium data were fitted well with the Langmuir isotherm model. The maximum adsorption capacity of LDH–GO@Fe(ii)₁₀ was 28.98 mg g⁻¹, higher those that of pure LDH–GO and LDH–GO@Fe(ii)₅₀. The increased sorption capacities could be explained by the increased specific surface area. Modification with Fe(ii) would lead to the generation of amorphous Fe oxides and Fe could occupy the binding sites for Cd(ii), thus excess Fe in the structure will restrain the adsorption of Cd(ii). The XRD and XPS patterns revealed the formation of Cd(OH)₂ after adsorption. Batch experiments indicated that precipitation and surface complexation were the main pathways for Cd(ii) removal.

Fe(ii)-decorated LDH–GO composites had a high capacity for Cd(ii) removal. The mechanisms were controlled by surface-induced precipitation and complex formation.     

N–C bond formation between two anilines coordinated to a ruthenium center in cis-form affording a 3,5-cyclohexadiene-1,2-diimine moiety

Ruthenium complexes containing two anilines or its derivatives, cis-[Ru^II(NH₂C₆H₅)₂(bpy)₂]²⁺ ([1]²⁺) and cis-[Ru^II(NH₂C₆H₄(4-CH₃))₂(bpy)₂]²⁺ ([2]²⁺), were oxidized by four molar equivalents of (NH₄)₄[Ce^IV(SO₄)₄]·2H₂O to give N¹-phenylcyclohexa-3,5-diene-1,2-diimineruthenium(ii) complexes, cis-[Ru^II(NHC₆H₄NC₆H₅)(bpy)₂]²⁺ ([4]²⁺) and cis-[Ru^II(NHC₆H₃(4-CH₃)NC₆H₄(4-CH₃))(bpy)₂]²⁺ ([5]²⁺), respectively, through an N–C bond formation between two aniline ligands cis-coordinated to the ruthenium center.

Four-electron oxidation of two anilines coordinated to a ruthenium(ii) center in a cis-form affords N¹-phenylcyclohexa-3,5-diene-1,2-diimine through an N–C bond formation with N–H and C–H bond activation.     

Zinc(ii) triazole meso-arylsubstituted porphyrins for UV-visible chloride and bromide detection. Adsorption and catalytic degradation of malachite green dye

Three new triazole meso-arylporphyrins (4a–c) were synthesized by the copper(i)-catalyzed azide alkyne cycloaddition (CuAAC) “click” reaction in high yield. The corresponding zinc(ii) coordination compounds (5a–c) have also been prepared. All 4a–c and 5a–c porphyrin species were fully characterized by elemental analysis, electrospray ionization and MALDI-TOF mass spectrometry, infrared spectroscopy, proton nuclear magnetic resonance, UV-visible, fluorescence and cyclic voltammetry. The zinc(ii) 5a–c complexes have been tested as detectors for Cl⁻ and Br⁻ anions. UV-visible titrations reveal that these host systems exhibit strong anion binding affinities. The efficiency of the adsorption of the malachite green dye (MG) dye on the 4a–c free base porphyrins and the corresponding zinc(ii) complexes 5a–c was investigated by a kinetic study using these synthetic porphyrin derivatives as adsorbents. The use of our triazole Zn(ii) complexes in the catalytic degradation of the MG dye is the first example where a metalloporphyrin is involved in the MG dye decolorization reaction. The degradation reactions were carried out using an ecological oxidant (H₂O₂), where the efficiency of the decolorization has been characterized by UV-visible spectroscopic analysis. Several factors affecting the degradation phenomenon have been studied. The energetic parameters concerning the degradation process have also been determined.

Three triazole porphyrins and there corresponding zinc complexes are described as well as their spectroscopic and electrochemical data. The chloride and bromide sensing efficiency and the degradation of the malachite green dye are also reported.     

Amino group dependent sensing properties of metal–organic frameworks: selective turn-on fluorescence detection of lysine and arginine

Recently, metal–organic frameworks (MOFs) have been extensively investigated as fluorescence chemsensors due to their tunable porosity, framework structure and photoluminescence properties. In this paper, a well-known Zr(iv)-based MOF, UiO-66-NH₂ was demonstrated to have capability for detection of l-lysine (Lys) and l-arginine (Arg) selectively from common essential amino acids in aqueous media via a fluorescence turn-on mechanism. Further investigation reveals its high sensitivity and strong anti-interference properties. Moreover, the possible mechanism for sensing Lys and Arg was explored by FT-IR and ¹H-NMR, and the results indicate that the enhancement of the fluorescence could be ascribed to the adsorption of Lys/Arg and the hydrogen bonding interactions between Lys/Arg and the amino group of UiO-66-NH₂. The difference of the sensing capacity and sensitivity between UiO-66 and UiO-66-NH₂ revealed that the amino group plays an essential role in the sensing performance. This work presents a unique example of the functional group dependent sensing properties of MOFs.

The amino group of UiO-66-NH₂ was demonstrated to play an important role in selective fluorescence turn-on sensing of lysine and arginine.     

Simultaneous removal of Sb(iii) and Cd(ii) in water by adsorption onto a MnFe2O4–biochar nanocomposite

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption. The MnFe₂O₄–BC nanocomposite was prepared via a co-precipitation method and analyzed using various techniques. The results confirm the successful decoration of the biochar surface with MnFe₂O₄ nanoparticles. The maximum Sb(iii) removal efficiency was found to be higher from bi-solute solutions containing Cd(ii) than from single-solute systems, suggesting that the presence of Cd(ii) enhances the removal of Sb(iii). The Langmuir isotherm model describes well Sb(iii) and Cd(ii) removal via adsorption onto the MnFe₂O₄–BC nanocomposite. The maximum adsorption capacities are 237.53 and 181.49 mg g⁻¹ for Sb(iii) and Cd(ii), respectively, in a bi-solute system. Thus, the prepared MnFe₂O₄–BC nanocomposite is demonstrated to be a potential adsorbent for simultaneously removing Sb(iii) and Cd(ii) ions from aqueous solutions.

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption.     

Covalently linked mercaptoacetic acid on ZrO2 coupled cellulose nanofibers for solid phase extraction of Hg(ii): experimental and DFT studies

Zirconium oxide (ZrO₂) nanoparticles were introduced onto cellulose nanofibers after being covalently functionalized with mercaptoacetic acid. We experimentally demonstrate that the nanocomposite is capable of selectively capturing Hg(ii) from aqueous samples down to trace level concentrations. Density functional theory (DFT) calculations indicate that energetically favorable R–S → Hg ← O–R bidentate complex formation enhances the rapid adsorption, leading to selective extraction of Hg(ii). Furthermore, the loss of ZrO₂ particles during flow-through studies is controlled and restricted after binding to CNF rather than being used directly in the column. The Hg(ii) selectivity is primarily due to the Lewis soft–soft acid–base chelation of Hg(ii) with the mercapto functionalities of the adsorbent. The experimental observations depict a high sorption capacity of 280.5 mg g⁻¹ for Hg(ii). The limit of detection and quantification of the proposed approach were found to be 0.04 μg L⁻¹ and 0.15 μg L⁻¹, respectively. Analytical method accuracy and validity were determined by analyzing Standard Reference Materials and by the standard addition method (recovery > 95% with a 5% RSD). The findings of a Student''s t-test were found to be lower than the critical Student''s t value. Real water samples were successfully analyzed using the developed procedure.

Optimized structures for Hg(ii) complexation with mercaptoacetic acid.     

Exploring unsymmetrical diboranes(4) as boryl ligand precursors: platinum(ii) bis-boryl complexes

A series of five unsymmetrical platinum(ii) bis-boryl complexes, bearing two distinct boryl ligands, are obtained by the oxidative addition reaction of unsymmetrical diborane(4) derivatives, bearing either two different dialkoxy or one dialkoxy and one diamino boryl moiety, with [(Ph₃P)₂Pt(C₂H₄)]. All five complexes were structurally and spectroscopically characterised. The bis-boryl platinum(ii) complexes exhibit slightly distorted square-planar cis-boryl structures with acute B–Pt–B angles, short B⋯B distances of 2.44–2.55 Å and relatively long trans-boryl P–Pt distances around 2.34 Å. The ³¹P–¹⁹⁵Pt NMR coupling constants are indicative for the strongly donating/trans-influencing boryl ligands. Despite the structural and spectroscopic data at hand no finally conclusive order of the donor properties/trans-influence of the boryl ligands can be deduced on the basis of these data. This may be explained by an (residual) interaction of two boryl ligands.

Five unsymmetrical platinum(ii) bis-boryl complexes are reported, the spectroscopic and structural data allow the first comparative study on these complexes.     

Functionalized biochar-supported magnetic MnFe2O4 nanocomposite for the removal of Pb(ii) and Cd(ii)

In this study, a novel magnetic biochar-MnFe₂O₄ nanocomposite (BC/FM) was prepared using low-cost corn straw and MnFe₂O₄ by sol–gel/pyrolyzing route using egg white, which has abundant functional groups (–NH₂ and –COOH). Following that, its composition, morphology and structure was characterized by various techniques including SEM-EDX, BET, XRD, and VSM. Batch experiment of the adsorption for Pb(ii) and Cd(ii) including influence of pH, kinetics, isotherm and thermodynamics was also studied. The results demonstrated that biochar could effectively support MnFe₂O₄, which displayed high dispersion on the surface of the biochar and possessed abundant functional groups and high surface area contributing to superior performance on Pb(ii) and Cd(ii) removal. Therein, MnFe₂O₄ with high magnetism is convenient for separating the magnetic BC/FM from an aqueous medium. Adsorption experiment results indicate that Pb(ii) and Cd(ii) removal by BC/FM was closely related to pH with the best value of pH 5.0, and the process reached equilibrium in 2 h. The adsorption process is well-described by the pseudo-second-order kinetic model and Sips (Freundlich–Langmuir) model. Thermodynamic studies suggest that the adsorption process is spontaneous and exothermic. The maximum experimental adsorption capacity of BC/FM is 154.94 and 127.83 mg g⁻¹ for Pb(ii) and Cd(ii), respectively, in single-solute system, which is higher than that of some of the other adsorbents of biochar or biochar-based composites. In bi-solute system, the preferential adsorption order of BC/FM for the two metals is Pb(ii) prior to Cd(ii). Finally, FTIR and XPS analysis verified that the main mechanism of Pb(ii) and Cd(ii) removal by BC/FM is by forming Pb/Cd–O or complexation of carboxyl and hydroxyl and ion exchange. Therefore, the prepared magnetic BC/FM composite, as an excellent adsorbent, exhibited potential applications for the removal of Pb(ii) and Cd(ii) from wastewater.

In this study, a novel magnetic biochar-MnFe₂O₄ nanocomposite (BC/FM) was prepared using low-cost corn straw and MnFe₂O₄ by sol–gel/pyrolyzing route using egg white, which has abundant functional groups (–NH₂ and –COOH).     

The kinetics process of a Pb(ii)/Pb(0) couple and selective fabrication of Li–Pb alloys in LiCl–KCl melts

The electrode reaction of Pb(ii) and co-reduction of Li(i) and Pb(ii) were investigated on a tungsten electrode in LiCl–KCl eutectic melts by a range of electrochemical techniques. From cyclic voltammetry and square wave voltammetry measurements, the reduction of Pb(ii) was found to be a one-step diffusion-controlled reversible process with the exchange of 2 electrons. The diffusion coefficients of Pb(ii) were computed, and they obey the Arrhenius law. Using the linear polarization technique, the kinetic parameters, such as exchange current intensity (j₀), standard rate constant (k⁰) and charge transfer resistance (R_ct) for the Pb(ii)/Pb(0) couple on a tungsten electrode were studied at different temperatures, and the activation energy is 27.32 kJ mol⁻¹, smaller than the one for diffusion of Pb(ii), which further confirmed that the reduction of Pb(ii) was controlled by diffusion. A depolarisation effect for Li(i) reduction was observed from the results of cyclic voltammetry, square wave voltammetry and chronopotentiometry due to the formation of Li–Pb alloys by co-reduction of Li(i) and Pb(ii). Furthermore, five Li–Pb intermetallic compounds, LiPb, Li₈Pb₃, Li₃Pb, Li₁₀Pb₃ and Li₁₇Pb₄ characterized by scanning electronic microscopy and X-ray diffraction, were selectively prepared by potentiostatic electrolysis on a tungsten electrode and galvanostatic electrolysis on a liquid Pb electrode, respectively.

Five Li–Pb intermetallic compounds are selectively prepared according to their deposition potentials and characterized by XRD and SEM.     

Synthesis of FeO@SiO2–DNA core–shell engineered nanostructures for rapid adsorption of heavy metals in aqueous solutions

Creating novel and innovative nanostructures is a challenge, aiming to discover nanomaterials with promising properties for environmental remediation. In this study, the physicochemical and adsorption properties of a heterogeneous nanostructure are evaluated for the rapid removal of heavy metal ions from aqueous solutions. Core–shell nanostructures are prepared using iron oxide cores and silica dioxide shells. The core is synthesized via the co-precipitation method and modified in situ with citric acid to grow a carboxyl layer. The shell was hydrolyzed/condensed and then functionalized with amine groups for ds-DNA condensation via electrostatic interaction. The characterization techniques revealed functional FeO@SiO₂–DNA nanostructures with good crystallinity and superparamagnetic response (31.5 emu g⁻¹). The predominant superparamagnetic nature is attributed to the citric acid coating. This improves the dispersion and stability of the magnetic cores through the reduction of the dipolar–dipolar interaction and the enhancement of the spin coordination. The rapid adsorption mechanism of FeO@SiO₂–DNA was evaluated through the removal of Pb(ii), As(iii), and Hg(ii). A rapid adsorption rate is observed in the first 15 min, attributed to a heterogeneous chemisorption mechanism based on electrostatic interactions. FeO@SiO₂–DNA shows higher adsorption efficiency of 69% for Pb(ii) removal compared to As(iii) (51%) and Hg(ii) (41%). The selectivity towards Pb(ii) is attributed to the similar acid nature to ds-DNA, where the ionic strength interaction provides good affinity and stability. The facile synthesis and rapid adsorption suggest a promising nanostructure for the remediation of water sources contaminated with heavy metal ions and can be extended to other complex molecules.

Facile synthesis of well-dispersed and magnetic FeO@SiO₂–DNA nanostructures with electrostatic active sites for interaction and rapid adsorption of heavy metals.     

Metal-bio functionalized bismuthmagnetite [Fe3−xBixO4/SiO2@l-ArgEt3+I−/Zn(ii)]: a novel bionanocomposite for the synthesis of 1,2,4,5-tetrahydro-2,4-dioxobenzo[b][1,4]diazepine malononitriles and malonamides at room temperature and under sonication

In this work, a new magnetized composite of bismuth (Fe_3−xBi_xO₄) was prepared and functionalized stepwise with silica, triethylargininium iodide ionic liquid, and Zn(ii) to prepare a multi-layered core–shell bio-nanostructure, [Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii)]. The modified bismuth magnetic amino acid-containing nanocomposite was characterized using several techniques including Fourier-transform infrared (FT-IR), X-ray fluorescence (XRF), vibrating sample magnetometer (VSM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDAX), thermogravimetric/differential scanning calorimetric (TGA/DSC) analysis, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), and inductively coupled plasma-optical emission spectrometry (ICP-OES). The magnetized bionanocomposite exhibited high catalytic activity for the synthesis of 1,2,4,5-tetrahydro-2,4-dioxobenzo[b][1,4]diazepine malononitriles via five-component reactions between 1,2-phenylenediamines, Meldrum''s acid, malononitrile, aldehydes, and isocyanides at room temperature in ethanol. The efficacy of this protocol was also examined to obtain malonamide derivatives via pseudo six-component reactions of 1,4-phenylenediamine, Meldrum''s acid, malononitrile, aldehydes, and isocyanides. When the above-mentioned MCRs were repeated under the same conditions with the application of sonication, a notable decrease in the reaction time was observed. The recovery and reusability of the metal-bio functionalized bismuthmagnetite were examined successfully in 3 runs. Furthermore, the characteristics of the recovered Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii) were investigated though FESEM and EDAX analysis.

In this work, a new magnetized composite of bismuth (Fe_3−xBi_xO₄) was prepared and functionalized stepwise with silica, triethylargininium iodide ionic liquid, and Zn(ii) to prepare a multi-layered core–shell bio-nanostructure, [Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii)].     

Pyrolytic behavior of a zero-valent iron biochar composite and its Cu(ii) removal mechanism

The reduction behavior of Fe³⁺ during the preparation of a zero-valent iron cocoanut biochar (ZBC8-3) by the carbothermic reduction method was analyzed. Fe³⁺ was first converted into Fe₃O₄, which was subsequently decomposed into FeO, and finally reduced to Fe⁰. A minor amount of γ-Fe₂O₃ was produced in the process. The isothermal thermodynamic data for the removal of Cu(ii) over ZBC8-3 followed a Langmuir model. The Langmuir equation revealed a maximum removal capacity of 169.49 mg g⁻¹ at pH = 5 for ZBC8-3. The removal of Cu(ii) over ZBC8-3 fitted well to a pseudo-first-order equation, which suggested that the rate limiting step of the process was diffusion. The Cu(ii) removal mechanism on ZBC8-3 involved the reduction of Cu(ii) by Fe⁰ to produce Cu⁰ and Cu₂O, while C C, C–O–, and –O–H formed a complex with Cu(ii).

The Cu(ii) removal mechanism on ZBC8-3 involved the reduction of Cu(ii) by Fe⁰ to produce Cu⁰ and Cu₂O, while C C, C–O–, –O–H formed a complex with Cu(ii).