Electrochemical properties of yttrium on W and Pb electrodes in LiCl–KCl eutectic melts

Cyclic voltammetry, square wave voltammetry, linear polarization, chronopotentiometry and chronoamperometry were performed to investigate the electrochemical properties of Y(iii) on W and Pb electrodes in LiCl–KCl eutectic melts. The diffusion coefficient of Y(iii) measured by various techniques was in the order of 10⁻⁵. The nucleation of Y on W electrode was found to comply with the instantaneous nucleation mechanism. With increasing temperature, the exchange current densities increased and the charge-transfer resistances decreased, and exchange current densities are distinctly larger on liquid Pb electrode compared with W electrode. In addition, the co-deposition mechanism of Y(iii) and Pb(ii) on W electrode was also studied and four Pb–Y intermetallics could be detected. The feasibility of extraction metallic Y from the melts was explored by co-deposition on W electrode and under-potential deposition on liquid Pb electrode and the extracted products consisted of Pb₃Y and Pb phases.

Cyclic voltammetry, square wave voltammetry, linear polarization, chronopotentiometry and chronoamperometry were performed to investigate the electrochemical properties of Y(iii) on W and Pb electrodes in LiCl–KCl eutectic melts.     

Electrolytic extraction of dysprosium and thermodynamic evaluation of Cu–Dy intermetallic compound in eutectic LiCl–KCl

The electrochemical reduction of dysprosium(iii) was studied on W and Cu electrodes in eutectic LiCl–KCl by transient electrochemical methods. Cyclic voltammogram and current reversal chronopotentiogram results demonstrated that dysprosium(iii) was directly reduced to dysprosium (0) on the W electrode through a single-step process with the transfer of three electrons. Electrochemical measurements on the Cu electrode showed that different Cu–Dy intermetallics are formed. Moreover, the thermodynamic properties of Cu–Dy intermetallic compounds were estimated by open circuit chronopotentiometry in a temperature range of 773–863 K. Using the linear polarization method, the exchange current density (j₀) of dysprosium in eutectic LiCl–KCl on the Cu electrode was estimated, and the temperature dependence of j₀ was studied to estimate the activation energies associated with Dy(iii)/Cu₅Dy and Dy(iii)/Cu_9/2Dy couples. In addition, potentiostatic electrolysis was conducted to extract dysprosium on the Cu electrode, and five Cu–Dy intermetallic compounds, CuDy, Cu₂Dy, Cu_9/2Dy, Cu₅Dy and Cu_0.99Dy_0.01 were identified by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometry. Meanwhile, the change of dysprosium(iii) concentration was monitored using inductively coupled plasma-atomic emission spectrometry, and the maximum extraction efficiency of dysprosium was found to reach 99.2%.

The electrochemical reduction of dysprosium(iii) was studied on W and Cu electrodes in eutectic LiCl–KCl by transient electrochemical methods.     

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.     

Molecular dynamics simulations of Y(iii) coordination and hydration properties

Y mainly exists in ionic rare-earth resources. During rare-earth carbonate precipitation, rare-earth ion loss in the precipitated rare-earth mother liquor often occurs due to CO₃²⁻ coordination and Y(iii) hydration. Microscopic information on the coordination and hydration of CO₃²⁻ and H₂O to Y(iii) has not yet been elucidated. Therefore, in this study, the macroscopic dissolution of Y(iii) in different aqueous solutions of Na₂CO₃ was studied. The radial distribution function and coordination number of Y(iii) by CO₃²⁻ and H₂O were systematically analyzed using molecular dynamics (MD) simulations to obtain the complex ion form of Y(iii) in carbonate solutions. Density functional theory (DFT) was used to geometrically optimize and calculate the UV spectrum of Y(iii) complex ions. This spectrum was then analyzed and compared with experimentally determined ultraviolet-visible spectra to verify the reliability of the MD simulation results. Results showed that Y(iii) in aqueous solution exists in the form of [Y·3H₂O]³⁺ and that CO₃²⁻ is present in the bidentate coordination form. In 0–0.8 mol L⁻¹ CO₃²⁻ solutions, Y(iii) was mainly present as the 5-coordinated complex [YCO₃·3H₂O]⁺. When the concentration of CO₃²⁻ was increased to 1.2 mol L⁻¹, [YCO₃·3H₂O]⁺ was converted into a 6-coordinated complex [Y(CO₃)₂·2H₂O]⁻. Further increases in CO₃²⁻ concentration promoted Y(iii) dissolution in solution in the form of complex ions. These findings can be used to explain the problem of incomplete precipitation of rare earths in carbonate solutions.

Based on MD results, DFT was used to geometrically optimize and calculate the UV spectrum of Y(iii) complex ions. Data validation was further performed using UV-vis experiments to reveal Y(iii) coordination and hydration properties.     

In situ electrochemical investigation of the reaction progress between Zr and a CuCl–SnCl2 mixture in a LiCl–KCl molten salt

The electrochemical behaviors of CuCl, SnCl₂ and a CuCl–SnCl₂ mixture were investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV). The reduction potentials of Cu(i) and Sn(ii) on CV curves are −0.49 and −0.36 V, respectively, while the reduction potentials of Cu(i)–Sn(ii) in the CuCl–SnCl₂ mixture almost overlap. The co-chlorination reaction progress between CuCl–SnCl₂ and Zr was also studied by monitoring the concentration changes of Cu(i), Sn(ii) and Zr(iv) ions in situ by CV, SWV and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analyses. The results indicate that during the reaction, the concentration of Zr(iv) ions increases gradually, while those of Cu(i) and Sn(ii) decrease rapidly until they disappear. When the molar ratios of Cu(i) to Sn(ii) are 1 : 1 and 1 : 0.5, the reaction between Cu(i) and Zr is faster but cannot exceed twice that of Sn(ii) and Zr in a short time. When the theoretical product of ZrCl₄ is a constant, and with the proportion of CuCl to SnCl₂ decreasing from 1 : 0 to 0 : 1, the chlorination reaction time periods increase from 40 to 170 min. Chloride products such as Cu_xSn_y, Sn_xZr_y, and Cu_xZr_y, are formed with different molar ratios. The coupling effect caused by the formation of alloys will promote the chlorination reaction when the ratios of CuCl to SnCl₂ are 0.66 : 0.17 and 0.5 : 0.25. The results provide a theoretical basis for the electrolytic refinement of zirconium.

A LiCl–KCl–ZrCl₄ melt was prepared via a co-chlorination reaction between a binary mixture of CuCl–SnCl₂ and Zr, and the reaction progress was electrochemically monitored.     

Pu(iii) and Cm(iii) in the presence of EDTA: aqueous speciation,redox behavior,and the impact of Ca(ii)

The impact of calcium on the solubility, redox behavior, and speciation of the An(iii)–EDTA (An = Pu or Cm) system under reducing, anoxic conditions was investigated through batch solubility experiments, X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-resolved laser fluorescence spectroscopy (TRLFS). Batch solubility experiments were conducted from undersaturation using Pu(OH)₃(am) as the solid phase in contact with 0.1 M NaCl–NaOH–HCl–EDTA–CaCl₂ solutions at [EDTA] = 1 mM, pH_m = 7.5–9.5, and [CaCl₂] ≤20 mM. Additional samples targeted brine systems represented by 3.5 M CaCl₂ and WIPP simulated brine. Solubility data in the absence of calcium were well-described by Pu(iii)–EDTA thermodynamic models, thus supporting the stabilization of Pu(iii)–EDTA complexes in solution. Cm(iii)–EDTA TRLFS data suggested the stepwise hydrolysis of An(iii)-EDTA complexes with increasing pH, and current Pu(iii)-EDTA solubility models were reassessed to evaluate the possibility of including Pu(iii)–OH–EDTA complexes and to calculate preliminary formation constants. Solubility data in the presence of calcium exhibited nearly constant log m(Pu)_tot, as limited by total ligand concentration, with increasing [CaCl₂]_tot, which supports the formation of calcium-stabilized Pu(iii)–EDTA complexes in solution. XAS spectra without calcium showed partial oxidation of Pu(iii) to Pu(iv) in the aqueous phase, while calcium-containing experiments exhibited only Pu(iii), suggesting that Ca–Pu(iii)–EDTA complexes may stabilize Pu(iii) over short timeframes (t ≤45 days). DFT calculations on the Ca–Pu(iii)–EDTA system and TRLFS studies on the analogous Ca–Cm(iii)–EDTA system show that calcium likely stabilizes An(iii)–EDTA complexes but can also potentially stabilize An(iii)–OH–EDTA species in solution. This hints towards the possible existence of four major complex types within Ca–An(iii)–EDTA systems: An(iii)–EDTA, An(iii)–OH–EDTA, Ca–An(iii)–EDTA, and Ca–An(iii)–OH–EDTA. While the exact stoichiometry and degree of ligand protonation within these complexes remain undefined, their formation must be accounted for to properly assess the fate and transport of plutonium under conditions relevant to nuclear waste disposal.

Combined advanced spectroscopy and solubility studies provide evidence for the formation of novel calcium-containing and hydrolyzed (Cm,Pu)(iii)–EDTA complex(es).     

The effects of Sn content on the corrosion behavior and mechanical properties of Mg–5Gd–3Y–xSn–0.5Zr alloys

The effects of Sn content on the corrosion behavior and mechanical properties of Mg–5Gd–3Y–0.5Zr alloy were studied by SEM, EDS, XRD and electrochemical testing. Results show that Sn can refine the grain size and promote the precipitation of Mg₅(Gd,Y) phase. When the Sn content is 1.5–2 wt%, a needle-like Mg₂Sn phase will be precipitated in the alloy. Mg–5Gd–3Y–1Sn–0.5Zr alloy had the lowest corrosion rate, which is attributed to the barrier effect of the grain boundary and dispersed Mg₅(Gd,Y) phase on corrosion. However, the Mg₂Sn phase formed by excessive Sn addition will accelerate galvanic corrosion. At the same time, Mg–5Gd–3Y–1Sn–0.5Zr alloy had best mechanical properties. In 1.5Sn and 2Sn alloys, the cleavage effect of the needle-like Mg₂Sn phase on the matrix reduced mechanical properties.

The effects of Sn content on the corrosion behavior and mechanical properties of Mg–5Gd–3Y–0.5Zr alloy were studied by SEM, EDS, XRD and electrochemical testing. Results show that Sn can refine the grain size and promote the precipitation.     

Enhanced hydrogen storage properties of 1.1MgH2–2LiNH2–0.1LiBH4 system with LaNi5-based alloy hydrides addition

Significant improvements in the hydrogen sorption properties of the Li–Mg–N–H system have been achieved by adding a small amount of LiBH₄. Herein, the hydrogen storage properties of the 1.1MgH₂–2LiNH₂–0.1LiBH₄ system are further enhanced by addition of LaNi₅-based (LaNi_3.8Al_0.75Mn_0.45, LaNi_4.5Mn_0.5, LaNi₄Co) alloy hydrides. The refinement of the Li–Mg–B–N–H particles and the metathesis reaction are facilitated by adding LaNi₅-based alloy hydrides during the ball milling process. The addition of LaNi₅-based alloy hydrides can enhance the hydrogen sorption kinetics, reduce the dehydrogenation temperature and promote a more thorough dehydrogenation of the Li–Mg–B–N–H system. The LaNi₅-based alloy hydrides are involved in hydrogen de/hydrogenation reaction. Among the three alloys, LaNi_4.5Mn_0.5 makes the most obvious improvement on the reaction kinetics, and the dehydrogenation peak temperature is reduced by 12 °C, while the activation energy is reduced by 11% with 10 wt% LaNi_4.5Mn_0.5 addition. The weakening of the N–H bond and the homogeneous distribution of the LaNi₅-based alloy hydrides in the Li–Mg–B–N–H composite have important roles in the reduction of the desorption barrier and the kinetics enhancement.

The weakening of N–H bond and the homogeneous distribution of LaNi₅-based alloy hydrides in the Li–Mg–B–N–H composite enhance its hydrogen storage properties.     

Separation of iron(iii), zinc(ii) and lead(ii) from a choline chloride–ethylene glycol deep eutectic solvent by solvent extraction

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii). The selective extraction of iron(iii) and zinc(ii) was studied from a feed of ethaline (1 : 2 molar ratio of choline chloride : ethylene glycol) and lactiline (1 : 2 molar ratio of choline chloride : lactic acid), with the former DES being more selective. A commercial mixture of trialkylphosphine oxides (Cyanex 923, C923) diluted in an aliphatic diluent selectively extracted iron(iii) from a feed containing also zinc(ii) and lead(ii). The subsequent separation of zinc(ii) from lead(ii) was carried out using the basic extractant Aliquat 336 (A336). The equilibration time and the extractant concentration were optimized for both systems. Iron(iii) and zinc(ii) were stripped using 1.2 mol L⁻¹ oxalic acid and 0.5 mol L⁻¹ aqueous ammonia, respectively. An efficient solvometallurgical flowsheet is proposed for the separation and recovery of iron(iii), lead(ii) and zinc(ii) from ethaline using commercial extractants. Moreover, the process was upscaled in a countercurrent mixer-settler set-up resulting in successful separation and purification.

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii).     

Reduced graphene oxide/TiO2(B) nanocomposite-modified separator as an efficient inhibitor of polysulfide shuttling in Li–S batteries

The shutting effect in lithium–sulfur (Li–S) batteries hinders their widespread application, which can be restrained effectively by a modified separator. In this work, a composite of reduced graphene oxide and beta-phase TiO₂ nanoparticles (RGO/TiO₂(B)) is designed as a separator modification material for improving the electrochemical behavior of Li–S batteries. The TiO₂(B) nanoparticles are in situ prepared and tightly adhere to the RGO layer. A series of examinations demonstrated that the RGO/TiO₂(B)-coated separator efficiently inhibits the polysulfide shuttling phenomenon by the cooperative effect of physical adsorption and chemical binding. Specifically, as modified separators, a comparison between TiO₂(B) and anatase TiO₂(A) each composited with RGO has been conducted. The TiO₂(B) sample not only exhibits a superior blocking character of migrating polysulfides, but also enhances battery electrochemical kinetics by fast Li ion diffusion.

Beta-phase TiO₂ nanoparticles were adhered onto RGO in situ to fabricate a multi-functional separator for high-performance lithium–sulfur (Li–S) batteries.     

A stable Ln(iii)-functionalized Cd(ii)-based metal–organic framework: tunable white-light emission and fluorescent probe for monitoring bilirubin

A novel anionic Cd(ii)-based metal–organic framework, H₂[Cd₉(DDB)₄(BPP)₄(H₂O)₁₄]·4H₂O·2DMA (1), was successfully obtained with a rigid carboxylate ligand 3,5-di(2′,4′-dicarboxylphenyl)benzoic acid (H₅DDB) and a flexible pyridyl ligand 1,3-bis(4-pyridyl)propane (BPP). Complex 1 contains two-dimensional (2D) honeycomb structures and one-dimensional (1D) chain structures. The adjacent 2D structures are linked by strong intermolecular hydrogen bonds to form an ABAB 3D supramolecular structure, where the 1D chain structures traverse the channels of the 2D structures. Due to the anionic framework, Ln(iii) ions (Ln = Eu and Tb) can be encapsulated in the framework of 1 by a post-synthetic modification process to obtain Ln(iii)@1, where 1.09Eu(iii)@1 (1a) and 0.658Tb(iii)@1 (1b) can be obtained by soaking complex 1 in a Eu(NO₃)₃·6H₂O or Tb(NO₃)₃·6H₂O aqueous solution for 48 h. The liquid-state emission spectra of Ln(iii)@1 can be tuned to be a white light emission by changing the Eu(iii)/Tb(iii) molar ratio in solution. Moreover, 1b can be used as a “turn-off” fluorescent probe for bilirubin with a low detection limit of 0.250 μM in phosphate buffer solution (pH = 7.4), which presents excellent sensitivity, high selectivity, and reusability. Furthermore, the devised fluorescent probe in serum also exhibits the fluorescence “turn-off” process with a low detection limit of 0.279 μM, and the recovery rate of bilirubin is 99.20–101.9%. The possible mechanisms of the fluorescence “turn-off” process can be explained by resonance energy transfer, and the weak interaction between 1b and bilirubin.

A novel anionic Cd(ii)-based metal–organic framework was used toencapsulateLn(iii) ions, which exhibits tunable luminescence and selective sensing of bilirubin.     

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.     

Inner filter effect between upconversion nanoparticles and Fe(ii)–1,10-phenanthroline complex for the detection of Sn(ii) and ascorbic acid (AA)

Dual-function and multi-function sensors can use the same material or detection system to achieve the purpose of detection of two or more substances. Due to their high sensitivity and specificity, dual-function and multi-function sensors have potential applications in many fields. In this article, we designed a dual-function sensor to detect Sn(ii) and ascorbic acid (AA) based on the inner filter effect (IFE) between NaYF₄:Yb,Er@NaYF₄@PAA (UCNPs@PAA) and Fe(ii)–1,10-phenanthroline complex. Fe(ii)–1,10-phenanthroline complex has strong absorption in most of the ultraviolet-visible light range (350 nm–600 nm), and this absorption band overlaps with the green emission peak of UCNPs@PAA at 540 nm; Fe(ii)–1,10-phenanthroline complex can significantly quench the green light emission of UCNPs@PAA. When Sn(ii) or AA is added to the UCNPs@PAA/Fe(iii)/1,10-phenanthroline, they can reduce Fe(iii) to Fe(ii). Fe(ii) can react with 1,10-phenanthroline to form an orange complex, thereby quenching the green light emission of UCNPs@PAA. And the quenching efficiency is related to the concentration of Sn(ii) and AA; there is a linear relationship between quenching efficiency and the concentration of Sn(ii) and AA, within a certain concentration range the detection limits of this dual-function sensor for Sn(ii) and AA are 1.08 μM and 0.97 μM, respectively. In addition, the dual-function sensor can also detect Sn(ii) and AA in tap and spring water.

Based on the inner filter effect (IFE), we use UCNPs to develop a dual-function sensors, which can realize sensitive and selective detection for the Sn(ii) and ascorbic acid (AA).     

Effect of heat treatment on corrosion behavior of Mg–5Gd–3Y–0.5Zr alloy

The effects of different heat treatment processes on the microstructure and corrosion behavior of Mg–5Gd–3Y–0.5Zr (GW53K) magnesium alloy were studied by means of microanalysis, weight loss test and electrochemical test. The results show that appropriate heat treatment can improve the corrosion resistance of the alloy. Among the tested alloys, the T6-12 h alloy has the best corrosion resistance, which is mainly attributed to the morphology and distribution of the Mg-RE phase. The corrosion rate of the T4 alloy is similar to that of the T6-12 h alloy. The corrosion resistance of the T4 alloy may be reduced under long-term corrosion due to the existence of surface corrosion microcracks.

The effects of different heat treatment processes on the microstructure and corrosion behavior of Mg–5Gd–3Y–0.5Zr (GW53K) magnesium alloy were studied by means of microanalysis, weight loss test and electrochemical test.     

Nitrogen–sulfur dual-doped porous carbon spheres/sulfur composites for high-performance lithium–sulfur batteries

A nitrogen–sulfur dual-doped porous carbon spheres/sulfur composite (PCS-NS/S) sample was prepared by a simple hydrothermal method with starch and l-methionine as carbon and nitrogen–sulfur resources, respectively. XRD, XPS, and N₂ adsorption–desorption tests were used to characterize the crystal and pore structure of the PCS-NS/S sample. The morphology and weight ratio of sulfur were investigated by SEM, TEM, and TG analyses. The sample was used as the positive electrode for lithium–sulfur batteries and found to exhibit excellent electrochemical performance.

Simultaneously introduced nitrogen–sulfur through one reagent. The as-prepared PCS-NS/S composites exhibited excellent electrochemical performance as positive electrode for Li–S battery.     

Nanoscale iron (oxyhydr)oxide-modified carbon nanotube filter for rapid and effective Sb(iii) removal

Herein, nanoscale iron (oxyhydr)oxide-coated carbon nanotube (CNT) filters were rationally designed for rapid and effective removal of Sb(iii) from water. These iron (oxyhydr)oxide particles (<5 nm) were uniformly coated onto the CNT sidewalls. The as-fabricated hybrid filter demonstrated improved sorption kinetics and capacity compared with the conventional batch system. At a flow rate of 6 mL min⁻¹, a Sb(iii) pseudo-first-order adsorption rate constant of 0.051 and a removal efficiency of >99% was obtained when operated in the recirculation mode. The improved Sb(iii) sorption performance can be ascribed to the synergistic effects of convection-enhanced mass transport, limited pore size, and more exposed active sorption sites of the filters. The presence of 1–10 mmol L⁻¹ of carbonate, sulfate, and chloride inhibits Sb(iii) removal negligibly. Exhausted hybrid filters can be effectively regenerated by an electrical field-assisted chemical washing method. STEM characterization confirmed that Sb was mainly sequestered by iron (oxyhydr)oxides. XPS, AFS and XAFS results suggest that a certain amount of Sb(iii) was converted to Sb(v) during filtration. DFT calculations further indicate that the bonding energy for Sb(iii) onto the iron (oxyhydr)oxides was 2.27–2.30 eV, and the adsorbed Sb(iii) tends to be oxidized.

Herein, nanoscale iron (oxyhydr)oxide-coated carbon nanotube (CNT) filters were rationally designed for rapid and effective removal of Sb(iii) from water.     

Synthesis of heterometallic metal–organic frameworks and their performance as electrocatalyst for CO2 reduction

Herein we report the solventless synthesis and doping of the benchmark HKUST-1(Cu) as a facile route to afford heterometallic metal–organic frameworks (MOFs) having proficient behavior as electrocatalytic materials in the reduction of carbon dioxide. Zn(ii), Ru(iii) and Pd(ii) were selected as doping metals (M_D) with the aim of partially replacing the Cu(ii) atoms of the pristine structure to afford HKUST-1(Cu,M_D) type materials. Apart from the high yield and good crystallinity of the obtained materials, the extremely high reagent concentration that the reaction conditions imply makes it feasible to control dopant loading in all cases. Prepared samples were processed as electrodes and assembled in a continuous flow filter-press electrochemical cell. Faraday efficiency to methanol and ethanol at Ru(iii)-based electrodes resulted in activity as high as 47.2%, although the activity of the material decayed with time. The interplay of the dopant metal and copper(ii), and the long-term performance are also discussed.

The solventless synthesis of heterometallic metal–organic frameworks and their proficient behavior as electrocatalysts in the CO₂ reduction to alcohols is presented.     

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.     

“Off–On” fluorescent sensing of organophosphate pesticides using a carbon dot–Au(iii) complex

Herein, we report novel “off–on” fluorescent sensing of organophosphate pesticides using a carbon dot (CD)–Au(iii) complex/acetylcholinesterase (AChE) system. The above sensor utilizes the quenching of CD fluorescence by Au(iii) and its subsequent recovery by thiocholine, which is generated by AChE-catalyzed hydrolysis of acetylthiocholine (ATCh) and effectively scavenges Au(iii). In the presence of organophosphates, the catalytic activity of AChE is inhibited, allowing these species to be quantified based on the decreased recovery of CD fluorescence intensity. The developed sensor was used to analyze a real pesticide-spiked sample (4.48 μM), achieving a recovery of 99.85% and exhibiting a linear response range of 0.45–44.80 μM.

Herein, we report novel “off–on” fluorescent sensing of organophosphate pesticides using a carbon dot (CD)–Au(iii) complex/acetylcholinesterase (AChE) system.     

Computational insights into Ir(iii)-catalyzed allylic C–H amination of terminal alkenes: mechanism,regioselectivity, and catalytic activity

Computational studies on Ir(iii)-catalyzed intermolecular branch-selective allylic C–H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference. The result suggests that the reaction proceeds through generation of active species, alkene coordination, allylic C–H activation, decarboxylation, migratory insertion, and protodemetalation. The presence of AgNTf₂ could thermodynamically promote the formation of catalytically active species [Cp*Ir(OAc)]⁺. Both the weaker Ir–C(internal) bond and the closer interatomic distance of N⋯C(internal) in the key allyl-Ir(v)-nitrenoid intermediate make the migratory insertion into Ir–C(internal) bond easier than into the Ir–C(terminal) bond, leading to branch-selective allylic C–H amidation. The high energy barrier for allylic C–H activation in the Co system could account for the observed sluggishness, which is mainly ascribed to the weaker coordination capacity of alkenes to the triplet Cp*Co(OAc)⁺ and the deficient metal⋯H interaction to assist hydrogen transfer.

DFT studies on Ir(iii)-catalyzed branch-selective allylic C–H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference.