Search

CO2 electroreduction reaction (CO2RR) has been considered as an effective technology to close the anthropogenic carbon cycle. Formate, a product of two-electron transfer in CO2RR, is an economically valuable feedstock. In this work, nanoporous tin oxides were controllable synthesized by a facile and scalable electrochemical anodic oxidation method. XPS result indicated that the increased Sn4+ species after anodic oxidation were beneficial to reduce the overpotential of formate formation. Operando Raman spectra revealed that the enhanced formate selectivity could be attributed to the high local pH within the porous structure, which suppresses hydrogen evolution reaction (competing reaction against CO2RR). Further flow cell test showed a formate partial current density of 285 mA·cm−2 with the selectivity of 96.4%, indicating a promising industrial application prospect.

This work investigated the influence of introduction methods of cerium and tin on the physicochemical properties as well as the activity and durability of titanium-based catalysts for the selective catalytic reduction of NO by NH3 (NH3-SCR). Precipitation and impregnation methods were adopted to synthesize a series of cerium-tin-titanium catalysts. These catalysts were characterized by XRD, Raman, N2 adsorption–desorption, HRTEM, EDS mapping, XPS, H2-TPR, NH3-TPD and in situ DRIFT. Notably, Ce/Sn/Ti(imp) catalyst prepared by stepwise-impregnation method could provide an interface between Ce and Sn for more facile electron transfer than Sn/Ce-Ti(co), Ce/Sn-Ti(co) and Sn/Ce/Ti(imp) catalysts. It promoted the redox equilibrium of Ce4+ + Sn2+ ↔ Ce3+ + Sn4+ shifting to right to produce adequate Ce3+ and surface adsorbed oxygen, resulting in optimal reducibility and surface acidity of Ce/Sn/Ti(imp) catalyst. Besides, the activation of NH3 and desorption of NOx readily occurred on the surface of Ce/Sn/Ti(imp), which were favorable for the proceeding of subsequent reactions and excellent performance of NH3-SCR.

Animal hair is a useful biomonitoring tool for assessing the occurrence of trace elements in ecosystems. Essential (chromium, copper, iron, manganese, nickel, and zinc) and nonessential (aluminum, arsenic, cadmium, mercury, lead, palladium, platinum, rubidium, tin, and vanadium) elements were investigated in hair of badger (Meles meles), wild boar (Sus scrofa), marmot (Marmota marmota), wolf (Canis lupus), fox (Vulpes vulpes) and deer (Cervus elaphus) from Northwestern Italy. Badger was found to be the highest bioaccumulator of metals, while wolf, fox and deer recorded the lowest values. Essential elements contribute in higher degree to the sum of metals for all species except for wild boar. Results have shown that animals with omnivorous diet such as badger, marmot and wild boar have metal content (especially Al, As, Cr, Cu, Fe, Ni, V) higher than carnivores (wolf and fox) and herbivores (deer) and could represent an effective sentinel of environmental exposure to metals.

The introduction of tin (Sn) into Zn-based catalyst can change its intrinsic properties of the electrochemically reduction of CO2 to CO, obtaining a high formate yield. The electron transfer from Zn to Sn lowers down the d-band center of Sn, leading to a more reliable surface adsorption of the *OCHO intermediate and resulting high formate selectivity. The obtained ZnSn catalyst enables formate formation with a drastically boosted Faradaic efficiency (FE) up to 94%, which is 2.04 and 1.34 times of pure Zn and Sn foils, respectively, indicating a synergistic effect between Zn and Sn. During the electrochemical CO2 reduction reaction (eCO2RR) process, the morphology of the ZnSn catalyst evolved from nanoparticles to nanosheets, nanoneedles and collapsed structures, corresponding to the activation, stabilization and decay stages, respectively. This study provides a facile and controllable approach for the construction of novel bimetallic catalyst favoring formate selectivity based on the synergistic effect.

Existing data demonstrate a significant correlation between autism spectrum disorder (ASD) and the status of biologically essential and toxic trace elements. However, there is still a lack of data on the steady state of trace elements in ASD. We performed a case-control study to explore the association between the risk of ASD and 23 trace elements in plasma. The results showed that children with ASD had considerably decreased lithium (Li), manganese (Mn), selenium (Se), barium (Ba), mercury (Hg), and tin (Sn) levels when compared to their age- and sex-matched controls. Meanwhile, children with ASD had considerably increased plasma chromium (Cr) and vanadium (V) concentrations. We also divided each group into subgroups based on age and gender and created element-related networks for each subgroup. We detected significant element correlations within or between subgroups, as well as changes in correlations that included all elements examined. Finally, more element correlations were observed among males, which may open a new avenue for understanding the complicated process behind the sex ratio of children with ASD. Overall, our data revealed a novel relationship between elements and ASD, which may extend current understanding about ASD.

Organotin complexes are studied as promising alternatives to the anticancer drug cisplatin. We report two monoorganotin(IV) complexes based on a dibenzyl phosphinoyldithioformate (H-DBPTF) ligand, containing either bromide (Sn-DBPTF-1) or chloride (Sn-DBPTF-2) anions. The complexes were characterized by standard analytical techniques and the structural details of these complexes were elucidated by single crystal X-ray diffraction. Sn-DBPTF-1 was cytotoxic at IC

Addition of redox active/ inactive dopants often promotes the battery performance of any anode material. In this research work, we report the tin antimony (SnSb) alloy anodes included with three different dopants viz. Cu, Ti and Ce. The relative performances of these three different alloys have been systematically analyzed and reported. The electrochemical studies carried out by cyclic voltammetry analysis exhibit amplified redox activity and better reversibility of doped samples compared to the pristine. The specific capacitance values for 50 cycles are found to be in the range of 34 mAhg−1, 52 mAhg−1, 47 mAhg−1 and 65 mAhg−1 when tested with aqueous LiNO3 electrolyte solution for the pristine, Cu, Ti and Ce doped SnSb alloys respectively. The room temperature AC Impedance analyses of these samples reveal the augmented electrical conductivities of the doped samples. Overall, SnSb: Cu and SnSb: Ce samples are found to offer better anodic properties compared to the other samples.

A series of different aryl-linked (frustrated) Lewis pairs with perfluoroethylsilyl and -stannyl functions as Lewis acids has been prepared. The 1,2-phenylene linked tin/phosphorus Lewis pair with a di-tert-butylphosphanyl unit as base shows a strong intramolecular donor-acceptor interaction, but still readily adds hydrogen chloride. At the same time, the analogous silicon/phosphorus Lewis pair could not be obtained due to the decomposition of at least one perfluoroethyl group. With a sterically more demanding 2,2,6,6-tetramethylpiperidine base, stable Lewis pairs could be obtained for both, silicon and tin. However, they do not show activity in small molecule activation with H-2, phenyl isocyanate, CS2 or SO2. Furthermore, 2-benzyl-linked tin/nitrogen and silicon/phosphorus Lewis pairs were synthesized. Studies on their reactions towards small molecules did not show any reactivity, probably caused by an unfavorable preorganization due to rotation of the benzyl position.

This is the third concluding part of a series of reviews devoted to the direct synthesis of organotin compounds. This review considers conditions and results of the interaction between metallic tin and carbofunctional organohalogenides. Efficiency of the catalysts application and advantages of the direct synthesis for the production of carbofunctional organotin compounds are analyzed.

A tin(II) complex coordinated by a sterically demanding o-phenylenediamido ligand is synthesized. The ligand is redox-active to reach a tin(II) complex with the diiminobenzosemiquinone radial anion in the oxidation by AgPF6. The tin(II) complex reacts with a series of nosylazides (x-NO2C6H4-SO2-N3; x = o, m, or p) at -30 °C to yield the corresponding nitrene radical bound tin(II) complexes. The nitrene radical complexes exhibit C(sp3)-H activation and amination reactivity.

The progress of tin-based halide perovskite solar cells (Sn-HaPSCs) is obstructed by their poor stability arising from tin oxidation. Herein, we introduced phenethylammonium thiocyanate (PEASCN) as...

Efficient and environmentally friendly tin leaching methods are of significant interest for the separation and recovery of tin from various materials such as tin-plated scraps and waste printed circuit boards. In this study, we investigated the oxidative dissolution of metallic tin in an alkaline solution. A pure tin specimen was leached at 30 °C using different oxidizing agents in a 1 M sodium hydroxide solution. The results demonstrated that iodate ion (IO3−) is one of the most effective oxidizing agents for dissolving tin in alkaline media. A fundamental mechanism for tin dissolution into the leaching solution containing IO3− is proposed based on electrochemical measurements. In addition to the rapid dissolution of tin without much heating, the benefits of using IO3− as an oxidizing agent include its electrochemical regenerability. Thus, alkaline leaching using IO3− as an oxidizing agent is a potentially efficient technique for separating and recovering tin.

The therapeutic potential of the Meitner-Auger- and conversion-electron emitting radionuclide 119Sb remains unexplored because of the difficulty of incorporating it into biologically targeted compounds. To address this challenge, we report the development of 119Sb production from electroplated tin cyclotron targets and its complexation by a novel trithiol chelate. The chelation reaction occurs in harsh solvent conditions even in the presence of large quantities of tin, which are necessary for production on small, low energy (16 MeV) cyclotrons. The 119Sb-trithiol complex has high stability and can be purified by HPLC. The third generation trithiol chelate and the analogous stable natSb-trithiol compound were synthesized and characterized, including by single-crystal X-ray diffraction analyses.

The interaction of isomeric dinitrobenzenes (DNBs) with titanium(III), tin(II), and vanadium(II) chlorides, which are reducing agents used as electron carriers in the electrosynthesis of diaminobenzenes, has been studied. Rate constants of the reduction of isomeric DNBs and nitrophenylhydroxylamines by SnCl2 and TiCl3 in a 2 M water-alcohol solution (10 vol.% C2H5OH) of HCl were measured, and activation energies of the reduction of isomeric DNBs were determined. The rates of interaction of DNBs with the listed mediators increase in the series SnCl2 < TiCl3 < VCl2. It is shown that the electrolysis of DNBs in the presence of an excess of these mediators makes it possible to obtain the corresponding diaminobenzenes with a yield of 60–90%.

Two alkali tin(II) phosphates, namely, Rb[SnF(HPO4)] and Rb(Sn3O)2(PO4)3, were synthesized through mild hydrothermal methods. They belong to the orthorhombic Pnma and Pbcn space groups, respectively. Rb[SnF(HPO4)] features a layered structure based on 1D [SnF(HPO4)]∞ chains interconnected by hydrogen bonds, with Rb+ cations located at the interlayer space. For Rb(Sn3O)2(PO4)3, each pair of [Sn3O]4+ clusters is bridged by a pair of [P(1)O4]3- tetrahedra to build a 1D [Sn-P-O]∞ chain. These 1D [Sn-P-O]∞ chains are further cross-linked though [P(2)O4]3- tetrahedra to construct a 3D network with 7- and 10-membered-ring channels. The tin(II) ions in Rb[SnF(HPO4)] and Rb(Sn3O)2(PO4)3 with stereochemically active lone pairs (SCALPs) significantly enhance the birefringences of metal phosphates: Δn = 0.147@1064 nm for Rb[SnF(HPO4)] and 0.082@1064 nm for Rb(Sn3O)2(PO4)3.

Two robust Sn(IV)-porphyrin-based supramolecular arrays (1 and 2) were synthesized via the reaction of trans-Pd(PhCN)2Cl2 with two precursor building blocks (SnP1 and SnP2). The structural patterns in these architectures vary from 2D to 3D depending on the axial ligation of Sn(IV)-porphyrin units. A discrete 2D tetrameric supramolecule (1) was constructed by coordination of {(trans-dihydroxo)[5,10-bis(4-pyridyl)-15,20-bis(phenyl) porphyrinato]}tin(IV) (SnP1) with trans-PdCl2 units. In contrast, the coordination between the {(trans-diisonicotinato)[5,10-bis(4-pyridyl)-15,20-bis(phenyl)porphyrinato]}tin(IV) (SnP2) and trans-PdCl2 units formed a divergent 3D array (2). Axial ligation of the Sn(IV)-porphyrin building blocks not only alters the supramolecular arrays but also significantly modifies the nanostructures, including porosity, surface area, stability, and morphology. These structural changes consequently affected the photocatalytic degradation efficiency under visible-light irradiation towards acid orange 7 (AO) dye in an aqueous solution. The degradation efficiency of the AO dye in the aqueous solution was observed to be between 86% to 91% within 90 min by these photocatalysts.

PtSn catalysts were synthesized by incipient-wetness impregnation using a dendritic mesoporous silica nanoparticle support. The catalysts were characterized by XRD, N2 adsorption–desorption, TEM, XPS and Raman, and their catalytic performance for propane dehydrogenation was tested. The influences of Pt/Sn ratios were investigated. Changing the Pt/Sn ratios influences the interaction between Pt and Sn. The catalyst with a Pt/Sn ratio of 1:2 possesses the highest interaction between Pt and Sn. The best catalytic performance was obtained for the Pt1Sn2/DMSN catalyst with an initial propane conversion of 34.9%. The good catalytic performance of this catalyst is ascribed to the small nanoparticle size of PtSn and the favorable chemical state and dispersion degree of Pt and Sn species.

Anatase/rutile heterojunctions were prepared using the sol–gel method and modified by La/Sn single doping and co-doping. Sn doping promoted the transformation from anatase to rutile, while La doping inhibited the phase transformation. La and Sn co-doping showed an inhibitory effect. The co-doping of La and Sn did not increase visible-light absorption, but exhibited a synergistic effect on inhibiting the recombination of photogenerated electrons and holes, which improved the photocatalytic activity on the basis of single-element modification. The first-order reaction rate constant of La/Sn co-doped sample was 0.027 min−1, which is 1.8 times higher than that of pure TiO2 (0.015 min−1). Meanwhile, the mechanism of photodegradation of methylene blue (MB) by La/Sn co-doped anatase/rutile heterojunctions was discussed through electrochemical measurements and free-radical trapping experiments.

The aryl(imino)stannylene MesTer[N(IDipp)]Sn could be obtained by treating NHILi (NHI=N(IDipp), IDipp=C[N‐(2,6‐iPr2C6H3)CH]2) with MesTerSnCl (MesTer=2,6‐Mes2C6H3) and offers a unique reactivity pattern compared to conventional single site tetrylene catalyzed CO2 reduction reactions. The Sn(II) center, stabilized by the NHI ligand enabled the sequestration and valorization of CO2 to C1 feedstock stoichiometrically, as well as catalytically, utilizing HBpin (pin=pinacolato) as reductant. The experimental comparison with aryl(amido)stannylene MesTer(NPh2)Sn and aryl(phosphinidene)stannylene MesTer[P(IDipp)]Sn, as well as computational analysis, rationalize the electronic features and key role of the NHI ligand in the CO2 reduction process. In case of the phosphorus congener, Sn−P bonding with pronounced double‐bond character is obtained, which prevents swift dissociation, thus preventing CO2 uptake. Instead, hard/soft mismatch between tin and the NHI induces zwitterionic and single‐bond character, switching on the intermediate dissociation of Sn(II)/NHI, followed by a tin hydride mediated reduction step, and thus allows for efficient catalysis under mild conditions.

Metal-organic frameworks (MOFs) and coordination polymers composed of thiolates as coordinating functional groups are interesting materials with unique optical and electronical properties. Herein, we report the preparation of KGF-4 and KGF-10, two Sn-MOF crystal structures with bonds between Sn and thiolate. KGF-10 was isolated as a pure phase and found to exhibit redox properties and a semiconducting band structure, as confirmed by first-principles (density functional theory) calculations.

A layered semiconductor, SrTiN2, has an interesting crystal structure as a two-dimensional (2D) electron system embedded in a three-dimensional bulk periodic structure because it has alternate stacking of a SrN blocking layer and a TiN conduction layer, in which the Ti 3dxy orbital forms the conduction band minimum (CBM) similar to the SrTiO3-based thin-film heterostructure. However, SrTiN2 has been reported to exhibit nearly degenerate conduction, but we reported that it would be due to the easy formation of nitrogen vacancies and oxygen impurities from air. In this paper, we extend the materials to family compounds, alkaline earth (AE) ion-substituted, AETiN2 (AE = Ca, Sr, and Ba), and investigated how we can suppress the defect formation by (hybrid) density functional theory calculations. All AETiN2 compounds possess thermodynamic stability in the wide nitrogen (N) chemical potential window. Especially, CaTiN2 is the most stable even against N-poor conditions. Unintentional carrier generation occurs due to the nitrogen vacancies (VN), oxygen substitution (ON), and hydrogen anion substitution (HN) at the nitrogen sites. The VN and HN impurities can be suppressed under N-moderate and N-rich conditions. The ON defect is easily formed in SrTiN2 and also in BaTiN2 under N-rich conditions, but its formation can be suppressed in CaTiN2. Present results suggest that high-purity CaTiN2 can be obtained under wider N chemical conditions, which would lead to the realization of the novel functional properties originating from Ti 3dxy 2D bands embedded in the bulk crystal structure.

application/pdf, European Journal of Inorganic Chemistry. 2021, 2021 (25), P.2539-2545

The results of development of physicochemical fundamentals for the synthesis and deep purification of tin tetrachloride have been described. The samples of SnCl4 have been prepared from elements in a specially designed quartz installation. Prepared SnCl4 has been purified by rectification on a perforated-plate column. It has been revealed by mass spectrometry that the content of lead admixture after SnCl4 rectification decreases from 120 to 2 ppm, and the content of admixtures of other metals decreases considerably. Separation factors in liquid–vapor system for hardly separable admixtures have been calculated. The purity of SnCl4 samples has been confirmed by IR and Raman spectroscopy. The prepared SnCl4 samples contained 10–4 wt % of admixtures.

Density and thermal expansion coefficient of metals are fundamental characteristics to describe the equation of state. Especially for liquid metals, the reported data for density and thermal expansion coefficient vary in the literature, even at ambient pressure. To determine the density of solid and liquid metals precisely at high temperatures and ambient pressure, we have developed a high-temperature furnace. The densities of solid Sn, Ni, and Fe were determined from the sample image with an uncertainty of 0.11–0.7% in the temperature range of 285–1803 K with increments of 1–10 K. The density of solid Sn decreased linearly with increasing temperature up to 493 K, and then the decrease became drastic until the melting temperature (Tm) was reached. By contrast, for solid Ni and Fe, the densities decreased linearly with increasing temperature up to the Tm (1728 and 1813 K) without any drastic density drop near Tm. This suggests that Ni and Fe do not exhibit the “premelting effect.” The density of liquid Fe was determined with an uncertainty of 0.4–0.7% in the range of 1818–1998 K with temperature increments of 5 K. The obtained thermal expansion coefficient (α) of liquid Fe was well approximated as either a constant value of α = 2.42(1) × 10–4 K–1 or a linear function of temperature (T); α = 1.37(10) × 10–3 – [6.0(6) × 10–7]T [K–1] up to at least 2000 K.

This study presents a brief account of the synthesis, spectroscopic and biochemical aspects of tetraazamacrocyclic complexes of managenese (II) and tin (II). The complexes of manganese (II) and tin (II) were prepared by the template condensation of metal salts with phthalic acid and diamines (1,3-diaminobutane and 1,4- diaminobutane) in 1:2:2 molar ratio. All the complexes are soluble in polar solvent. The structures were investigated using elemental analyses, molecular weight determinations, conductivity measurements, electronic, infrared and X-Ray diffraction spectral studies. The elemental analyses are consistent with the formation of complexes of the type [M(Macn)Cl2] (where, n=1-2, M=Mn(II), Sn (II)). An octahedral geometry around the metal ion is suggested for these complexes. All the complexes were screened against several fungi and bacteria to assess its biological properties and results are discussed.The importance of this method includes shorter reaction time and high yield.

The use of an amino-functionalized β-diketiminate (′N-nacnac′) ligand in low-valent silicon chemistry is investigated. In particular, the use of (LDipp)SiCl (LDipp=HC{(Me2N)CNDipp}2) to generate silicon-containing products via metathesis chemistry is explored, in light of previously reported complications arising from heterocycle ring contraction. In the case of Na[C5H5], chloride metathesis is accompanied not by rearrangement of the N-nacnac ligand, but by a C-to-Si hydrogen migration process, generating the hydridosilicon(IV) species (LDipp)Si(H)(C5H4), which features a silafulvene core. The potential intermediate arising from initial chloride/cyclopentadienide substitution can be modelled by the chemistry of the corresponding Ge(II) and Sn(II) systems, which generate (LDipp)E(η1−C5H5) (E=Ge, Sn) via straightforward metathesis chemistry. A Si(II) hydride species can be generated from (LDipp)SiCl via metathesis by making use of a d-block reagent which can act as both hydride source and coordinative trap for (LDipp)SiH. Thus, the reaction of (LDipp)SiCl with K[(η5−C5H4Me)Mn(CO)2H] leads to the formation of (η5−C5H4Me)Mn(CO)2{Si(H)LDipp} – the first silylene complex containing this half-sandwich manganese fragment.