Sn Bond Research Articles

Degradation of sulfamethoxazole in a falling film dielectric barrier discharge system: Performance, mechanism and toxicity evaluation

The ubiquitous presence of sulfonamides (SAs) in wastewater poses serious risks to human health and ecosystem safety. This study evaluated the performance of a falling film dielectric barrier discharge (DBD) system on the removal of five SAs, namely sulfamethoxazole (SMX), sulfisoxazole (SIZ), sulfathiazole (STZ), sulfadiazine (SDZ) and sulfamerazine (SMR). Removal efficiencies >99 % were observed for all target SAs within 30 min of treatment, with pseudo-first order rate constants varying between 0.17 and 0.27 min−1. Superior removal efficiencies were achieved under acidic conditions compared to neutral and alkaline conditions. Using SMX as a model compound, mechanistic investigations revealed that the synergy of reactive oxygen species (ROS) and reactive nitrogen species (RNS) led to its efficient degradation, with peroxynitrites (ONOO−/ONOOH) and hydroxyl radical (OH) playing pivotal roles. SMX degradation pathways encompassing nitration/nitrosation, hydroxylation, deamination, CS and SN bond cleavage were proposed. The toxicity evaluation results demonstrated that the solution toxicity diminished following the plasma treatment under specific conditions. In particular, the solution treated with air or oxygen discharge enhanced the growth of wheat seedlings, suggesting the potential for reusing plasma-treated wastewater in agriculture. This study enhances our understanding of the underlying mechanisms involved in the plasma degradation of SAs and reveals the significant potential of plasma technology as a sustainable approach for treating wastewater.

The curious case of S4N4 − A reinvestigation

This work employs quantum chemical methods to explore electronic properties and bonding of the S4N4 molecule. We utilized calculations of multidimensional off-nucleus magnetic shielding, anisotropy of the induced current density (ACID), natural bond orbitals (NBOs), and atoms in molecules (AIM). The unique S4N4 system comprises bent bonding, absence of NN, weakness in the centers of SS bonds, and polar SN bonds. Our findings uncover coexisting of both electron localization and delocalization in S4N4. The magnetic analysis discloses curved connections between the nitrogen atoms and the SS bonds, drawing possible electron delocalization pathways as two pyramid-like regions of magnetic activity. Our magnetic calculations were performed at DFT/GIAO-B3LYP using Jorge-TZP-DKH and 6-311++G(2d,2p) basis sets. No remarkable qualitative differences were noticed between the obtained magnetic features from these two basis sets. Capturing the magnetic details associated with structural features shows superiority of ZZ component of the magnetic shielding tensor (σzz(r)) over the isotropic magnetic shielding (σiso(r)).

First-principles study of phase-dependent carrier transport mechanism for MASnI3 Sn-based halide perovskite

Organic-inorganic hybrid perovskites have attracted tremendous attentions owing to their excellent properties as next-generation photovoltaic devices. With soft covalent framework, organic-inorganic hybrid perovskites exhibit different phases at different temperatures. The band-edge features of perovskites are mainly contributed by inorganic framework, which means the structural differences between these phases would lead to complex carrier transport. We investigated the carrier transport of Sn-based organic-inorganic hybrid perovskite CH3NH3SnI3 (MASnI3), considering acoustic deformation potential scattering, ionized impurity scattering, and polar optical phonon scattering. It is found that the electron mobility of each phase of MASnI3 is strongly correlated with the Sn–I–Sn bond angle and there is in-plane/out-of-plane anisotropy. The projected crystal orbital Hamilton population analysis suggested that the tilt and rotation of the [SnI6]4− octahedron influence the Sn(p)–I(p) orbital electron coupling and the electron transport, leading to different band-edge features in multiple phases. The carrier mobility with respect to temperature was further calculated for each phase of MASnI3 in respective temperature intervals, showing lower carrier mobility in high temperature. Comparing the contribution of different scattering mechanisms, it was found that the dominant scattering mechanism is polar optical phonon scattering, while multiple scattering mechanisms compete in individual cases.

Visible Light Catalyzed Stannylation of Aryl Halides

AbstractA visible light‐mediated strategy for the preparation of aromatic stannanes from aryl halides (mostly aryl bromides) is presented herein. The reaction proceeds under metal‐ and additive‐free conditions and exhibits a broad substrate scope. The products obtained have been employed in the C−C bond formation via Stille cross‐coupling reactions. Mechanistic investigation evidenced the key role of both aryl radical and trimethylstannyl radical in Ar−Sn bond formation.

A tin analogue of propadiene with cumulated C[double bond, length as m-dash]Sn double bonds.

The synthesis, structure, and properties of a stable, linear 2-stannapropadiene are reported. The identical C[double bond, length as m-dash]Sn bonds in this 2-stannapropadiene are the shortest hitherto reported C-Sn bonds. This 2-stannapropadiene features a 119Sn NMR signal at 507 ppm for the central tin atom, indicative of an unsaturated Sn4+ oxidation state. Due to the inert-pair effect, the tin atom displays a pronounced preference for the +2 oxidation state over the +4 oxidation state. Nevertheless, by employing silyl substituents, it is possible to disrupt the inert-pair effect, leading to the formation of an isolable 2-stannapropadiene with a linear structure centered on a Sn4+ atom. Treatment of this 2-stannapropadiene with SnBr2·dioxane resulted in the formation of a novel four-membered cyclic 1,1-dibromo-1,3-distannetane, which was subsequently reduced to afford the corresponding stable four-membered cyclic bis(stannylene).

Controllable single phase enables superior thermal stability in Sb-Sn-S films

Sb-Sn-S thin films were prepared by magnetron sputtering, and the effects of the SnS content on the macroscopic performance and microstructure of Sb were investigated. Results show that Sb55(SnS)45 exhibited the best performance, with a crystallization temperature of 210 °C, solving the issue of spontaneous Sb crystallization. However, the thermal stability of Sb37(SnS)63 film could no longer be significantly improved. The investigated crystallization mode revealed that Sb55(SnS)45 exhibited a growth-dominated crystallization behavior, maintaining a high crystallization rate while substantially improving the thermal stability. In terms of the microstructure, high-energy Sb–S and Sb–Sn bonds were formed, breaking the originally unstable Sb–Sb bonds. In the case of Sb37(SnS)63, the internal Sb–S and Sb–Sn bonding environment reached a saturation state, and the excessive introduction of SnS resulted in the stacking arrangement of the Sb–Sn–S amorphous alloy, leading to lattice distortion. However, an appropriate amount of Sb–Sn–S amorphous alloy polymerized around the SbSn grains, limiting the grain growth and the element segregation, thereby enhancing the long-term stability of the phase-change thin film.

A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene

Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Herein, we report the synthesis of a silylene-stabilized ditin(0) complex (2) by reduction of a silylene-supported dibromostannylene (1) with 1 equivalent of magnesium (I) dimer in toluene. The structure of 2 was established by single crystal X-ray diffraction analysis. Density Functional Theory calculations revealed that complex 2 bears a Sn=Sn double bond and one lone pair of electrons on each of the Sn(0) atoms. Remarkably, complex 2 is readily methylated to give a mixed-valent methylditin cation (4), which undergoes topomerization in solution though a reversible 1,2-Me migration along a Sn=Sn bond. Computational studies showed that the three-coordinate Sn atom in 4 is the dominant electrophilic center, and allows for facile reaction with KHBBus3 furnishing an unprecedented N-heterocyclic silylenes-stabilized distannavinylidene (5). The synthesis of 2, 4 and 5 demonstrates the exceptional ability of N-heterocyclic silylenes to stabilize low valent tin complexes.

Trends in ionization energies for group 14 catenates and influence of substituent nature on them

Adiabatic ionization energies for a series of acyclic and cyclic compounds containing M–M and M=M (M = C, Si, Ge, and Sn) bonds were calculated using DFT-TPSS/D3/def2-TZVPP and DFT-PBE0-DH/def2-TZVPP. Their changes when moving down group 14, as well as the influence of the substituent nature on them, were discussed.

Atomically Dispersed Sn Confined in FeS2 for Nitrate‐to‐Ammonia Electroreduction

AbstractElectrocatalytic NO3− reduction to NH3 (NO3RR) is an efficient strategy to simultaneously mitigate NO3− contamination and produce sustainable NH3. Herein, atomically dispersed Sn confined in FeS2 (Sn‐FeS2) is reported as an effective and robust NO3RR catalyst, achieving a maximum NH3‐Faradaic efficiency of 96.7% with a corresponding NH3 yield rate of 15.8 mg h−1 cm−2, along with an excellent catalytic stability. Atomic coordination characterizations of Sn‐FeS2 unravel that single‐atomic Sn bonds with the surrounding Fe atoms to construct the unique p‐d hybridized Sn‐Fe pair sites. Combining theoretical investigations and operando spectroscopic measurements unveil that Sn‐Fe pair sites can synergistically promote the NO3− activation and N═O bond dissociation, accelerate the protonation energetics of NO3−‐to‐NH3 pathway and suppress the competing hydrogen evolution, eventually drastically enhancing the NO3RR activity and selectivity.

Structural, Spectroscopic, and Bonding Analyses of La(III)/Ce(III)-Tetrel Ate-Complexes.

In comparison with the research of transition-metal-tetrel complexes, the chemistry of lanthanide tetrel complexes, especially for these bearing heavier tetrel element ligands, is still relatively underexplored. In this research, K[Cp3Ln(III)CH2Ph], [(DME)3Li][Cp3Ln(III)GePh3], and [(DME)3Li][Cp3Ln(III)SnPh3] [Ln(III) = La(III), Ce(III)] have been synthesized by reacting [(DME)3Na][Cp3La(μ-Cl)LaCp3] or Cp3Ce(THF) with alkali metal alkyl, germyl, and stannyl reagents. Additionally, [(DME)3Li][Cp3Ce(III)SnPh3] is the first example of Ce(III)-Sn bond containing complex. All the obtained early Ln(III) tetrel ate-complexes were structurally analyzed by single-crystal X-ray diffraction. The formal shortness ratios of the Ln(III)-C, Ln(III)-Ge, and Ln(III)-Sn bonds are in the range of 1.03-1.11. Together with the previously reported [(DME)3Li][Cp3Ln(III)SiPh3], a group of tetrel (up to Sn) lanthanocene ate-complexes with an analogous coordination pattern are presented. Computational studies suggest the strongly polarized nature of the Ln(III)-E (E = C, Si, Ge, Sn) bonds in these complexes, with 77-85% atomic orbital contribution from tetrel elements and 15-23% atomic orbital contribution from Ln(III). The UV-vis measurements of this series of complexes show that the characteristic absorptions are hypsochromically shifted for Ln(III) heavier tetrel complexes in comparison to their lighter congeners. Moreover, the HOMOs, in which the Ln(III)-E σ-bonding orbitals are the dominant components, of these series complexes act as donor orbitals of the major electron transitions, as being disclosed by the time-dependent density functional theory analysis.

In-situ non-destructive removal of tin particles by low-energy plasma for imitation of EUV optical mirrors self-cleaning

In this study, the feasibility was explored of realizing in-situ and non-destructive self-cleaning of the multilayers mirror (MLM) by utilizing hydrogen plasma at low input power (<10 W). The hydrogen plasma generated by the electrode at low power was comprehensively diagnosed using the Langmuir probe and the retarding field ion energy analyzer (RFEA). Meanwhile, the ion concentration ratios and atomic density in hydrogen plasma were calculated by constructing a zero-dimensional plasma chemical model. These experimental results show that the plasma distribution at 1 W is more uniform than that at 10 W, and the peak ion energy at 1 W is lower than 22 eV. Cleaning rates of 0.3–0.75 nm min−1 are achieved to remove discontinuous tin particles at different powers. According to the experiment and calculation results, the chemical etching of ions (breaking the Sn–Sn bond) occurred at 1 W. The etching yield is 0.23–0.87 Sn/ion for 10–40 eV. The analysis of surface morphology and cross-sectional morphology shows that the removal of tin particles is realized by top-down cleaning with hydrogen plasma at low power. This study is of great significance for understanding the detailed mechanism of MLM self-discharge cleaning tin pollutants at low power. It has made a comprehensive calculation and diagnosis of plasma parameters.

Oxygen Storage by Tin Oxide Monolayers on Pt3Sn(111)

The high performance of platinum–tin catalysts for oxidation reactions has been linked to the formation of tin oxides at the metal surface, but little is known about the structure of these oxides or the chemical behavior that determines their catalytic properties. We show here how surface oxides on Pt3Sn(111) incorporate oxygen at the metal interface, which may be subsequently removed by reaction with CO. The storage mechanism, where oxygen uptake occurs without loss of interfacial Pt–Sn bonds, is enabled by the peculiar asymmetrical coordination state of Sn2+. O atoms are bound at pocket sites in the 2D oxide sheet between these outward-buckled Sn atoms and metallic Sn in the alloy surface below.

Directed Dehydration of Na4Sn2S6 ⋅ 5H2O Generates the New Compound Na4Sn2S6: Crystal Structure and Selected Properties

AbstractThe new thiostannate Na4Sn2S6 was prepared by directed crystal water removal from the hydrate Na4Sn2S6 ⋅ 5H2O at moderate temperatures. While the structure of the hydrate comprises isolated [Sn2S6]4− anions, that of the anhydrate contains linear chains composed of corner‐sharing SnS4 tetrahedra, a structural motif not known in thiostannate chemistry. This structural rearrangement requires bond‐breakage in the [Sn2S6]4− anion, movements of the fragments of the opened [Sn2S6]4− anion and Sn−S−Sn bond formation. Simultaneously, the coordination environment of the Na+ cations is significantly altered and the in situ formed NaS5 polyhedra are joined by corner‐ and edge‐sharing to form a six‐membered ring. Time‐dependent in situ X‐ray powder diffraction evidences very fast rehydration into Na4Sn2S6 ⋅ 5H2O during storage in air atmosphere, but recovery of the initial crystallinity requires several days. Impedance spectroscopy demonstrates a mediocre room‐temperature Na+ ion conductivity of 0.31 μS cm−1 and an activation energy for ionic transport of Ea=0.75 eV.

Structure and 119Sn Mössbauer-spectroscopic characterization of BaRhSn2

Abstract The stannide BaRhSn2 was synthesized by induction melting of an arc-melted RhSn2 precursor compound with barium in a sealed tantalum ampoule. The structure of BaRhSn2 was refined from single-crystal X-ray diffractometer data: MgCuAl2 type, Cmcm, a = 437.56(4), b = 1242.35(10), c = 767.30(6) pm, wR2 = 0.0845, 469 F 2 values and 16 variables. The rhodium and tin atoms form a two-dimensional [RhSn2] δ− polyanionic network with short Rh–Sn (273–274 pm) and Sn–Sn (303–312 pm) distances. The large barium atoms lead to a substantial orthorhombic distortion of the (lonsdaleite-related) tin substructure, forcing a break of the Sn–Sn bond in b direction. This change in the tin substructure is reflected in the 119Sn Mössbauer spectrum. The tin atoms exhibit a higher s electron density which is expressed in an increased isomer shift of δ = 2.08(1) mm s−1 as compared to the previously reported stannide CaRhSn2 with a three-dimensional [RhSn2] δ− polyanionic network and δ = 1.96(4) mm s−1.

Co3O4@SnO2/graphdiyne type-II heterojunction and p–n heterojunction jointly enhance photocatalytic hydrogen production: Co–O–Sn bond as a bridge for electron transfer

Various characterization methods were used to study the photocatalytic reaction mechanism of Co3O4@SnO2/GDY composite photocatalysts. The interface Co–O–Sn bond acts as a bridge for photogenerated electron transfer, whilst GDY promotes charge transfer and enables efficient H2 production.

Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E-H bonds (E = B, Si, Ge, Sn) using deuterium gas.

A series of ruthenium nanoparticles (Ru·MIC) stabilized with different mesoionic 1,2,3-triazolylidene (MIC) ligands were prepared by decomposition of the Ru(COD)(COT) (COD = 1,5-cyclooctadiene; COT = 1,3,5-cyclooctatriene) precursor with H2 (3 bar) in the presence of substoichiometric amounts of the stabilizer (0.1-0.2 equiv.). Small and monodisperse nanoparticles exhibiting mean sizes between 1.1 and 1.2 nm were obtained, whose characterization was carried out by means of transmission electron microscopy (TEM), including high resolution TEM (HRTEM), inductively coupled plasma (ICP) analysis and X-ray photoelectron spectroscopy (XPS). In particular, XPS measurements confirmed the presence of MIC ligands on the surfaces of the nanoparticles. The Ru·MIC nanoparticles were used in the isotopic H/D exchange of different hydrosilanes, hydroboranes, hydrogermananes and hydrostannanes using deuterium gas under mild conditions (1.0 mol% Ru, 1 bar D2, 55 °C). Selective labelling of the E-H (E = B, Si, Ge, Sn) bond in these derivatives, with high levels of deuterium incorporation, was observed.

Synthesis, structure and properties of coordination complexes of tin(ii) phthalocyanine and naphthalocyanine with transition metal fragments

Tin(ii) phthalocyanine and naphthalocyanine form stable M–Sn bonds yielding coordination complexes with transition metal fragments. In this review, we discuss the syntheses, structures and properties of such complexes.

Interface and Structure Engineering of Tin‐Based Chalcogenide Anodes for Durable and Fast‐Charging Sodium Ion Batteries

AbstractTransition metal dichalcogenides with high theoretical capacity usually suffer from poor intrinsic electronic conductivity and drastic volumetric change upon cycling, degrading their attractiveness for electrochemical high‐power and long‐term applications. Herein, a high‐efficiency and extensible synthetic strategy for in situ encapsulating nanostructured SnSe0.5S0.5 into N‐doped graphene (SnSe0.5S0.5 @ NG) by robust interfacial CSeSn bonds with formation of 3D porous network nanohybrids, is reported. Systematic electrochemical studies indicate that interface and structure engineering on SnSe0.5S0.5, including defects implantation, chemical bonding interaction, and nanospace confinement design, endow it with robust structural stability, ultrafast Na+ storage kinetics, and highly reversible redox reaction. In addition, the introduction of foreign Se ligand not only facilitates the transport of electrons/ions by enhancing the conductivity and decreasing the diffusion energy barrier but also generates more reactivity sites, as demonstrated by density functional theory calculations. By virtue of these superiorities, the SnSe0.5S0.5 @ NG exhibits superior sodium storage performance with high‐rate capability and long durability over 2000 cycles at 2 A g−1. Impressively, the full battery, when coupling SnSe0.5S0.5 @ NG anode with Na3V2(PO4)3/C cathode, can deliver high energy density of 213 Wh kg−1. This work provides an effective structural engineering strategy to design advanced electrode material with potential application for sodium‐ion batteries.

Efficient ozone catalysis by manganese iron oxides/activated carbon for sulfamerazine degradation

In this study, the manganese iron oxides/activated carbon (MnxFeyOz/AC) was prepared via the simple co-precipitation method, characterized and used for ozone catalytic degradation of sulfamerazine (SMZ). The best catalytic ozonation activity of MnxFeyOz/AC was obtained at a ratio of Fe/Mn = 1:11.2. The degradation ratio (~90.5 %) was improved by 25.7 % compared to that of ozonation system. The effects of various factors, including SMZ concentrations, ozone dosage, catalyst dosage, and initial pH on the catalytic performance were investigated. The presence of organic matter and ions in rivers, tap-water, and secondary effluent could decrease the catalytic performance. The MnxFeyOz/AC could promote more ozone dissolution in solution, while the surface hydroxyl as active sites could promote the production of hydroxyl radicals. The hydroxyl radical could destroy the SMZ structure by the cleavage of SN and CS bonds, and hydroxylation of aniline. The results of toxicity assessment indicated that catalytic ozonation could effectively control the acute and chronic toxicity of the SMZ water samples. In addition, the results of characterization of MnxFeyOz/AC before and after the ozonation experiments were discussed, and a possible degradation mechanism was proposed. Importantly, the electrical energy per order value was about 1.37 kW·h/(m3 h−1), which was lower than those of other technologies. This work presents an efficient and promising catalytic ozonation technique for the elimination of SMZ from solution, and provides interesting information for the elucidation of the mechanism of action.

L-cysteine boosted Fe(III)-activated peracetic acid system for sulfamethoxazole degradation: Role of L-cysteine and mechanism

Sulfamethoxazole (SMX), a widely used and frequently detected antibiotics, may pose threat to water safety and environmental sustainability. In this study, L-cysteine (L-Cys) was used to boost the Fe(III)/peracetic acid (PAA) system for SMX degradation. After the addition of L-Cys, the degradation efficiency of Fe(III)/PAA system for SMX increased from 26.2% to 96.7%. Appropriate increase in initial concentration of Fe(III), L-Cys or PAA promoted the SMX degradation. The role of L-Cys, including the promotion of Fe(III)/Fe(II) cycle and the improvement of pH suitability by complexation, in boosted SMX degradation was proposed. Results of methyl phenyl sulfoxide probe assays, electron paramagnetic resonance tests and quenching experiments showed that FeIVO2+ as well as HO play major roles while carbon-centered radicals hardly contribute in SMX degradation. Degradation intermediates identified by LC/MS showed that SMX was degraded to less toxic small molecules through SN bond breaking, SC bond breakage, self-coupling and hydroxylation. Besides, L-Cys/Fe(III)/PAA system showed ideal tolerance to Cl– and humic acid, while HCO3– significantly inhibited the SMX degradation. Further, the satisfactory degradations of SMX were obtained in three real waters. This study provides a feasible strategy for enhancing the oxidation capacity of the Fe(III)/PAA system and an effective technique for the treatment of SMX in real waters.