Sn-O Bond Research Articles

CO2 detection using In and Ti doped SnO2 nanostructures: Comparative analysis of gas sensing properties

This research explores the gas-sensing characteristics of undoped SnO2, as well as indium (In:SnO2) and titanium (Ti:SnO2) doped SnO2 nanostructures, which were synthesized using a homogeneous precipitation technique. Structural analyses indicate the presence of a tetragonal rutile phase with a preferred orientation along the (110) plane, with both doped samples showing shifts towards higher angles. Raman spectroscopy confirms the vibrational modes associated with SnO2 in both the pure and In: SnO2 samples, while the Ti: SnO2 sample reveals vibrational modes corresponding to both SnO2 and TiO2. Fourier-transform infrared (FTIR) spectroscopy indicates shifts in the O-Sn-O and Sn-O bonds in the doped samples, suggesting the effects of doping. X-ray photoelectron spectroscopy (XPS) results imply a combination of SnO and SnO2 phases in the undoped SnO2, while In: SnO2 samples display In-O bonding and the presence of metallic indium, and Ti: SnO2 shows Ti-O bonding. Scanning electron microscopy (SEM) images show agglomerated particles in the pure and In-doped samples, whereas the Ti-doped samples exhibit a flake-like structure. Transmission electron microscopy (TEM) analysis verifies the integration of dopants into the SnO2 crystal lattice, with average crystallite sizes measured at 44.46 nm for undoped, 34.06 nm for In: SnO2, and 42.63 nm for Ti: SnO2. Gas-sensing experiments for CO2 detection reveal that In: SnO2 demonstrates the most significant sensing response. These results underscore the impact of doping on the structural, morphological, and gas-sensing attributes of SnO2 nanostructures, offering important insights for the advancement of efficient carbon dioxide sensors.

Investigating the Local Bonding Structure of Amorphous Zinc Tin Oxide to Elucidate the Effect of Altering the Intercation Ratio.

In this paper, the local bonding structure in amorphous zinc tin oxide (a-ZTO) is probed using a combination of XANES and EXAFS techniques at the Zn and Sn K-edges to gain insight into charge carrier generation in the material. a-ZTO is prepared using two growth methods; spray pyrolysis and magnetron sputtering. It is seen that a-ZTO grown by magnetron sputtering shows no changes in the chemical environment as the cation ratio is varied; meanwhile, XANES analysis of spray pyrolysis grown samples shows alterations to spectra likely due to the effects caused by different precursors. Although a slight shift in Sn-O bond length is visible between magnetron sputtered and spray grown samples, no correlation could be discerned between bond length and variation in cation ratio. It is concluded that a-ZTO, while amorphous over longer ranges, is locally composed of ZnO and SnO2 "building blocks". An alteration in the cation ratio changes the hybridization at the conduction band minimum, resulting in the observed variation in the mobility, charge carrier concentration, and bandgap.

Structural and optical study of RF-magnetron sputtering SnO2 thin films: impact of post annealing temperature

Tin oxide (SnO2) thin films are prepared using radio frequency magnetron sputtering (RF) method and then annealed at different temperatures in the range of 550–750 °C for 1 h. The effects of annealing temperature on the structural and optical properties of the films are investigated using x-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and spectrophotometer. It is evident that the annealed films have flat surface with smooth morphology. Based on the XRD graph, as deposited films were amorphous and the annealed films had polycrystalline nature and contain the SnO2 tetragonal rutile phase. According to Raman spectra, the annealed films revealed three vibration modes Eg, A1g and B2g at the frequencies of Sn-O bond vibrations, which related to the SnO2 phase. The samples exhibit an average optical transmittance with more than 80 % between 400 − 700 nm. The refractive index values were in the range of 0.9-2.4 at visible wavelength. It is found that with increasing annealing temperature the films become more transparence while the refractive index and the extinction coefficient increased. The optical band gap energy decreases with increasing annealing temperature that means that the optical quality of annealed films is improved.

Dual Modification for Low-Strain Ni-Rich Cathodes Toward Superior Cyclability in Pouch Full Cells.

Rapid capacity fading, interfacial instability, and thermal runaway due to oxygen loss are critical obstacles hindering the practical application and commercialization of Ni-rich cathodes (LiNi0.8Co0.1Mn0.1O2, NCM811). Herein, a Sn4+/F- codoping and LiF-coated Ni-rich cathode, denoted as NCM811-SF, is structurally fabricated that demonstrates very high cyclic and thermal stabilities. The introduction of Sn4+ regulates the local electronic structure and facilitates the conversion of the layered structure into a spinel phase; F- captures lithium impurities to form LiF coatings and forms TM-F bonds to reduce Ni/Li disordering. The compositionally complex codoping strategy reduces the internal structure strain, inhibits the Li+/Ni2+ intermixing during cycling and degradation of the nanoscale structure, and further improves the thermal stability and the crystal structure. The cathodic electrode showed a little volume shift at 2.8-4.5 V, which significantly decreased lattice flaws and fractures generated by local strain, based on detailed analyses performed using COMSOL simulations, X-ray diffraction, and scanning transmission electron microscopy. Benefiting from this, after 300 cycles, our as-prepared NCM811-SF cathode maintains 85.4% of its initial capacity at 4.5 V and has an excellent reversible capacity equal to 169 mAh·g-1 at 1 C. In addition, the NCM811-SF/graphite cell in a pouch-type complete cell retained 94.8% of its starting capacity following 500 cycles. These findings underscore the effectiveness of introducing the Sn-O and TM-F bonds in improving the durability and electrochemical efficiency of the cathode material, which makes it a good choice for high-efficiency Li-ion batteries.

Interfacial engineering dominated passivation strategy to facilitate performance improvement of CsSnCl3 PSCs by induced Sn–O bonds: Insight from DFT calculations and device simulations

Defect passivation of perovskite surface not only reduces non-radiative recombination due to defect trapping charge, but also modulates the interfacial structure and energy levels, making it an effective means of solving the stability problem of perovskite materials. This work provides a passivation strategy for CsSnCl3 perovskite, and the interfacial interactions between CsSnCl3 and the passivation agent (PbSO4 and PbCO3) are explored based on first-principles density functional theory. By introducing PbSO4 and PbCO3 with multifunctional quantum dots, strong Sn-O bonds are formed with unsaturated coordination and dangling bonds on the surface of CsSnCl3. Binding sites of water molecules and impurities would be occupied by these bonds, to achieve surface passivation and dehumidification effects, and significantly improve the optical properties of CsSnCl3. PbCO3/SnCl and PbSO4/SnCl constructed the satisfactory interfacial energy level structures. PbCO3/SnCl exhibited excellent light absorption performance ranging in 0 ∼ 1200 nm. Introducing PbSO4 and PbCO3 reduced the refractive index of CsSnCl3 exhibiting excellent extinction properties. According to the simulation of Solar Design, perovskite solar cells (PSCs) constructed by (PbSO4, PbCO3)/CsSnCl3 as the active layer achieved power conversion efficiencies of 15.1946 % and 17.3783 %, respectively. This work’s research and design results provide a passivation strategy and PSCs design scheme for CsSnCl3 surface defects, which is of great significance for further modification of CsSnCl3 to better apply in photovoltaic field.

Exploring the bifunctional electrocatalytic activity of tin sulfide decorated manganese iron oxide in alkaline and urea contaminated water

Efficient, affordable, and stable electrocatalysts are pivotal for large-scale water splitting. Herein, we report an optimized decoration of tin sulfide (SnS) bundles on porous manganese ferrite (MnFe2O4) on nickel foam for enhancing the overall water splitting. This decoration yielded an interfacial Sn-O bond between MnFe2O4 and SnS, stabilized the structure, and provided optimistic adsorption energies for oxygen and hydrogen. The decorated electrode exhibited overpotentials of 383 mV for the oxygen evolution reaction (OER) and 127 mV for the hydrogen evolution reaction (HER) at 20 mA.cm−2. Moreover, the decorated sample demonstrated reduced overpotentials of 272 mV and 75 mV (at 20 mA cm−2) for OER and HER in urea-contaminated water. The augmented double layer capacitance (Cdl) electrochemical surface area (ECSA) and X-ray photoelectron spectroscopy (XPS) studies of the decorated sample corroborated the enhanced performances and effectiveness of the SnS decoration. Furthermore, SnS-decorated MnFe2O4 showed outstanding performance in a two-cell configuration with a cell voltage of 1.69 V and 1.52 V (@10 mA cm−2) under alkaline KOH and urea (0.33 M) electrolyte, respectively. Further, the chronoamperometry and post-X-ray photoelectron spectroscopy studies demonstrated the stability and promising potential of this electrode for future non-noble metal-based bifunctional catalytic applications.

Sustainable and efficient oil-water separation using bio tin oxide-based superhydrophobic membrane

IntroductionSuperhydrophobic materials are considered an ideal method for oil-water separation. However, existing oil-water separation methods have the problem of manufacturing complex and toxic chemical reagents. To address the limitation, we proposed a novel approach to sustainable and efficient oil-water separation using a superhydrophobic membrane based on the Bio Tin oxide nanoparticles (Bio-SnO2 NPs).MethodsThe study involves synthesizing Bio-SnO2 NPs from the sunflower leaf extract which was natural and non-toxic and modifying textile fabric with a superhydrophobic coating (S.T.F.). Characterization techniques including SEM, FTIR, and BET analysis are employed to assess the structural and textural properties of the modified membrane.Results and DiscussionThe textile fabric was modified with a superhydrophobic coating (S.T.F.), demonstrating enhanced wettability, oil absorption capacity, and oil-water separation performance. The Bio-SnO2 NPs exhibited crystalline structures with a length of 90 nm and a diameter of 20 nm, as confirmed by SEM analysis. FTIR results revealed characteristic peaks at 3410 cm-1 and 642 cm-1, indicating the presence of hydroxyl group and Sn-O bonds confirming the successful synthesis of Bio-SnO2 NPs. BET analysis showed a substantial specific surface area of 413 m2/g and a pore volume of 0.19 cm3/g, emphasizing the textural properties. The FTIR and SEM techniques were used to study the characteristics of the textile fabric before and after modification with the superhydrophobic coat. The S.T.F. exhibited remarkable superhydrophobicity with a water contact angle of 152° and a water sliding angle of 4°. Absorption capacities for coconut oil, diesel, and hexane were found to be 70.4 g/g, 63.5 g/g, and 49.6 g/g, respectively, with excellent cyclic stability. Separation efficiency for hexane, diesel, and coconut oil was found to be 99.5, 97.1%, and 96.3%, respectively, with excellent cyclic stability. Mechanical stability test revealed superhydrophobicity retention even after an abrasion length of 200 mm. The chemical stability test indicated that the superhydrophobicity was maintained in the pH range of 3-11. Moreover, the flux for hexane, diesel, and coconut oil was 9400 L m−2 h−1, 8800 L m−2 h−1, and 8100 L m−2 h−1, respectively, highlighting the membrane’s efficient oil-water separation capabilities. These results collectively position the developed S.T.F. as a promising and sustainable solution for diverse oil-water separation applications.

Hardness of surface hydroxyls and its pivotal role in the flotation of cassiterite from quartz via lead ions activation

Current research has trouble explaining the selective flotation mechanism realized by metal ions, which hinders the advancement of effective flotation techniques. In this work, the selective activation flotation of cassiterite from quartz with Pb2+ is taken as an example to illustrate the pivotal roles of surface hydroxyls in selective flotation. Accordingly, flotation, adsorption amount, and X-ray photoelectron spectroscopy (XPS) measurements and systematic first-principles calculations have been used to investigate the roles of hydroxyl groups on the selective adsorption of Pb2+. The obtained flotation, adsorption amount, and XPS test results consistently show that the Pb2+ can more strongly interplay with cassiterite than quartz resulting in selective flotation of cassiterite from quartz. The electron localization functional results illustrate that the electron localization of oxygen of Si-O bonds is stronger than the Sn-O bond resulting in the weaker electron migration ability (high hardness) of oxygen atoms of quartz than oxygen atoms of cassiterite. This makes the cassiterite surface hydroxyl groups less hard than quartz. Further crystal orbital Hamilton population and partial density of states show that the Pb2+ interacts with the oxygen atoms on cassiterite forming chemical bonds before and after the adsorption of benzohydroxamic acid (BHA). On the other hand, the interaction of Pb2+ with quartz is physical in the presence of BHA. The strong adsorption of Pb2+ on cassiterite makes it easier for BHA adsorption which accounts for the selective flotation of cassiterite from quartz. This work sheds new light on establishing a consistent and dependable theory that the hardness of surface hydroxyls is the original factor affecting the selective adsorption of metal ions on oxide mineral surfaces.

Thermally Induced Lattice-Defective Oxygen Breathing in Perovskite-Structure Stannates with High-Contrast Reversible Thermochromism.

Inorganic thermochromic materials exhibit a tunable color gamut and a wide chromatic temperature range, indicating their potential for intelligent adaptive applications in thermal warning, temperature indication, thermal regulation, and interactive light-to-thermal energy conversion. However, most metal-oxide-based thermochromic materials show weak chromaticity adaption with the change of temperature, which needs further understanding of the microscopic principle to clarify the potential route to improve the contrast and identifiability for fabricating better thermochromic materials. Using perovskite-structure (AMO3) alkaline earth metal stannate (Ba1-xSrxSnO3, 0.0 ≤ x ≤ 1.0) as a model system, this paper reports for the first time the mechanism of the properties of thermally induced defect-enhanced charge transfer-type (CTT) thermochromic materials and the strategy for regulating their thermochromic properties by A-site cations. BaSnO3 exhibits continuously reversible thermochromic properties with high contrast from weak light yellow (b* = 11) to strong bright yellow (b* = 58) between room temperature and 550 °C. In-situ high-temperature X-ray diffraction (in-situ XRD), in-situ UV-vis absorption spectroscopy (in-situ UV-vis), thermogravimetric (TG), and electron paramagnetic resonance (EPR) spectra indicate that this excellent thermochromic phenomenon is attributed to the weakening of Sn-O bond hybridization at high temperatures, as well as the formation of a large number of oxygen vacancies at the top of the valence band, and the enhanced charge transfer resulting from the generation of impurity levels in the Sn2+ 5s2 intermediate. Replacing Ba2+ by Sr2+ in Ba1-xSrxSnO3 successfully tuned the thermochromic properties, which is attributed to the Sr2+ doping level-directed oxygen defect concentration and deoxygenation rate. The demonstrated defect-enhanced charge transfer behavior promotes a feasible route for lattice oxygen-mediated thermochromic materials and provides a fundamental relationship between thermally induced defects and colorimetry.

Unveiling the Versatile Realm of CdSnO3 Nanoparticles for Advanced Sensing Applications

This study presents the synthesis and characterization of CdSnO3 thin films at different deposition temperatures 400, 500 and 600 °C. The prepared samples were characterized by XRD, FTIR, SEM, EDAX, TEM, optical and ammonia gas sensing properties respectively. X-ray diffraction confirms the orthorhombic crystal structure, with prominent peaks corresponding to the (111), (112), (103), (130), and (133) planes. The mean crystallite size is determined to be 84 nm. Scanning electron microscopy reveals morphological changes with varying substrate temperatures. Energy-dispersive X-ray spectroscopy shows elemental composition variations, highlighting non-stoichiometric CdSnO3 thin films. Transmission electron microscopy images depict larger spherical thin films with clear lattice fringes. Fourier-transform infrared spectra confirm the presence of Cd-O and Sn-O bonds. Optical properties yield a calculated band gap was decreased with increase in temperature. Gas sensing tests demonstrate significant sensitivity to ammonia gas concentrations, with responses affected by ammonia concentrations. Overall, CdSnO3 thin films show promise for applications in diverse fields due to their tunable properties and potential for tailored performance.

Structural, morphological, optical and low temperature magnetic studies on SnSeO3/ZnSeO3 nanocomposite

Nanocomposite SnSeO3/ZnSeO3 has been synthesized by hydrothermal method. EDAX and XRD confirm the perfect formation of SnSeO3/ZnSeO3 nano composite. It shows an interesting morphology of rectangular bar. Particle size is determined as 137.3nm. It is an effective applicant for applications in optoelectronic field. The energy gap of SnSeO3/ZnSeO3 nanocomposite is 5.52 eV. Urbach energy value obtained is 0.0635 eV. Refractive index obtained from optical energy gap is 1.926. PL emission spectrum obtains a strong efficient emission in UV (~387.7 nm) region, weak emission in green (~520.7 nm) region, and moderate emission in red (~788.7 nm) region. The UV emission at 387.7 nm shows radiative electron-hole recombination and it makes the candidate suitable for display applications. The emission peaks in the visible range may be attributed to different surface imperfections of Schottky and Frenkel kinds, oxygen vacancies and Sn – interstitials or Zn -interstitials. The FTIR bands are well assigned and confirms Se-O, ZnO, Sn-O bonds in finger print region. The sample exhibits diamagnetic nature at 300K and 5K. It also exhibits interesting super paramagnetic nature at 5K between -0.15Tesla to 0.15Tesla.

Experimental and theoretical study of the Sn-O bond formation between atomic tin and molecular oxygen.

The merging of the electronic structure calculations and crossed beam experiments expose the reaction dynamics in the tin (Sn, 3Pj) - molecular oxygen (O2, X3Σ-g) system yielding tin monoxide (SnO, X1Σ+) along with ground state atomic oxygen O(3P). The reaction can be initiated on the triplet and singlet surfaces via addition of tin to the oxygen atom leading to linear, bent, and/or triangular reaction intermediates. On both the triplet and singlet surfaces, formation of the tin dioxide structure is required prior to unimolecular decomposition to SnO(X1Σ+) and O(3P). Intersystem crossing (ISC) plays a critical role in the reaction mechanism and extensively interosculates singlet and triplet surfaces. The studied reaction follows a mechanism parallel to that for the gas phase reaction of germanium and silicon with molecular oxygen, however, the presence of the tin atom enhances and expands ISC via the "heavy atom effect".

Physical mechanism of Ge doping enhanced Ruddlesden-Popper structure quasi-2D Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic hybrid improper ferroelectricity

Hybrid improper ferroelectricity with quasi-two-dimensional (quasi-2D) structure has attracted much attention recently due to its great potential in realizing strong magnetoelectric coupling and room-temperature multiferroicity in a single phase. However, recent studies show that there appears high coercive field and low remnant polarization in ceramics, which severely hinders the applications of this material. In this work, high-quality Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> and Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub> ceramics with a Ruddlesden-Popper (R-P) structure are successfully prepared, and their crystal structures and electrical properties are investigated in detail. It is found that the Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic exhibits a lower coercive field that is close to that of Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> single crystal. Moreover, via a small amount of Ge doping, the polarization reaches 0.34 μC/cm<sup>2</sup> for Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> and 0.61 μC/cm<sup>2</sup> for Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub>. Combining crystal lattice dynamic studies, we analyze the Raman and infrared responses of the samples, showing the information about the tilting and rotation of the oxygen octahedra in the samples. The improved ferroelectricity after doping may be attributed to the increased amplitude of the tilt mode and the reduced amplitude of rotation mode. Besides, the enhanced ferroelectric properties through Ge doping and its mechanism are further investigated by the Berry phase approach and the Born effective charge method. Furthermore, via the UV-visible spectra, the optical bandgap is determined to be 3.91 eV for Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic and 3.95 eV for Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub> ceramic. Using the Becke-Johnson potential combined with the local density approximation correlation, the bandgap is calculated and is found to be in close agreement with the experimental result. And the electronic excitations can be assigned to the charge transfer excitation from O 2p to Sn 5s (Ge 4s). The effects of Ge doping on the ability of Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> to gain and lose electrons and the bonding strength of Sn-O bond are analyzed via two-dimensional charge density difference. In conclusion, this study provides insights into the synthesis method and modulation of ferroelectric properties of hybrid improper ferroelectrics Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub>, potentially facilitating their widespread applications in various capacitors and non-volatile memory devices.

Quantifying variation in cooperative B-H bond activations using Os(ii) and Os(iii) κ2-N,S-chelated complexes: same, but different.

In an effort to investigate small molecule activation by heavier transition metal (TM) based κ2-N,S-chelated species, we have synthesised a series of bis-κ2-1,3-N,S-chelated complexes of osmium, [Os(PPh3)2(κ2-N,S-La/Lb)2], 2a-b, and [Os(PPh3)(La/Lb)(κ2-N,S-La/Lb)2], 3a-b (2a and 3a: La[double bond, length as m-dash] = C7H4NS2; 2b and 3b: Lb = C5H4NS), from the thermolysis of [Os(PPh3)3Cl2], 1, with a potassium salt of heterocyclic ligands La and Lb. The former complexes are diamagnetic in nature, while the EPR spectra, XPS study and density functional theory (DFT) calculations have substantiated the paramagnetic behaviour of 3a-b with a significant spin contribution from non-innocent ligands. These species were engaged in B-H activation of boranes utilizing the combined effect of hemilability and metal-ligand cooperativity (MLC), where 2a-b upon treatment with BH3·SMe2 yielded Os(σ-borate)hydride complexes, [Os(PPh3)2(H){κ3-H,S,S'-BH2(La/Lb)2}], 4a-b (4a: La = C7H4NS2; 4b: Lb = C5H4NS). The formation of 4a-b was emphasized on the basis of possible dual B-H activation that involved a few concerted steps, i.e., (i) cleavage of one hemilabile Os-N bond and cooperative B-H bond activation, (ii) cleavage of another hemilabile Os-N bond and formation of a B-N bond and (iii) activation of another B-H bond. In stark contrast, the paramagnetic bis-κ2-1,3-N,S-chelated species 3a-b manifested diverse activation patterns in the light of the different electronic nature of non-innocent ligands. While the reaction of 3b with borane generated dihydridoborate species, [Os(PPh3)(κ2-N,S-Lb)(κ3-H,H,S'-BH2(OH)C5H4NS)], 5, complex 3a led to the formation of an Os(σ-borate) complex, [Os(PPh3)(κ2-N,S-La)(κ3-H,S,S'-BH2L2 a)], trans-6. As the σ-borate entity shows a tendency to adapt to different spatial arrangements around the metal center, we have established a modified synthetic strategy to isolate the cis isomer of 6 that involved the reaction of [Os(PPh3)3Cl2], 1, with NaBH2La 2. In a similar fashion, the treatment of [Os(PPh3)3Cl2], 1, with NaBH2Lb 2 yielded [Os(PPh3)(κ2-N,S-Lb)(κ3-H,S,S'-BH2L2 b)], cis-7. The kinetic and thermodynamic stability of these isomeric species were investigated on the basis of extensive density functional theory (DFT) calculations. Theoretical calculations also provided insightful information on the electronic nature of the species, generated from B-H activations of boranes.

Investigating the temperature and frequency dependence of dielectric response using AC impedance spectroscopy on SnO2

In this investigation, we explored tin oxide's dielectric properties and impedance spectroscopy, focusing on its temperature dependence across a frequency range of 20 Hz to 2 MHz. We analyzed the x-ray diffraction pattern using Rietveld refinement and established that the sample has a tetragonal phase with P42/mnm space group. Afterward, the surface structure of the SnO2 was examined using (FESEM) and Raman spectroscopy. Through FESEM, we analyzed the morphology of the prepared sample, which were nanospheres in structure. In contrast, we discovered the non-degenerated A1g and B2g modes through Raman spectroscopy, which matches well with the literature and displays the contraction and expansion of Sn-O bonds. We performed dielectric studies at varying frequencies and temperatures to further analyze the properties. We discovered that the ac conductivity increased as temperature and frequency increased. The activation energy was calculated using dc electrical conductivity measurement. The DC conductivity exhibits a temperature dependence that can be described by the Arrhenius equation, which reveals that the tin oxide has to conduct behavior with an estimated activation energy of 0.025 eV, 0.035 eV, and 0.082 eV for three temperature ranges of 80–120 K, 120–175 K, and 175–270 K, respectively. Additionally, the AC conductivity data conforms to Jonscher's universal power law. The frequency-dependent parameter “s” increases as the temperature elevates. A transition from the QMT (Quantum mechanical tunneling) model to NSPT (non-overlapping small polaron tunneling) was employed to analyze the data.

Study the Electronic and Spectroscopic Characteristics of p-n Heterojunction Hybrid (Sn10O16/C24O6) via Density Functional Theory (DFT)

The electronic characteristics, including the density of state and bond length, in addition to the spectroscopic properties such as IR spectrum and Raman scattering, as a function of the frequency of Sn10O16, C24O6, and hybrid junction (Sn10O16/C24O6) were studied. The methodology uses DFT for all electron levels with the hybrid function B3-LYP (Becke level, 3-parameters, Lee–Yang-Parr), with 6-311G (p,d) basis set, and Stuttgart/Dresden (SDD) basis set, using Gaussian 09 theoretical calculations. The geometrical structures were calculated by Gaussian view 05 as a supplementary program. The band gap was calculated and compared to the measured values. The density of state of the hybrid junction (Sn10O16/C24O6) increased because of the increased number of degeneracy states. Theoretical values of bonds for C=C, C=O, and Sn-O are equal to 1.33, 1.20 and 2.27 Å respectively, these bonds values are in good agreement with experimental values of bond length of 1.34 for the C=C bond, 1.23 for the C=O bond, and 2.3 for the Sn-O bond. . The spectroscopic properties, such as IR spectra have shown a peak which is comparable to longitudinal modes of GO and tin dioxide SnO2 at (1582 and 690) cm-1, respectively.

Cation-Radius-Controlled Sn-O Bond Length Boosting CO2 Electroreduction over Sn-Based Perovskite Oxides.

Despite the intriguing potential shown by Sn-based perovskite oxides in CO2 electroreduction (CO2 RR), the rational optimization of their CO2 RR properties is still lacking. Here we report an effective strategy to promote CO2 -to-HCOOH conversion of Sn-based perovskite oxides by A-site-radius-controlled Sn-O bond lengths. For the proof-of-concept examples of Ba1-x Srx SnO3 , as the A-site cation average radii decrease from 1.61 to 1.44 Å, their Sn-O bonds are precisely shortened from 2.06 to 2.02 Å. Our CO2 RR measurements show that the activity and selectivity of these samples for HCOOH production exhibit volcano-type trends with the Sn-O bond lengths. Among these samples, the Ba0.5 Sr0.5 SnO3 features the optimal activity (753.6 mA ⋅ cm-2 ) and selectivity (90.9 %) for HCOOH, better than those of the reported Sn-based oxides. Such optimized CO2 RR properties could be attributed to favorable merits conferred by the precisely controlled Sn-O bond lengths, e.g., the regulated band center, modulated adsorption/activation of intermediates, and reduced energy barrier for *OCHO formation. This work brings a new avenue for rational design of advanced Sn-based perovskite oxides toward CO2 RR.

Raman Spectroscopic Characterization of Chemical Bonding and Phase Segregation in Tin (Sn)-Incorporated Ga2O3.

Using detailed Raman scattering analyses, the effect of tin (Sn) incorporation on the crystal structure, chemical bonding/inhomogeneity, and single-phase versus multiphase formation of gallium oxide (Ga2O3) compounds is reported. The Raman characterization of the Sn-mixed Ga2O3 polycrystalline compounds (0.00 ≤ x ≤ 0.30), which were produced by the high-temperature solid-state synthesis method, indicated that the Sn-induced changes in the chemical bonding and phase segregation were significant. Furthermore, the evolution of Sn-O bonds with increasing Sn concentration (x) was confirmed. While the monoclinic β-Ga2O3 was unperturbed for lower x values, Raman spectra revealed the nucleation of a composite with a distinct SnO2 secondary phase. A higher Sn content led to the formation of a Ga-Sn-O + SnO2 mixed phase compound, which was reflected in shifts in the high-frequency stretching and bending of the GaO4 tetrahedra that structurally formed the β-Ga2O3 phase. Thus, a chemical composition/phase/chemical bonding correlation was established for the Sn-incorporated Ga2O3 compounds.

Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum

Due to their intrinsic high reactivity, isolation of heavier analogues of carbynes remains a great challenge. Here, we report the synthesis and characterization of a neutral monosubstituted Sn(I) radical (2) supported by a sterically hindered hydrindacene ligand, which represents the first tin analogue of a free carbyne. Different from all Sn(I/III) species reported thus far, the presence of a sole Sn-C σ bond in 2 renders the remaining two Sn 5p orbitals energetically almost degenerate, of which one is singly occupied and the other is empty. Consequently, its S = 1/2 ground state possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, as evidenced by one component of its g matrix (1.957, 1.896, and 1.578) being considerably less than 2. Consistent with this unique electronic structure, 2 can bind to an N-heterocyclic carbene to afford a neutral two-coordinate Sn(I) radical and initiate a one-electron transfer to benzophenone to furnish a Sn(II)-ketyl radical anion adduct. As a manifestation of its Sn-centered radical nature, 2 reacts with diphenyl diselenide and p-benzoquinone to form Sn-S and Sn-O bonds, respectively.

P2-Type Moisture-Stable and High-Voltage-Tolerable Cathodes for High-Energy and Long-Life Sodium-Ion Batteries.

P2-Na0.67Ni0.33Mn0.67O2 represents a promising cathode for Na-ion batteries, but it suffers from severe structural degradation upon storing in a humid atmosphere and cycling at a high cutoff voltage. Here we propose an in situ construction to achieve simultaneous material synthesis and Mg/Sn cosubstitution of Na0.67Ni0.33Mn0.67O2 via one-pot solid-state sintering. The materials exhibit superior structural reversibility and moisture insensitivity. In-operando XRD reveals an essential correlation between cycling stability and phase reversibility, whereas Mg substitution suppressed the P2-O2 phase transition by forming a new Z phase, and Mg/Sn cosubstitution enhanced the P2-Z transition reversibility benefiting from strong Sn-O bonds. DFT calculations disclosed high chemical tolerance to moisture, as the adsorption energy to H2O was lower than that of the pure Na0.67Ni0.33Mn0.67O2. A representative Na0.67Ni0.23Mg0.1Mn0.65Sn0.02O2 cathode exhibits high reversible capacities of 123 mAh g-1 (10 mA g-1), 110 mAh g-1 (200 mA g-1), and 100 mAh g-1 (500 mA g-1) and a high capacity retention of 80% (500 mA g-1, 500 cycles).