Sb Ions Research Articles

What Can Chemical Bonding Tell Us about Photoinduced Phase Transition Reactions in Inorganic Semiconductors? Insight from Bismuth-Antimony Selenide.

Photoreactive self-healing semiconductors with suitable bandgaps for solar energy conversion offer an intriguing path to making resilient and low-cost photovoltaic devices through the introduction of a self-recovery path. However, only a few inorganic photovoltaic materials have such quality, and the underlying chemical properties that enable it are unknown, which poses a significant limit to our ability to study and discover new self-healing semiconductors. Recently, we have found that antimony trichalcogenide (Sb2Se3 and Sb2S3) and chalcohalides (e.g., SbSeI) can undergo a reversible photoinduced phase transition (PIPT) in which the structure is restored after photoinduced damage incurs to the materials. This group of materials offer a unique opportunity for studying PIPT and its limits. In particular, this group of materials facilitate the study of functional permutation to specific crystalline sites and to finding the limits of PIPT occurrence, which sheds light on the origin of the PIPT and self-recovery of this class of materials. Using Raman spectroscopy of thin films, and following signature vibrations of transition species, we have found that the PIPT magnitude decays upon gradual BiSb(1) substitution in a Sb2-xBixSe3 homologous series, until nearly one in five Sb ions is substituted with Bi. Then, the PIPT diminishes completely. The homologous series occurs along a transition from covalent to metavalent chemical bonding. By expanding our search, we find that a correlation between bonding type and photoreactivity does exist but conclude that it is an insufficient condition. Instead, we suggest, based on bond order and additional DFT calculations, that sufficient bonding states at the bottom of the conduction band are also required. This joint experimental and computational study pushes the limits of designing self-healing inorganic semiconductors for various applications and provides tools for further expansion.

Polyindole-Functionalized RGO-NiFe2O4-SiO2 Nanocomposite: A Dual-Functional Nanomaterial for Efficient Antimony Adsorption and Subsequent Application in Supercapacitor.

Effective wastewater treatment remains a critical challenge, especially when dealing with hazardous pollutants like antimony (Sb(III)). This study addresses this issue by using innovative nanocomposites to remove Sb(III) ions from water, while simultaneously repurposing the spent adsorbents for energy storage applications. We developed reduced graphene oxide-NiFe2O3-SiO2-polyindole nanocomposites (RGO-NiFe2O3-SiO2-PIn NCs) via a hydrothermal synthesis method, achieving a high removal efficiency of 91.84% for Sb(III) ions at an initial concentration of 50 mg/L at pH 8. After adsorption, the exhausted adsorbent was repurposed for energy storage, effectively minimizing secondary pollution. The Sb(III)-loaded adsorbent (RGO-NiFe2O3-SiO2-PIn@SbOx) exhibited excellent performance as an energy storage material, with a specific capacitance (Cs) of 701.36 F/g at a current density of 2 A/g and a retention rate of 80.15% after 10,000 cycles. This dual-purpose approach not only advances wastewater treatment technologies but also contributes to sustainable and economical recycling practices, particularly in the field of energy storage.

Incorporating Sb (III) and Bi (III) ions into Cs2AgNaInCl6 perovskite toward efficient white-light emission with high color rendering index

Single phosphor with efficient and high quality white-light emission is necessary for lighting applications. In this work, we report a double perovskite, Cs2AgNaInCl6 with Bi3+ and Sb3+ incorporation, which demonstrates excellent white-light properties including tunable emission component and correlated colour temperature (CCT). Using the broad-band emission of self-trapped excitons (STEs) associated with Bi3+ and Sb3+ in the Cs2AgNaInCl6 host, the blue and orange dual-band STEs emission located at 460 and 565 nm covers the entire visible range to achieve high-quality white light emission. The relative intensity of the dual emission components can be adjusted flexibly by modulating the doping ratio of Bi3+ and Sb3+. The dual STEs emission shares the same optimal excitation wavelength at 340 nm. The optimal sample of Bi3+ (1 %) and Sb3+ (10 %) codoped Cs2Ag0.1Na0.9InCl6 exhibits high color rendering index (CRI) of up to 93, and high photo-luminescence quantum yield (PLQY) of 76 %. This codoping in double perovskite approach represents a promising method for achieving high-quality white lighting application within a single phosphor.

Synthesis, Electrochemistry and Photochemistry of Hypervalent Phosphorus(V) Porphyrin and Antimony(V) Porphyrin Black Dyes

In the last few years, our focus has been on push-pull type hypervalent Group 15 porphyrins with intramolecular charge transfer (ICT) properties. Insertion of P(V) or Sb(V) ion in the porphyrin cavity results in a highly electron-deficient porphyrin center, under this condition the presence of electron-rich units in porphyrin meso-positions results in charge transfer within the molecules. Recently, we extended this strategy to 5,10,5,20-tetrakis(triphenylamine)porphyrin derivative where strong electron donor triphenylamine (TPA) units are in meso-positions. Upon insertion of the P(+5) and Sb(+5) ion, the resulting hypervalent Group 15 porphyrins manifested a strong ICT from the TPA units to the central porphyrin ring. The existence of ICT makes the absorption profiles cover the entire visible region with high molar extinction coefficients. Due to this reason, the studied hypervalent Group 15 porphyrins appear as black dyes. Here, I will present these porphyrins and discuss their structural, redox, and remarkable photophysical properties. Figure 1

Efficient removal of Sb(III) from wastewater using selenium nanoparticles synthesized by Psidium guajava plant extract.

Antimony (Sb) pollution in aquatic ecosystems has emerged as a critical environmental issue on a global scale, emphasizing the urgent need for cost-effective and user-friendly technologies to remove Sb compounds from water sources. In this study, a novel adsorbent, selenium nanoparticles (SeNPs), was synthesized using the aqueous extract of Psidium guajava L. leaves (AEP) for the purpose of eliminating Sb(III) from aqueous solutions. The biosynthesized SeNPs was characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence spectrometer (XRF), Fourier Transform-Infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis techniques. Additionally, the removal efficiency of the SeNPs for Sb(III) was systematic investigated under the effects of SeNPs dose, temperature, pH and re-usability. The results of this study showed that the adsorption data fitted well into pseudo-second order model, while the Sips modeling demonstrated a high adsorption capacity (62.7mg/g) of SeNPs for Sb(III) ions at 303.15K from aqueous solution. The exothermic enthalpy change of - 22.59kJ/mol and negative Gibbs free energy change assured the viability of the adsorption process under the considered temperature conditions. Surface functional groups on SeNPs like carboxyl, amide, hydroxyl, carbonyl, and methylene significantly facilitate the adsorption processes. Furthermore, the removal efficiencies of Sb in the two actual Sb mine wastewater samples were remarkably high, achieving nearly to 100% with 1.5g/L SeNPs within 48h. This outcome underscores the potential of SeNPs as a highly promising solution for efficiently remediating Sb from aquatic environments, owing to their cost-effectiveness, ease of regeneration, and rapid uptake capabilities.

Sb3+/Sm3+ Codoped Cs2NaScCl6 All-Inorganic Double Perovskite: Blue Emission of Self-Trapped Excitons and Red-Emission via Energy Transfer.

The lead-free halide perovskites possess nontoxicity and excellent chemical stability, whereas relatively weak luminescence intensity limits their potential in practical applications. Therefore, strengthening the luminescence intensity and expanding application fields are urgent tasks for the development of lead-free halide perovskites. In this paper, antimony-doped Cs2NaScCl6 crystals synthesized by a solvothermal method emit bright, deep blue photoluminescence at 447 nm. The photoluminescence (PL), photoluminescence excitation (PLE), and absorption spectra demonstrate that Sb3+ doping effectively activate the intrinsic "dark self-trapped exciton (STE)," leading to an impressive photoluminescence quantum yield (PLQY) value of 78.31% for 1% Sb3+ doping. Furthermore, the luminescence intensity remains above 92% compared with the fresh sample without secondary phases detected even after 90 days under environmental conditions. To expand the emission spectra, rare-earth Sm3+ is further incorporated into Cs2NaScCl6:1% Sb3+ crystals. The results show that Sb ions not only enhance intrinsic STE luminescence but also serve as sensitizers to boost the red-light emission of Sm3+, leading to a significant 500-fold increase in red emission intensity. Finally, the PLQY reaches a stunning 86.78%. These findings provide valuable insights in the design of Sb ion-doped lead-free double perovskites, broadening the application fields in various optoelectronic devices.

Tuning Intramolecular Charge Transfer in Antimony(V) Porphyrin through Axial Fluorination.

Modulation of intramolecular charge transfer (ICT) has been tested in two antimony(V) porphyrins, SbT(DMP)P(OMe)2·PF6 and SbT(DMP)P(OTFE)2·PF6, where the meso-positions are occupied by 3,5-dimethoxyphenyl (DMP), and the axial positions are linked with either methoxy (OMe) or trifluoroethoxy (OTFE) units, respectively. The presence of the Sb(+5) ion makes the porphyrin center electron poor. Under this situation, placing electron-rich units in the meso-position creates a condition for push-pull type ICT in the SbT(DMP)P(OMe)2·PF6. Remarkably, it is shown that the ICT character can be further enhanced in SbT(DMP)P(OTFE)2·PF6 with the help of electron-withdrawing TFE units in the axial position, which makes the porphyrin center even more electron scarce. The steady-state and transient studies as well as solvatochromism studies establish the ICT in SbT(DMP)P(OMe)2·PF6 and SbT(DMP)P(OTFE)2·PF6, and the strength of the ICT can be modulated by exploiting the structural properties of antimony(V) porphyrin. The existence of ICT is further supported by density functional theory calculations. The transient studies show that upon excitation of these porphyrin, their charge-transfer states convert to a full charger-separated states with appreciable lifetimes.

Investigation of use of hydrophilic/hydrophobic NADESs for selective extraction of As(III) and Sb(III) ions in vegetable samples: Air assisted liquid phase microextraction and chemometric optimization

In this paper, a green, cost-effective sample preparation method based on air assisted liquid phase microextraction (AA-LPME) was developed for the simultaneous extraction of As(III) and Sb(III) ions from vegetable samples using hydrophilic/hydrophobic natural deep eutectic solvents (NADESs). Central composite design was used for the optimization of extraction factors including NADES volume, extraction cycle, pH, and curcumin concentration. Limits of detection for As(III) and Sb(III) were 1.5 ng L−1 and 0.06 ng L−1, respectively. Working ranges for As(III) and Sb(III) were 0.2–300 ng L−1 (coefficient of determination (R2 = 0.9978) and 5–400 ng L−1 (R2 = 0.9996), respectively. Relative standard deviations for As(III) and Sb(III) were 2.2–2.8% and 2.9–3.2%, respectively. Enrichment factor of the method was 184 for As(III) and 172 for Sb(III). The accuracy and precision of the AA-NADES-LPME method were investigated by intraday/interday studies and standard reference material analysis, respectively. Finally, the AA-NADES-LPME method was successfully applied to microwave digested vegetable samples using the standard addition approach and acceptable recoveries were achieved.

Au-Pt alloy nanoislands for highly sensitive localized surface plasmon resonance sensing of antimony(III) ions

Alloy nanomaterials exhibit superior plasmonic properties that can exceed traditional single-metal nanomaterials. Hence, they hold great potential for developing highly sensitive sensors capable of detecting small analytes in nanoscale. The self-assembly Au-Pt alloy nanoislands structure is used, for the first time, for localized surface plasmon resonance sensing. Its nanostructure has been studied and characterized by using various microscopy and spectroscopy techniques. It was found that Au0.94-Pt0.06 was the optimum composition with the best sensitivity toward the change of refractive index over various concentrations of NaCl solution and double the sensitivity than that of pure Au nanoislands. The Au-Pt chip with its surface functionalized with nitrotyrosine was successfully developed for highly sensitive detection of antimony (III) ion, the electronic properties of the interaction between nitrotyrosine and Sb during the biosensing was explored using density functional theory simulation to explain their strong adsorption to make nitrotyrosine a successful receptor. The sensor achieved a limit of detection of 0.0504 ppb, which is the best ever value among all those reported for Sb(III) ions sensing. With its high selectivity tested among 14 other common elements, the present Sb(III) ion LSPR sensor also possesses attributes of label-free, easy to fabricate and simple to operate.

Resonant x-ray diffraction measurements in charge ordered kagome superconductors KV3Sb5 and RbV3Sb5

We report on (resonant) x-ray diffraction experiments on the normal state properties of kagome-lattice superconductors KV3Sb5 and RbV3Sb5. We have confirmed previous reports indicating that the charge density wave (CDW) phase is characterized by a doubling of the unit cell in all three crystallographic directions. By monitoring the temperature dependence of Bragg peaks associated with the CDW phase, we ascertained that it develops gradually over several degrees, as opposed to CsV3Sb5, where the CDW peak intensity saturates promptly just below the CDW transition temperature. Analysis of symmetry modes indicates that this behavior arises due to lattice distortions linked to the formation of CDWs. These distortions occur abruptly in CsV3Sb5, while they progress more gradually in RbV3Sb5 and KV3Sb5. In contrast, the amplitude of the mode leading to the crystallographic symmetry breaking from P6/mmm to Fmmm appears to develop more gradually in CsV3Sb5 as well. Diffraction measurements close to the V K edge and the Sb L1 edge show no sensitivity to inversion- or time-symmetry breaking, which are claimed to be associated with the onset of the CDW phase. The azimuthal angle dependence of the resonant diffraction intensity observed at the Sb L1 edge is associated with the difference in the population of unoccupied states and the anisotropy of the electron density of certain Sb ions.

Fabrication and characterization of different PbO borate glass systems as radiation-shielding containers

Three borate glasses of 50, 35, and 15 mol% PbO-doped Ce, Sb, or Mn ions were fabricated via the melting-annealing procedure. Their structural features were inspected before and after 250 kGy of gamma irradiation using FTIR and ESR techniques. The spectra of the ESR and FTIR vibrational bands remain constant, with a minor reduction in N4 and an enhancement in density values after irradiation, indicating the large structural stability and glass compactness. Many radiation shielding parameters were studied, such as gamma dose rate (µSv/h), dose transmission %, lifetime cancer risk %, macroscopic effective removal cross-section (∑R), mass stopping power, and projected range values ​​were considered for protons particles by SRIM Monte Carlo simulation code and ESTAR program. The whole data reveals the high radiation shielding efficiency of the glasses compared to other standard shields to be used as glass immobilizers for radioactive wastes or storage containers, e.g., for nuclear medicine units in hospitals.

Over 10% Efficient Sb2(S,Se)3 Solar Cells Enabled by CsI-Doping Strategy.

Antimony selenosulfide (Sb2(S,Se)3) is an emerging quasi-1D photovoltaic semiconductor with exceptional photoelectric properties. The low-symmetry chain structure contains complex defects and makes it difficult to improve electrical properties via doping method. This article reports a doping strategy to enhance the efficiency of Sb2(S,Se)3 solar cells by using alkali halide (CsI) as the hydrothermal reaction precursor. It is found that the Cs and I ions are effectively doped and atomically coordinate with Sb ions and S/Se ions. The CsI-doping Sb2(S,Se)3 absorbers exhibit enhanced grain morphologies and reduced trap densities. The consequential CsI-doping Sb2(S,Se)3 based solar cells demonstrate favorable band alignment, suppressed carrier recombination, and improved device performance. An efficiency as high as 10.05% under standard AM1.5 illumination irradiance is achieved. This precursor-based alkali halide doping strategy provides a useful guidance for high-efficiency antimony selenosulfide solar cells.

Effect of Sb-Bi alloying on electron-hole recombination time of Cs2AgBiBr6 double perovskite.

The double perovskite material Cs2AgBiBr6, characterized by high stability, low toxicity, and excellent optoelectronic properties, has emerged as a promising alternative to lead-based halide perovskites in photovoltaic applications. However, its photovoltaic conversion efficiency after integration into solar cell devices is less than 3%, significantly lower than that of traditional perovskite solar cells. While alloying methods have been widely applied in the design of photovoltaic materials, their specific role in modulating the lifetime of photo-generated charge carriers in double-perovskite solar cells remains inadequately explored. In this study, through nonadiabatic molecular dynamics (NAMD) simulations, the excited-state dynamics properties of Cs2AgBiBr6 and alloyed Cs2AgSb0.375Bi0.625Br6 samples were compared. The results revealed that the introduction of Sb ions into the double perovskite structure induces lattice deformation upon heating to 300 K, leading to distortion of Bi-Br bonds and enhanced valence band delocalization. Using the decoherence-induced surface hopping method, the capture and recombination processes of charge carriers between different states were simulated. It was suggested that hole lifetime serves as the primary limiting factor for carrier lifetime in Cs2AgBiBr6, and replacing 0.375 proportion of Bi with Sb can decelerate the hole capture rate, extending carrier lifetime by 3-4 times. This study demonstrates that alloying offers a viable approach to optimizing the optoelectronic performance of the Cs2AgBiBr6 perovskite, thereby advancing the application of double perovskite materials in the field of photovoltaics.

Incorporation of Antimony Ions in Heptaisobutyl Polyhedral Oligomeric Silsesquioxanes

The direct incorporation of Sb(V) ions into a polycondensed silsesquioxane network based on heptaisobutyl POSS units (Sb(V)-POSSs) through a corner-capping reaction is reported for the first time in this work. As a reference sample, a completely condensed monomeric Sb(III)-POSS was prepared using a similar synthetic protocol. The chemical properties of both Sb-containing POSSs were investigated with different analytical and spectroscopic techniques. The analyses confirm the success of the corner-capping reaction for both samples and indicate that an Sb(V)-POSS sample is characterized by a heterogenous multimeric arrangement with an irregular organization of POSS cages linked to Sb(V) centers, and has a more complex structure with respect to the well-defined monomeric Sb(III)-POSS.

Synergetic effect of Sb ion implantation on the optical and structural properties of single crystal rutile TiO2 (110)

The present study investigates the synergetic influence of Sb ion implantation on the optical and structural properties of single crystal rutile TiO2 (110). The Implantation was carried out at various fluences using 2 MeV Sb ions. X-ray diffraction, X-ray photoelectron spectroscopy, and Photoluminescence studies reveal the occurrence of an ion-induced annealing process which is remarkably responsible for the healing of defect states in the absence of any thermal treatment. Surprisingly, the ion-induced annealing appears to get activated only for the fluences of 1 × 1015 ions/cm2 and higher. At the fluence of 5 × 1015 ions/cm2, reduction in defect states, increase in crystallinity, increase in the photo absorption response (130 % in visible and 165 % in ultraviolet range), improved band-edge luminescence, and bandgap reduction (by ∼0.26 eV) is observed. The ion-induced annealing process effectively improves photo absorption properties without any thermal treatment. These results can play a pivotal role in photocatalysis applications.

The Preparation, Characterization, and Pressure-Influenced Dihydrogen Interactions of Tetramethylphosphonium Borohydride.

Tetramethylphosphonium borohydride was synthesized via an ion metathesis reaction in a weakly-coordinating aprotic environment. [(CH3)4P]BH4, in contrast to related [(CH3)4N]+ compounds which tend to crystallize in a tetragonal system, adopts the distorted wurtzite structure (P63mc), resembling some salts containing analogous ions of As and Sb. [(CH3)4P]BH4 decomposes thermally in several endo- and exothermic steps above ca. 240 °C. This renders it more stable than [(CH3)4N]BH4, with a lowered temperature of decomposition onset by ca. 20 °C and solely exothermic processes observed. Raman spectra measured at the 0-10 GPa range indicate that a polymorphic transition occurs within 0.53-1.86 GPa, which is further confirmed by the periodic DFT calculations. The latter suggests a phase transition around 0.8 GPa to a high-pressure phase of [(CH3)4N]BH4. The P63mc phase seems to be destabilized under high pressure by relatively closer dihydrogen interactions, including the C-H…H-C contacts.

Tuning of internal electric field and diffusion distance boosting the charge separation for photocatalytic electricity generation

Solar-light driven electricity generation from organic molecule oxidation emerges as a green technology for energy conversion and sewage recycling. However, low charge separation efficiency severely restricts the photocatalytic electricity generation and photooxidation. Herein, we introduce a novel monolayered Sb-BiOCl nanosheets fabricated via injecting Sb ions and hydrophobic chains of cetyltrimethylammonium (CTA+) for photocatalytic electricity generation. By visible light irradiation and addition of organic molecule fuel to artificially construct the photo fuel cell system, the BiOCl with 10% Sb dopant converts electricity with 3.9-fold increase compared to the bulk BiOCl. The enhanced electrical output is primarily attributed to their efficient charge separation facilitated by the boosted internal electric field (IEF) and reduced diffusion distance. DFT calculation and electrochemical test demonstrate that the nonuniform charge distribution between [Bi2O2] and [Cl] slices resulting from the electron donor Sb doping contributes to 92-fold increase of IEF parallel to [010] zone. Significantly, the shortened transport channel of charge carriers further promotes the photogenerated charge anisotropic separation. This work proves that the cooperative effect of IEF and diffusion distance tuning can boost the charge separation of photocatalysts, which offers a useful strategy for constructing effective solar-light driven electricity generation system.

Influence of Antimony Species on Electrical Properties of Sb-Doped Zinc Oxide Thin Films Prepared by Pulsed Laser Deposition.

This study systematically investigates the influence of antimony (Sb) species on the electrical properties of Sb-doped zinc oxide (SZO) thin films prepared by pulsed laser deposition in an oxygen-rich environment. The Sb species-related defects were controlled through a qualitative change in energy per atom by increasing the Sb content in the Sb2O3:ZnO-ablating target. By increasing the content of Sb2O3 (wt.%) in the target, Sb3+ became the dominant Sb ablation species in the plasma plume. Consequently, n-type conductivity was converted to p-type conductivity in the SZO thin films prepared using the ablating target containing 2 wt.% Sb2O3. The substituted Sb species in the Zn site (SbZn3+ and SbZn+) were responsible for forming n-type conductivity at low-level Sb doping. On the other hand, the Sb-Zn complex defects (SbZn-2VZn) contributed to the formation of p-type conductivity at high-level doping. The increase in Sb2O3 content in the ablating target, leading to a qualitative change in energy per Sb ion, offers a new pathway to achieve high-performing optoelectronics using ZnO-based p-n junctions.

Impact of Sb degrees of freedom on the charge density wave phase diagram of the kagome metal CsV3Sb5

Elucidating the microscopic mechanisms responsible for the charge density wave (CDW) instability of the AV$_3$Sb$_5$ (A=Cs, K, Rb) family of kagome metals is critical for understanding their unique properties, including superconductivity. In these compounds, distinct CDW phases with wave-vectors at the $M$ and $L$ points are energetically favorable, opening the possibility of tuning the type of CDW order by appropriate external parameters. Here, we shed light on the CDW landscape of CsV$_3$Sb$_5$ via a combination of first-principles calculations and phenomenology, which consists of extracting the coefficients of the CDW Landau free-energy expansion from density functional theory. We find that while the main structural distortions of the kagome lattice in the staggered tri-hexagonal CDW phase are along the nearest-neighbor V-V bonds, distortions associated with the Sb ions play a defining role in the energy gain in this and all other CDW states. Moreover, the coupling between ionic displacements from different unit cells is small, thus explaining the existence of multiple CDW instabilities with different modulations along the c-axis. We also investigate how pressure and temperature impact the CDW phase of CsV$_3$Sb$_5$. Increasing pressure does not change the staggered tri-hexagonal CDW ground state, even though the $M$-point CDW instability disappears before the $L$-point one, a behavior that we attribute to the large nonlinear coupling between the order parameters. Upon changing the temperature, we find a narrow regime in which another transition can take place, toward a tri-hexagonal Star-of-David CDW phase. We discuss the implications of our results by comparing them with experiments on this compound.

ИЗВЛЕЧЕНИЕ ИОНОВ Ag(I) И Sb(III) ИЗ ВОДНЫХ СРЕД ФОСФАТОТИТАНОВЫМИ СОРБЕНТАМИ

The use of sorbents based on titanium(IV) oxohydroxophosphates for deep purification of liquid radioactive waste of complex chemical composition from Ag(I) and Sb(III) ions is shown to be promising. It has been established that Ag(I) cations are effectively extracted in an alkaline medium, Sb(III) cations - in an acidic region as a result of ionic substitution of H+ hydrophosphate groups for metal cations. Since Sb(III) is present in the anionic form in an alkaline medium, the Sb(III) anions are extracted as a result of ion exchange for the OH--groups of the sorption matrix.