Bismuth-based Compounds Research Articles

Interfacial Coupling toward Bismuth Sulfide/MXene Heterostructures Empowering Reversible Magnesium Storage.

Bismuth-based compounds based on conversion-alloying reactions of multielectron transfer have attracted extensive attention as alternative anode candidates for rechargeable magnesium batteries (rMBs). However, the inadequate magnesium storage capability induced by the sluggish kinetics, poor reversibility, and terrible structural stability impedes their practical utilization. Herein, monodispersed Bi2S3 anchored on MXene has been prepared via a simple self-assembly strategy to induce the interfacial bonding of Ti-S and Ti-O-Bi. Unique superiority, including good electrical conductivity, high mechanical strength, and rapid charge transfer, is cleverly integrated together in the Bi2S3/MXene heterostructures, which endowed heterostructures with enhanced magnesium storage performance. Density functional theory calculations combined with kinetic behavior analyses confirm the favorable charge transfer and low ion diffusion barrier in hybrids. Furthermore, a stepwise insertion-conversion-alloying reaction mechanism is revealed in depth by ex situ investigations, which may also account for promoting performance. This work provides significant inspirations for constructing ingenious multicompositional hybrids by strong interfacial coupling engineering toward high-performance energy storage devices.

Study on the Preparation and PEC-Type Photodetection Performance of β-Bi2O3 Thin Films.

Bismuth-based compounds have been regarded as a kind of promising material due to their narrow bandgap, high carrier mobility, low toxicity, and strong oxidation ability, showing potential applications in the field of photoelectrochemical (PEC) activities. They can be applied in sustainable energy production, seawater desalination and treatment, optical detection and communication, and other fields. As a member of the broader family of bismuth-based materials, β-Bi2O3 exhibits significant advantages for applications in engineering, including high photoelectric response, stability in harsh environments, and excellent corrosion resistance. This paper presents the synthesis of β-Bi2O3 thin films utilizing the mist chemical vapor deposition (CVD) method at the optimal temperature of 400 °C. Based on the β-Bi2O3 thin film synthesized at optimal temperature, a PEC-type photodetector was constructed with the highest responsivity R of 2.84 mA/W and detectivity D of 6.01 × 1010 Jones, respectively. The photodetection performance was investigated from various points like illumination light wavelength, power density, and long-term stability. This study would broaden the horizontal and practical applications of β-Bi2O3.

Mist Chemical Vapor Deposition of Bi13S18I2 for Photoelectrochemical-type Photodetection.

Bismuth-based ternary compounds have attracted much attention owing to their various merits, such as low toxicity and tunable electrical and optical properties. However, these compounds are yet to be understood due to the lack of suitable targets limited by immature synthesis techniques. In this work, we aimed at the synthesis, properties investigation, and photodetection application of Bi13S18I2. Mist chemical vapor deposition was adopted for the deposition of the Bi13S18I2 thin film for the first time. The deposition mechanism was discussed from the perspective of crystal phase and surface morphology. Based on the Bi13S18I2 thin film synthesized at optimal temperature, we constructed a photoelectrochemical-type photodetector. The photodetection performance was evaluated from the points of electrolyte composition, working temperature, and bias voltage. This study would pave the way for the controllable synthesis and applications of bismuth-based ternary compounds.

A high-performance and self-powered polarization-sensitive photoelectrochemical-type Bi2O2Te photodetector based on a quasi-solid-state gel electrolyte.

Among the two-dimensional (2D) Bi2O2X (X = S, Se, and Te) series, Bi2O2Te has the smallest effective mass and the highest carrier mobility. However, Bi2O2Te has rarely been investigated, most likely due to the lack of feasible methods to synthesize 2D Bi2O2Te. Herein, 2D Bi2O2Te nanosheets are successfully synthesized by low-temperature oxidation of Bi2Te3 nanosheets synthesized using a solvothermal method. The performance of a quasi-solid-state photoelectrochemical-type (PEC-type) photodetector based on 2D Bi2O2Te nanosheets is systematically investigated. Remarkably, the device has a high responsivity of 20.5 mA W-1 (zero bias) and fast rise/fall times of 6/90 ms under 365 nm illumination, which is superior to the majority of PEC-type photodetectors based on bismuth-based compounds. More importantly, due to the strong anisotropy of 2D Bi2O2Te nanosheets, the device achieves a dichroic ratio as high as 52, which belongs to the state-of-the-art polarized photodetectors. Besides, the capacity of 2D Bi2O2Te for high-resolution polarization imaging is demonstrated. This work provides a promising strategy for the synthesis of 2D Bi2O2Te nanosheets to fabricate a high-performance and polarization-sensitive photodetector.

Mechanistic insights into bismuth(iii) inhibition of SARS-CoV-2 helicase.

The COVID-19 pandemic caused by SARS-CoV-2 resulted in a global public health crisis. In addition to vaccines, the development of effective therapy is highly desirable. Targeting a protein that plays a critical role in virus replication may allow pan-spectrum antiviral drugs to be developed. Among SARS-CoV-2 proteins, helicase (i.e., non-structural protein 13) is considered as a promising antiviral drug target due to its highly conserved sequence, unique structure and function. Herein, we demonstrate SARS-CoV-2 helicase as a target of bismuth-based antivirals in virus-infected mammalian cells by a metal-tagged antibody approach. To search for more potent bismuth-based antivirals, we further screened a panel of bismuth compounds towards inhibition of ATPase and DNA unwinding activity of nsp13 and identified a highly potent bismuth compound Bi(5-aminotropolonate)3, namely Bi(Tro-NH2)3 with an IC50 of 30 nM for ATPase. We show that bismuth-based compounds inhibited nsp13 unwinding activity via disrupting the binding of ATP and the DNA substrate to viral helicase. Binding of Bi(iii) to nsp13 also abolished the interaction between nsp12 and nsp13 as evidenced by immunofluorescence and co-immunoprecipitation assays. Finally, we validate our in vitro data in SARS-CoV-2 infected mammalian cells. Notably, Bi(6-TG)3 exhibited an EC50 of 1.18 ± 0.09 μM with a selective index of 847 in VeroE6-TMPRSS2 infected cells. This study highlights the important role of helicase for the development of more effective antiviral drugs to combat SARS-CoV-2 infection.

Room temperature high thermoelectric performance of Bi-based full-Heusler compounds CsxRb[formula omitted]Bi with strong anharmonicity

Bismuth-based compounds have been identified as a class of promising candidates for the realization of high-performance thermoelectrics, derived from their exceptional electrical conductivity and intrinsic low lattice thermal conductivity κL. Here, we employed first-principles calculations, self-consistent phonon theory, and compressive sensing technique in conjunction with the Boltzmann transport equation to investigate the anharmonic thermoelectric properties of full-heusler bismuth compounds CsxRb3−xBi. As the Cs content increases, the κL of CsxRb3−xBi decreases due to impurity scattering effects, and then increases. Among them, at 300 K, Rb3Bi has the largest κL of 0.69 Wm−1K−1, while Cs2RbBi has the smallest κL of 0.45 Wm−1K−1, both of which are lower than the κL of traditional bismuth-based thermoelectric materials. The ultralow κL originates from the strong lattice anharmonicity. In addition, the coexistence of high dispersion and flat band edges leads to high thermoelectric power factor at optimal doping concentration. As a result, the largest thermoelectric figure of merit ZT values of 2.59 (4.19) at 300 (500) K were obtained for CsRb2Bi at optimal hole doping level. These findings suggest that CsxRb3−xBi compounds are superior for thermal management and thermoelectric applications.

Unusual Hybrid Magnesium Storage Mechanism in a New Type of Bi2O2CO3 Anode.

Bismuth and bismuth-based compounds have been extensively studied as anodes as prospective candidates for rechargeable magnesium batteries (rMBs). However, the unsatisfactory magnesium-storage capability caused by the typical alloying reaction mechanism severely restricts the practical option for anodes in rMBs. Herein, polyaniline intercalated Bi2O2CO3 nanosheets are prepared by an effective interlayer engineering strategy to fine-tune the layer structure of Bi2O2CO3, achieving enhanced magnesium-storage capacity, rate performance, as well as long cycle life. Excitedly, a stepwise insertion-conversion-alloying reaction is aroused to stabilize the performance, which is elucidated by in/ex situ investigations. Moreover, first-principles calculations confirm that the coupling of Bi2O2CO3 and polyaniline not only increases the conductivity induced by the strong density of states and the interior self-built-in electric field but also significantly reduces the energy barrier of Mg shuttles. Our findings shed light on exploring new electrode materials with an appropriate working mechanism toward high-performance rechargeable batteries.

Biological Activities of Bismuth Compounds: An Overview of the New Findings and the Old Challenges Not Yet Overcome.

Bismuth-based drugs have been used primarily to treat ulcers caused by Helicobacter pylori and other gastrointestinal ailments. Combined with antibiotics, these drugs also possess synergistic activity, making them ideal for multiple therapy regimens and overcoming bacterial resistance. Compounds based on bismuth have a low cost, are safe for human use, and some of them are also effective against tumoral cells, leishmaniasis, fungi, and viruses. However, these compounds have limited bioavailability in physiological environments. As a result, there is a growing interest in developing new bismuth compounds and approaches to overcome this challenge. Considering the beneficial properties of bismuth and the importance of discovering new drugs, this review focused on the last decade's updates involving bismuth compounds, especially those with potent activity and low toxicity, desirable characteristics for developing new drugs. In addition, bismuth-based compounds with dual activity were also highlighted, as well as their modes of action and structure-activity relationship, among other relevant discoveries. In this way, we hope this review provides a fertile ground for rationalizing new bismuth-based drugs.

Perovskite-Like Strontium Bismuth Oxyhalides: Synthesis, Characterisation, Photocatalytic Activity and Degradation Mechanism

Recent studies have demonstrated that bismuth oxyhalides with a 2D structure inhibit the recombination of electron–hole pairs. Further, perovskite-like strontium bismuth-based compounds with a special layered Sillen X1 structure have shown potential for use as effective visible-light photocatalysts. Here, a series of strontium bismuth oxyhalide composites were prepared under different calcination conditions. The sample compositions were controlled by modulating the calcination temperature and the secondary calcination time. The synthesised catalysts were characterised by various techniques to identify the product compositions. Under visible-light irradiation, the degradation efficiencies and photocatalytic activities of the different catalysts towards rhodamine B (RhB) and 2-hydroxybenzoic acid (2-HBA) were measured via UV–Vis PDA and electron paramagnetic resonance analyses. To explore the degradation mechanism, scavengers were utilised to detect the radicals produced in the photodegradation test. SrBiO2Cl exhibited the best RhB degradation efficiency, of 0.0685 h−1, and SrBiO2Br exhibited a rate of 0.0984 h−1. At 25 °C and 1 atm, the CO2–CH4 photocatalytic conversion efficiencies of the optimised SrBiO2Cl and SrBiO2Br samples increased to 0.037 and 0.053 μmol g−1 h−1, respectively. The findings confirm that the catalysts are highly recyclable and effective for environmental remediation, achieving the objectives of green chemistry.

Bismuth-Based Metal Clusters─From Molecular Aesthetics to Contemporary Materials Science.

ConspectusBismuth-based research has become a highly topical field in recent years, yielding remarkable prospects for new fundamental insights and new materials applications, ranging from innovative catalysts to novel pharmaceuticals, due to this heavy metal's virtually nonradioactive and nontoxic properties. Given that the 6s2 electron pair can be stereochemically active under certain circumstances, bismuth atoms adopt a variety of coordination modes and bonding environments with oxidation states ranging from (formally) +V to -III. As a consequence, bismuth-based compounds cover the entire spectrum from simple coordination compounds to much more unusual cluster cations and cluster anions exhibiting metal-metal bonding in a homoatomic manner, or in concert with other s-, d-, p-, or f-block metal atoms. Such bismuth clusters show high potential for the development of new bismuth-based materials, but they are also interesting objects by themselves. Given the relatively recent development of bismuth-rich cluster molecules, a deep understanding of their properties─including unprecedented structural features, complex electronic structures, substantial heavy metal aromaticity, as well as their formation pathways─is still in its infancy. The topic thus spans a broad range from highly sophisticated synthetic chemistry through interdisciplinary experimental and theoretical analyses to materials science.Based on our recent work and several notable reports from other groups, this article will highlight the successful access to a number of novel bismuth-rich cluster ions emerging from both solution-based approaches and solid-state chemistry. It will shed light on the unique structural and electronic properties that cause chemical and physical peculiarities of such compounds. Selected examples include, but are not limited to, (1) the first encapsulation of actinide ions in intermetalloid clusters which additionally served to manifest substantial all-metal π-aromaticity with a (calculated) record ring current per electron; (2) a large metalloid {Zn12} unit stabilized in a porphine-related {Zn8Bi16} moiety in [K2Zn20Bi16]6-; (3) the largest assembly of bismuth atoms within one molecule, observed in [{Ru(cod)}4Bi18]4- that consists of two Bi-Bi-linked "[{Ru(cod)}2Bi9]2-" subunits.Notably, cluster growth has remained largely a black box, which is starting to be revealed, however. We discuss possible formation pathways of such (multi)metallic nanoarchitectures on the basis of smaller subunits that were detected by mass spectrometric analyses and could also be captured upon reaction with organometallic complexes. In addition to the intrinsic structural and electronic properties of the cluster anions and cluster cations reviewed herein, we will briefly introduce the emerging usage of bismuth-based compounds in material science and give an outlook to future developments.

Interfacial bond endowing FeS2/Bi2S3 composites superb OER performance

Developing high-efficient main group element Bismuth-based OER electrocatalysts is of great significance to sustainable energy storage and conversion. However, they still suffer from structural deficiencies such as poor electroconductivity, lack of active sites and high absorption energy barriers. Constructing Fe-contained Bismuth-based compounds is regarded as an effective strategy to ameliorate the above deficiencies. In this study, core-shell structured FeS2/Bi2S3 composites are achieved successfully with solvothermal and sulfurization method by constructing interfacial bond Bi–S–Fe. Through in-depth analysis, we confirm that the interfacial chemical bond Bi–S–Fe, act as a bridge to the linkage of FeS2 and Bi2S3, enhance electron transport efficiency and hydrophilicity by regulating charge ordering. Moreover, the proportion of metal active centers (Fe3+, Fe2+, Bi3+, Bi2+) with different absorption/desorption energy could also be modulated by Bi–S–Fe, thus endowing FeS2/Bi2S3 composites a superb OER performance. As expected, FeS2/Bi2S3-0.33 shows ultralow overpotentials of 313 and 419 mV at current densities of 10 and 100 mA cm−2, respectively, and a Tafel slope as low as 25 mV dec−1, which outperforms most of Bismuth-based and even noble/transition metal-based electrocatalysts. This work may shed light on construction of interfacial bond for rational design of high-performance OER catalysts.

Bismuth-based compounds as efficient sulfur hosts for novel lithium-sulfur batteries

Bismuth-based compounds as efficient sulfur hosts for novel lithium-sulfur batteries

Synthesis of Co3O4 Nanoparticles-Decorated Bi12O17Cl2 Hierarchical Microspheres for Enhanced Photocatalytic Degradation of RhB and BPA

Three-dimensional (3D) hierarchical microspheres of Bi12O17Cl2 (BOC) were prepared via a facile solvothermal method using a binary solvent for the photocatalytic degradation of Rhodamine-B (RhB) and Bisphenol-A (BPA). Co3O4 nanoparticles (NPs)-decorated BOC (Co3O4/BOC) heterostructures were synthesized to further enhance their photocatalytic performance. The microstructural, morphological, and compositional characterization showed that the BOC microspheres are composed of thin (~20 nm thick) nanosheets with a 3D hierarchical morphology and a high surface area. Compared to the pure BOC photocatalyst, the 20-Co3O4/BOC heterostructure showed enhanced degradation efficiency of RhB (97.4%) and BPA (88.4%). The radical trapping experiments confirmed that superoxide (•O2-) radicals played a primary role in the photocatalytic degradation of RhB and BPA. The enhanced photocatalytic performances of the hierarchical Co3O4/BOC heterostructure are attributable to the synergetic effects of the highly specific surface area, the extension of light absorption to the more visible light region, and the suppression of photoexcited electron-hole recombination. Our developed nanocomposites are beneficial for the construction of other bismuth-based compounds and their heterostructure for use in high-performance photocatalytic applications.

Temperature-controlled electrochemical sensor based on environmentally responsive polymer/BiPO4/BiOCl/multi-walled carbon nanotube composite for the detection of catechol in water

Catechol is a phenolic environmental pollutant that is highly toxic to living organisms and is released into the environment, where it is difficult to degrade in the ecosystem, thereby contaminating the environment and groundwater. Here, P(NIPAM-co-BMA)/BiPO4/BiOCl/MWCNTs nanocomposites were synthesized, and a temperature-controlled "on/off" electrochemical sensor was constructed. In addition, the P(NIPAM-co-BMA)/BiPO4/BiOCl/MWCNTs/GCE sensor shows good thermal sensitivity and electrochemical detection of catechol. Reproducible "on/off" switching on the CVs curve can be achieved by controlling the temperature of the solution. Under optimal conditions, the sensor was able to detect catechol in the linear range of 0.5–86.51 μM with a limit of detection of 0.2 μM (S/N = 3). Satisfactory results were obtained for the detection of natural environmental samples (tap water). In addition, the redox mechanism and electrochemical reaction sites of catechol were investigated by scanning rates. This work demonstrates for the first time the combination of temperature-sensitive polymers, bismuth-based compounds and multi-walled carbon nanotubes as electrochemical sensors for the detection of catechol, opening a new window for the sensitive detection of catechol. At the same time, the constructed switch-like electrochemical sensors can be better applied to different special scenarios.

Comparative DFT calculations on Bismuth-based compounds: new connection between optoelectronic properties and 209Bi and 51 V NMR and EFG

Comparative DFT calculations on Bismuth-based compounds: new connection between optoelectronic properties and 209Bi and 51 V NMR and EFG

Polymer-coated BiOCl nanosheets for safe and regioselective gastrointestinal X-ray imaging.

Bismuth-based compounds are considered to be the best candidates for computed tomography (CT) imaging of gastrointestinal (GI) tract due to high X-ray absorption. Here, we report the introduction of polymer-coated bismuth oxychloride (BiOCl) nanosheets for highly efficient CT imaging in healthy mice and animal with colitis. We demonstrate simple, low cost and fast aqueous synthesis protocol which provides gram-quantity yield of chemically stable BiOCl nanosheets. The developed contrast gives 2.55-fold better CT enhancement compared to conventional contrast with negligible in vivo toxicity. As a major finding we report a regioselective CT imaging of GI tract by using nanoparticles coated with differentially charged polymers. Coating of nanoparticles with a positively charged polymer leads to their fast accumulation in small intestine, while the coating with negatively charged polymers stimulates prolonged stomach retention. We propose that this effect may be explained by a pH-controlled aggregation of nanoparticles in stomach. This feature may become the basis for advancement in clinical diagnosis of entire GI tract.

Rapid Aqueous-Phase Synthesis and Photoluminescence Properties of K0.3Bi0.7F2.4:Ln3+ (Ln = Eu, Tb, Pr, Nd, Sm, Dy) Nanocrystalline Particles

Trivalent lanthanides (Ln3+) doped bismuth-based inorganic compounds have attracted considerable interest as promising candidates for next-generation inorganic luminescent materials. Here, a series of K0.3Bi0.7F2.4 (KBF) nanocrystalline particles with controlled morphology have been synthesized through a low-temperature aqueous-phase precipitation method. Using KBF as the host matrix, Eu3+, Tb3+, Pr3+, Nd3+, Sm3+, and Dy3+ ions are introduced to obtain K0.3Bi0.7F2.4:Ln3+ (KBF:Ln) nanophosphors. The as-prepared KBF:Ln nanophosphors exhibit commendable photoluminescence properties, in which multicolor emissions in a single host lattice can be obtained by doping different Ln3+ ions when excited by ultraviolet light. Moreover, the morphology and photoluminescence performance of these nanophosphors remain unchanged under different soaking times in water, showing good stability in a humid environment. The proposed simple and rapid synthesis route, low-cost and nontoxic bismuth-based host matrix, and tunable luminescent colors will lead the way to access these KBF:Ln nanophosphors for appealing applications such as white LEDs and optical thermometry.

Bismuth-based mixed-anion compounds for anode materials in rechargeable batteries.

A facile solvothermal synthesis approach for chemical composition control in ternary Bi-S-I systems is reported by simply controlling the sulfide concentration. We demonstrate the application of these bismuth-based ternary mixed-anion compounds as high capacity anode materials in rechargeable batteries. Cells utilising Bi13S18I2 achieved an initial capacity value of 807 mA h g-1, while those with BiSI/Bi13S18I2 a value of 1087 mA h g-1 in lithium-ion battery systems.

Effect of Bi/Ti ratio on (Na0.5Bi0.5)TiO3/Bi4Ti3O12 heterojunction formation and photocatalytic performance

Bismuth-based metal oxide compounds are promising candidates as novel photocatalysts for environmental remediation. However, their low quantum efficiencies and rapid electron-hole recombination times have hindered their uptake for photocatalytic applications. The present work reports an investigation of the effects of variable Bi/Ti ratio during hydrothermal synthesis on the phase assemblage, nanostructure, surface chemistry, band gap, and photocatalytic performance. Increasing Ti concentration resulted in variations in characteristics and properties according to the sequential formation of the principal phases α-Bi2O3 (BO), Bi4Ti3O12 (BTO), and (Na0.5Bi0.5)TiO3 (NBT). Samples fabricated with precursors having a Bi/Ti ratio of 12/12 exhibited the highest methylene blue (MB) photodegradation rate of 92% under UV irradiation for 2 h. This excellent photocatalytic performance is attributed to the formation of an NBT/BTO heterojunction with advantageous band alignment.

Synthesis of Thin Bi9 O7.5 S6 Nanosheets for Improved Photodetection in a Wide Wavelength Range.

Bismuth-based compounds possess layered structures with a variety of stacking modes, endowing the compounds with diverse properties. As one type of bismuth oxysulfides, Bi9 O7.5 S6 nanocrystals has great applications in photodetection; however, the responsivity of bulky Bi9 O7.5 S6 is limited due to the poor charge separation. Herein, single-crystalline Bi9 O7.5 S6 thin nanosheets are successfully synthesized by using a solvothermal method. The thickness of the obtained Bi9 O7.5 S6 nanosheets is down to 15 nm and can be easily tuned by varying the reaction period. Moreover, the Bi9 O7.5 S6 nanosheets show strong light absorption in the visible and near infrared range, making it a promising candidate in optoelectronics. As a demonstration, the thin Bi9 O7.5 S6 nanosheets are used as active layer in an optoelectronic device, which exhibits sensitive photoelectric response to light in a wide range of 400-800 nm. The responsivity of the device reaches up to 1140 μA W-1 , and the performance of the device is stable after long-period illumination. This work demonstrates a great potential of the thin Bi9 O7.5 S6 nanosheets in optoelectronic devices, and these nanosheets may also be extended to various optoelectronic applications.