Exploiting Two‐Dimensional Bi2O2Se for Trace Oxygen Detection

We exploit a high‐performing resistive‐type trace oxygen sensor based on 2D high‐mobility semiconducting Bi₂O₂Se nanoplates. Scanning tunneling microscopy combined with first‐principle calculations confirms an amorphous Se atomic layer formed on the surface of 2D Bi₂O₂Se exposed to oxygen, which contributes to larger specific surface area and abundant active adsorption sites. Such 2D Bi₂O₂Se oxygen sensors have remarkable oxygen‐adsorption induced variations of carrier density/mobility, and exhibit an ultrahigh sensitivity featuring minimum detection limit of 0.25 ppm, long‐term stability, high durativity, and wide‐range response to concentration up to 400 ppm at room temperature. 2D Bi₂O₂Se arrayed sensors integrated in parallel form are found to possess an oxygen detection minimum of sub‐0.25 ppm ascribed to an enhanced signal‐to‐noise ratio. These advanced sensor characteristics involving ease integration show 2D Bi₂O₂Se is an ideal candidate for trace oxygen detection.     

Highly sensitive,humidity-tolerant and flexible NO2 sensors based on nanoplate Bi2Se3 film

Recently, two-dimension (2D) materials have fueled considerable interest in the field of gas sensing to cope urgent demands at specific scenarios. Unfortunately, the susceptibility to ambient humidity, and/or fragile operation stability always frustrate their further practicability. To overcome these drawbacks, we proposed one novel flexible gas sensor based on bismuth selenide (Bi₂Se₃) nanoplates for sensitive NO₂ detection at room temperature. The as-prepared Bi₂Se₃ sensor exhibited favorable sensing performance, including remarkable NO₂ selectivity, high response of 120% and fast response time of 81 s toward 5 ppm NO₂, an ultralow detection limit of 100 ppb, and nice stability. Besides, the excellent humidity tolerance and mechanical flexibility endowed Bi₂Se₃ sensors with admirable reliability under harsh working conditions. The first-principles calculation further revealed the insights of extraordinary NO₂ selectivity and the underlying gas-sensing mechanism.     

Thermochemische Untersuchungen zum System Bi/Se/O. I. Das Phasendreieck Bi2Se3/Bi2O2Se/Se

Thermochemical Investigation on the System Bi/Se/O. I The Phase Triangle Bi₂Se₃/Bi₂O₂Se/Se By total pressure measurements of compositions in the subsystem Bi₂Se₃/Bi₂O₂Se/Se was shown, that in thermodynamic equilibrium the three phases Bi₂Se₃/Bi₂O₂Se/Se coexist. The barogram of the triangle reduces to the barogram of the line Bi₂Se₃? Se, the compound Bi₂O₂Se is not from influence of the total pressure in the investigated temperature range.     

Sensitive Electrochemical Detection of Pb(II) and H2O2 via a Dual-functional Sn-doped Defective Bi2S3 Microspheres

In this work, a dual-functional electrochemical sensor has been proposed based on Sn-doped defective Bi₂S₃ (TDDB) microspheres, which exhibited the excellent electrochemical performance on Pb(II) and H₂O₂ detection. The TDDB offered a satisfied detection limit of 8.0 nM towards Pb(II) with a sensitivity of 96.7 μA ⋅ μM⁻¹. As a H₂O₂ sensor, a high sensitivity of 3540 μA mM⁻¹ cm⁻² was obtained in a linear range from 0.45 mM to 10 mM with a detection limit of 10 nM. Moreover, the electrochemical detection of Pb(II) in Taihu Lake and H₂O₂ in human serum was achieved with high reliability and good recovery.     

Die Kristallstruktur von Bi2O2Se

Bi₂O₂Se crystallizes in the (Na_0.25Bi_0.75)₂O₂Cl type structure (space group I4mmm–D _4h ¹⁷ ;a=3.891 Å,c=12.21₃ Å). The crystal chemical properties of the bismuth oxiselenide are discussed in connection with the other compounds having this structure type.

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Herrn Prof. Dr.F. Hecht zum 70. Geburtstag gewidmet.     

In-Situ Hydrogen-Bond Tailoring To Construct Ultrathin Bi2O2O/Bi2O2(OH)(NO3) Nanosheets: Interactive CO2RR Promotion and Bismuth-Oxygen Moiety Preservation

Bismuth–oxygen moieties are beneficial for high-efficiency electrochemical CO₂ reduction (CO₂RR) to produce formate; however, preserving bismuth-oxygen moieties while applying a cathodic potential is challenging. This work reports the preparation of ultrathin Bi₂O₂O/Bi₂O₂(OH)(NO₃) nanosheets (BiON-uts) by in-situ tailoring of hydrogen bonds in a Bi₂O₂(OH)(NO₃) precursor. The BiON-uts exhibits a formate faradaic efficiency of 98 % with higher partial current density than that of most reported bismuth-based catalysts. Mechanistic studies demonstrate that the ultrathin nanosheet morphology facilitates ion-exchange between BiON-uts and the electrolyte to produce Bi₂O₂CO₃ as intermediate, and adsorption of CO₂ with surface Bi₂O₂O. DFT calculations reveal that the rate-limiting first electron transfer is effectively improved by the high electron affinity of Bi₂O₂CO₃. More importantly, high-efficiency CO₂RR in turn protects the bismuth–oxygen moieties from being reduced and thus helps to maintain the excellent CO₂RR activity. This work offers an interactive mechanism of CO₂RR promotion and bismuth–oxygen moiety preservation, opening up new opportunities for developing high-performance catalysts.     

Application of radiochloramine-T for the determination of trace amounts of hydrogen sulphide

Hydrogen sulphide at trace level can be determined by radiorelease technique using radiochloramine-T. The minimum detection level is 0.25 ppm. Zinc acetate is used to fix H₂S from air samples. CS₂ does not interfere. Interference by SO₂ can be eliminated by oxidizing it with H₂O₂.     

3D Nano‐structure L‐cysteine/AuNPs/Bi2O3 Modified Glass Carbon Electrode as Chemical Sensor for Highly Sensitive and Selective Detection Cu (II)

It was first time using the l‐cysteine self‐assembled on the surface of gold nanoparticles and Bi₂O₃ nano‐structured materials modified GCE composed l‐cysteine/AuNPs/Bi₂O₃/GCE sensor. The sensor possessed three‐dimensional nanostructure and exhibited a higher ratio of activity sites, large active surface, fast electron transfer rate, excellent catalytic, sensing characteristics and larger affinity to Cu (II). The sensor was determined to have an excellent sensitivity and selectivity for the detection of Cu (II). The characterization of sensor as well as the optimization of the analytical procedure was reported. The optimized conditions parameters allowed the detection of Cu (II) concentration following short analysis time, a detection limit of 5×10^?11 M at 80 s of preconcentration time was obtained using the as‐prepared sensor, and also show excellent stability and good repeatability, and, thus, could be used for detection of Cu (II) in environment.     

Untersuchung der Phasenbeziehungen in quaternären Systemen Bi2O3/Bi2Ch/Bi2Ch (Ch = S,Se, Te)

Investigations of the Phase Relations in the Quaternary Systems Bi₂O₃/Bi₂Ch /Bi₂Ch (Ch = S, Se, Te) The stability ranges in the pseudobinary systems Bi₂O₂S/Bi₂O₂Se, Bi₂O₂S/Bi₂O₂Te and Bi₂O₂Se/Bi₂O₂Te have been studied by solid state and chemical transport reactions. A complete mixed crystal Bi₂O₂(Te_xSe_1–x), 0 ≤ x ≤ 1 exists between the ternary compounds Bi₂O₂Te and Bi₂O₂Se. The thermal behaviour of the mixed crystal and the coexistence ranges have been determined by x‐ray and thermal analysis.     

Oxygen-vacancy-enhanced Catalytic Activity of Au@Co3O4/CeO2 Yolk-shell Nanocomposite to Electrochemically Detect Hydrogen Peroxide

Biomimetic electrochemical sensors are very promising not only due to their lower expense and longer stability than conventional enzymatic ones, but they also often suffer from simultaneously achieving high sensitivity and good selectivity. Here we present a well-defined Au@Co₃O₄/CeO₂ yolk-shell nanostructure (YSN) that is first synthesized and exploited as highly efficient electrocatalysts for hydrogen peroxide (H₂O₂) detection. The introduced CeO₂ in Co₃O₄ matrix greatly facilitates the migration of lattice oxygen, which increases the concentration of surface oxygen vacancies (O_a), remarkably enhancing the adsorption ability of H₂O₂ and promoting the decomposition of H₂O₂ for faster electron transfer than pristine Au@Co₃O₄ core-shell nanostructure (CSN). The abundant O_a of Au@Co₃O₄/CeO₂ YSN is confirmed by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The as-prepared biomimetic sensor delivers a wide dynamic range (5.0 nM to 5.4 μM), a low limit of detection (LOD) (2.74 nM), and a high sensitivity (35.67 μA μM⁻¹ cm⁻²), paving a new way to construct an ultrasensitive and selective enzyme-free biomimetic electrochemical sensor. Furthermore, the sensor is used to real-time monitor H₂O₂ released from human cervical cancer cells (HeLa) and human umbilical vein endothelial cells (HUVEC), demonstrating its great potential in practical applications.     

Two-step colloidal synthesis of micron-scale Bi2O2Se nanosheets and their electrostatic assembly for thin-film photodetectors with fast response

Recently discovered bismuth oxychalcogenide (Bi₂O₂Se) has aroused great interest due to its ultrahigh carrier mobility, tunable band gap and good environmental stability, making it a promising candidate for high-performance electronics and optoelectronics. Their synthesis by colloidal approaches represents a cost-effective alternative to well-established chemical vapor deposition methods, and the resulting electronic-grade inks are important for large-area printed or wearable electronics. However, it is still challenging to control the colloidal growth of Bi₂O₂Se nanosheets in solution in addition to their assembly into high-performance thin films. Here, we report a two-step colloidal synthesis of Bi₂O₂Se nanosheets by separating the seeding and growth steps, thereby achieving controllable production of nanosheets with a lateral size of 1.4 μm and a thickness of 10 nm at optimized reaction conditions. These Bi₂O₂Se nanosheets are electrostatically assembled into large-area thin films, from which a photodetector is fabricated with a responsivity of 6.1 A/W and a short response time of 368 μs under the 520-nm laser illumination. The device exhibits fast response to modulations as high as 100 kHz, along with a −3 dB bandwidth of 1 kHz. This work provides an important understanding of the controlled colloidal synthesis of Bi₂O₂Se nanosheets, and demonstrates their potential applications in fast photodetectors.     

A nanosized Y(2)O(3)-based catalytic chemiluminescent sensor for trimethylamine

The development of a catalytic chemiluminescent trimethylamine (TMA) sensor is demonstrated in the present paper. Intensive chemiluminescence (CL) is detected when TMA is introduced over the surface of nanosized catalysts and subsequently catalytically oxidized by O₂ from the air, and four catalysts are investigated with the strongest CL intensity obtained on nanosized Y₂O₃. This effect is utilized to develop a novel nanosized Y₂O₃-based catalytic CL sensor for TMA which under optimal conditions exhibits a wide linear range of 60-42,000 ppm and a detection limit of 10 ppm. An attractive advantage of this novel CL sensor is its high selectivity to TMA with negligible responses to many other gases such as NH₃ and organic vapors. This CL sensor has a short response time of less than 3 s, and shows good stability when examined by continual introduction of TMA into the sensor for 96 h. The applicability of this sensor to actual fish samples is also demonstrated in the paper.     

Direct in situ spectroscopic evidence of the crucial role played by surface oxygen vacancies in the O2-sensing mechanism of SnO2

Conductometric gas sensors (CGS) provide a reproducible gas response at a low cost but their operation mechanisms are still not fully understood. In this paper, we elucidate the nature of interactions between SnO₂, a common gas-sensitive material, and O₂, a ubiquitous gas central to the detection mechanisms of CGS. Using synchrotron radiation, we investigated a working SnO₂ sensor under operando conditions via near-ambient pressure (NAP) XPS with simultaneous resistance measurements, and created a depth profile of the variable near-surface stoichiometry of SnO_2−x as a function of O₂ pressure. Our results reveal a correlation between the dynamically changing surface oxygen vacancies and the resistance response in SnO₂-based CGS. While oxygen adsorbates were observed in this study we conclude that these are an intermediary in oxygen transport between the gas phase and the lattice, and that surface oxygen vacancies, not the observed oxygen adsorbates, are central to response generation in SnO₂-based gas sensors.

NAP-XPS characterisation of SnO₂ under operando conditions shows that resistance change, band bending and surface O-vacancy concentration are correlated with ambient O₂ concentration, challenging current preconceptions of gas sensor function.     

A fiber-optic evanescent wave sensor for dissolved oxygen detection based on novel hybrid fluorinated xerogels immobilized with [Ru(bpy)3]2+

We have prepared a novel fiber-optic evanescent wave sensor (FEWS) for dissolved oxygen (DO) detection. The sensor fabrication was based on coating a decladded portion of an optical fiber with a microporous coating, which was prepared from 3,3,3-trifluoropropyltrimethoxysilane and n-propyltrimethoxysilane. The fluorophores were immobilized in the porous coating and excited by the evanescent wave field produced on the core surface of the optical fiber. The sensitivity of the sensor was quantified by the ratio of the fluorescence intensities in pure deoxygenated (I ₀) and in pure oxygenated environments (I). Results show that the quenching response of DO is increased with the enhancement of the coating surface hydrophobicity using the presented hybrid fluorinated ORMOSILs. The calibration curve of I ₀/I to [O₂] is linear from 0 to 40 ppm and the detection limit is 0.05 ppm (3σ) with a short response time of 15 s for DO detection. Figure       

A Novel Hydrogen Peroxide Amperometric Sensor Based on Hierarchical 3D Porous MnO2−TiO2 Composites

A novel nanocomposite electrode based on hierarchical 3D porous MnO₂?TiO₂ for the application in hydrogen peroxide (H₂O₂) sensors has been explored. This electrode was fabricated by growing TiO₂ cross‐linked nanowires on a commercial fluorine tin oxide (FTO) glass via a hydrothermal process and subsequent deposition of 3D honeycomb‐like MnO₂ nanowalls using an electrodeposition method (denoted as 3D MNS‐TNW@FTO). The obtained 3D MNS‐TNW@FTO electrode was characterized by scanning electron microscopy (SEM), Raman spectroscopy, X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). Based on such a unique 3D porous framework and the existence of MnO₂, the electrode demonstrates a good performance in the detection of H₂O₂, with two linear ranges from 9.8 to 125 μM and 125 μM–1.0 mM, a good selectivity of 8.02 μA mM^?1 cm^?2, and a low detection limit of 4.5 μM. In addition, the simplicity of the developed low‐cost fabrication process provides an efficient method for the mass production of electrocatalytical MnO₂?TiO₂ nanocomposites on commercial FTO glass for H₂O₂ sensing applications and can be adapted for other electrochemical sensors for various biochemical targets. It thus is beneficial for the practical usage in bioanalysis.     

Bulk Modification of Carbon Paste Electrode with Bi2O3 Nanoparticles and Its Application as an Electrochemical Sensor for Selective Sensing of AntiHIV Drug Nevirapine

Bi₂O₃ nanoparticles were synthesized by solution combustion method and utilized for fabrication of an electrochemical sensor [carbon paste electrode modified with Bi₂O₃ (CPE‐Bi₂O₃)] for nevirapine (NVP). Electrode materials were characterized by XRD, FTIR, TG‐DTA, AFM and SEM‐EDS methods. CPE‐Bi₂O₃ was electroreduced (Er) in KOH in the potential range of ?1.3–0 V to obtain CPE‐ErBi₂O₃. CPE‐ErBi₂O₃ exhibited electrocatalytic activity towards the oxidation of NVP. Under optimized conditions, linearity between the peak current and NVP concentration was observed in the range of 0.05–50 µM. Further, the sensor was used for the assay of NVP in tablets and biological samples.     

Indium-organic framework CPP-3（In） derived Ag/In2O3 porous hexagonal tubes for H2S detection at low temperature

There is a great demand for high-performance hydrogen sulfide（H₂S） sensors with low operating temperatures. Ag/In₂O₃ hexagonal tubes with different proportions were prepared by the calcination of Ag+-impregnated indium-organic frameworks(CPP-3（In）), and the developed sensors exhibit enhanced gassensing performance toward H₂S. Gas sensing measurements indicate that the response of Ag/In₂O₃（2.5 wt%） sensor to 5 ppm H₂S ha...     

Preparation and visible light photocatalytic activity of Bi2O3/Bi2WO6 heterojunction photocatalysts

The Bi₂O₃/Bi₂WO₆ heterojunction photocatalysts were prepared by a two-step solvothermal process using Bi(NO₃)₃-ethylene glycol solution as Bi source. The catalysts were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflection spectroscopy. The heterostructure catalysts are composed of Bi₂O₃ nanoparticles as modifier and 3D Bi₂WO₆ microspheres as substrate. Bi₂O₃ nanoparticles with diameters of about 10-15 nm are tightly grown on the lateral surface of the Bi₂WO₆ microspheres. The hierarchical Bi₂O₃/Bi₂WO₆ microspheres exhibit higher photocatalytic activity than the single phase Bi₂WO₆ or Bi₂O₃ for the degradation of rhodamine B under visible light illumination (λ>420 nm). The enhancement of the photocatalytic activity of the Bi₂O₃/Bi₂WO₆ heterojunction catalysts can be ascribed to their improved light absorption property and the reduced recombination of the photoexcited electrons and holes during the photocatalytic reaction. The effect of loading amount of Bi₂O₃ on the catalytic performance of the heterojunction catalysts was also investigated and the optimal content of Bi₂O₃ is 3 wt%. The Bi₂O₃/Bi₂WO₆ heterojunction photocatalysts are essentially stable during the photocatalytic process.     

Gas-sensitivity properties of nanoscale Au-In<Subscript>2</Subscript>O<Subscript>3</Subscript> materials

A possibility was demonstrated of producing the chemical sensors based on Au-In₂O₃ obtained using a sol-gel technology. The sensors exhibit high sensitivity and selectivity toward CO. The differences in gas-sensitivity properties of In₂O₃ sensor with respect to CO and CH₄ at different ways of doping with Au(III) was examined. The effect of the gold nanoparticles size and the state of the indium oxide surface on the characteristics of Au-In₂O₃ and Au/In₂O₃ sensors at the detection of CO and CH₄ was examined.     

Copper Nanoflowers on Carbon Cloth as a Flexible Electrode Toward Both Enzymeless Electrocatalytic Glucose and H2O2

Herein, a novel electrochemical sensor for glucose and hydrogen peroxide (H₂O₂) detection was successfully developed through the use of Cu nanoflowers (CuNFs) combined with flexible carbon cloth (CC) substrate. The 3D flower-like CuNFs in size uniformly and firmly grow on CC substrate by a facile, scalable, one-step hydrothermal strategy. Morphology, size and surface property of the prepared CuNFs/CC were examined by SEM, EDS and TEM, respectively. The electrochemical mechanism of CuNFs/CC for glucose and H₂O₂ detection was investigated by cyclic voltammetry. High electrochemical performances were displayed with amperometric i-t curves including a wide linear range from 1.0 nM to 6.0 mM for glucose and from 1.0 μM to 36.66 mM for H₂O₂, respectively. Good sensitivity, repeatability, and stability, as well as anti-interference ability, the carbon cloth-supported CuNFs will be the promising materials for fabricating practical non-enzymatic glucose and H₂O₂ sensors.