Effective ethanol-to-CO_(2) electrocatalysis at iridium-bismuth oxide featuring the impressive negative shifting of the working potential

Since low overpotential for the anodic ethanol oxidation reaction(EOR)can favor the higher output voltage and power of direct ethanol fuel cells(DEFCs),it is critical to design new EOR catalysts with efficient ethanol-to-CO_(2)activity at low applied potentials.Thereby,carbon-supported Ir-Bi_(2)O_(3)(Ir-Bi_(2)O_(3)/C)catalysts with highly dispersive bismuth oxide on the iridium surface are designed and prepared,which can merit splitting the ethanol C–C bond and promoting the oxidation of C1 intermediates at the bifunctional interfaces.The as-obtained Ir-Bi2O3/C catalysts show superior EOR mass activity of up to ca.2250 m A mgIr-1.Moreover,they exhibit the record lowest onset oxidation potentials(0.17–0.22 V vs.RHE)and the peak potential(ca.0.58 V vs.RHE),being 130–300 m V lower than the previous landmark noble metallic catalysts.Furthermore,an apparent C1 pathway faraday efficiency(FEC1)of 28%±5.9%at 0.5 V vs.RHE can be obtained at Ir-Bi_(2)O_(3)/C.This work might provide new insights into the new anodic EOR catalysts for increasing the power of DEFCs.

Preparation of bismuth oxide/titania composite particles and their photocatalytic activity to degradation of 4-chlorophenol

Bismuth oxide/titania, one interfacial composite semiconductor with high photocatalytic activity under solar light, was prepared at low temperature. The structure was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, brunauer-emmett-teller （BET）, X-ray photoelectron spectroscopy （XPS） and diffuse reflection spectra （DRS）. The results indicate that deposited titania nanoparticles on bismuth oxide surface have micro-nano structure, and this composite material exhibits porosity and increased surface hydroxyl groups. Furthermore, the as-prepared photocatalyst shows higher photocatalytic activity to the degradation of 4-chlorophenol than pure titania or P25 under sunlight.

Preparation of bismuth subcarbonate by liquid ball-milling transformation method from bismuth oxide

In order to solve the problems of environment pollution and high cost in traditional process of bismuth subcarbonate preparation, a new process using ball-milling transformation method from NH4HCO3 and Bi2O3 was proposed. Additionally, the kinetics of bismuth subcarbonate preparation was studied. Effects of reaction temperature, particle size of bismuth oxide, solid-to-liquid ratio and concentrations of ammonium bicarbonate on the conversion rate of bismuth oxide were studied. The results indicate that the conversion rate of bismuth oxide significantly increased under the conditions of higher temperature, smaller particle size, higher concentration of ammonium bicarbonate and smaller solid-to-liquid ratio. The XRD and ICP-AES analyses show that the purity of product is high. The reaction kinetics with activation energy of 9.783 kJ/mol was analyzed by shrinking core model, and the whole transformation process is controlled by solid product layer diffusion. A semi-empirical kinetics equation was obtained to describe the conversion process.

Conversion of Catalytically Inert 2D Bismuth Oxide Nanosheets for Effective Electrochemical Hydrogen Evolution Reaction Catalysis via Oxygen Vacancy Concentration Modulation

Oxygen vacancies(Vo)in electrocatalysts are closely correlated with the hydrogen evo-lution reaction(HER)activity.The role of vacancy defects and the effect of their concentration,how-ever,yet remains unclear.Herein,Bi2O3,an unfavorable electrocata-lyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy(ΔGH*),is utilized as a perfect model to explore the func-tion of Vo on HER performance.Through a facile plasma irradia-tion strategy,Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process.Unexpectedly,while the generated oxygen vacancies contribute to the enhanced HER performance,higher Vo concentrations beyond a saturation value result in a significant drop in HER activity.By tunning the Vo concentration in the Bi_(2)O_(3)nanosheets via adjusting the treatment time,the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52×10^(24)cm^(−3)demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm^(−2),a Tafel slope of 80 mV dec−1,and an exchange current density of 316 mA cm−2 in an alkaline solution,which approaches the top-tier activity among Bi-based HER electrocatalysts.Density-functional theory calculations confirm the preferred adsorption of H*onto Bi2O3 as a function of oxygen chemical potential(ΔμO)and oxygen partial potential(PO2)and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity.This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.

Role of Bismuth Oxide in Bi-MCo_2O_4(M=Co,Ni,Cu,Zn) Catalysts for Wet Air Oxidation of Acetic Acid

Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD,TEM,ESR,UV\|DRS and XPS,and the interaction between Co and Bi was studied as well. It has been found that nano\|sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)\|containing spinel are still maintained. The shift of the binding energy of Bi\-\{\%4f\%\-\{7/2\}\} is related to the catalytic activity of these catalysts doped with bismuth oxide.

Reduction smelting on bismuth oxide residue in FeO-SiO2-CaO ternary slag system

Reduction smelting of the bismuth oxide residue from pressure leaching of bismuth sulfide was investigated in the FeO-SiO_2-CaO ternary slag system.The results show that all the recovery ratios of Bi,Ag,Cu and Pb increase with the increase of reductive coal proportion,reaction temperature and time,while too much reductive coal would help Fe enter metal phase;CaO/SiO_2and Fe O/SiO_2 of the chosen slag system should be 0.5-0.75 and 1.25-1.75,respectively,for the reason that the slag system has the optimum mobility and is beneficial for the recovery of metals.The corresponding optimum conditions are determined as follows:the added coal proportion is 7%of the leaching residue,CaO/SiO_2 mass ratio in the chosen slag system is 0.5 and FeO-SiO_2 is 1.5,the reaction temperature is 1300°C and the reaction time is 40 min.Under the above conditions,the recovery ratios of Bi,Ag,Cu and Pb are 99.6%,99.8%,97.0%and 97.3%,respectively.

Boosting CO_(2) electroreduction to formate via bismuth oxide clusters

Supported metal(oxide)clusters,with both rich surface sites and high atom utilization efficiency,have shown improved activity and selectivity for many catalytic reactions over nanoparticle and single atom catalysts.Yet,the role of cluster catalysts has been rarely reported in CO_(2)electroreduction reaction(CO_(2)RR),which is a promising route for converting CO_(2)to liquid fuels like formic acid with renewable electricity.Here we develop a bismuth oxide(BiOn)cluster catalyst for highly efficient CO_(2)RR to formate.The BiOn cluster catalyst exhibits excellent activity,selectivity,and stability towards formate production,with a formate Faradaic efficiency of over 90%at a current density up to 500 mA·cm^(−2)in an alkaline membrane electrode assembly electrolyzer,corresponding to a mass activity as high as 3,750 A·gBi−1.The electrolyzer with the BiOn cluster catalyst delivers a remarkable formate production rate of 0.56 mmol·min−1 at a high single-pass CO_(2)conversion of 44%.Density functional theory calculations indicate that Bi4O_(3)cluster is more favorable for stabilizing the HCOO^(*)intermediate than Bi(001)surface and single site BiC_(4)motif,rationalizing the improved formate production over the BiOn cluster catalyst.This work highlights the great importance of cluster catalysts in activity and selectivity control in electrocatalytic CO_(2)conversion.

Visible light photocatalytic bismuth oxide coatings are effective at suppressing aquatic cyanobacteria and degrading free-floating genomic DNA

Access to safe drinking water free from microbial pollution is an issue of global concern. The use of photocatalytic thin films in water treatment has focused on titanium dioxide, which requires UV-activation, proving a potential barrier to upscaling and implementation in the real world. Visible-light-activated photocatalytic thin films, such as bismuth oxide, have recently been shown to have antimicrobial properties. However, more understanding of the photocatalytic effect on the microbial population in water is required. Glass beads coated with bismuth oxide were incubated with either Microcystis aeruginosa, Anabaena sp. or free-floating genomic DNA. The presence of bismuth oxide-coated glass beads was able to rapidly stop a population of cyanobacteria from increasing. The coated beads were also able to degrade genomic DNA. Leachate from the beads showed no increase in toxicity against human liver cells. This data demonstrates the efficacy of bismuth oxide-coated glass beads for controlling potentially dangerous cyanobacterial populations, whilst potentially reducing the amount of free-floating genomic DNA(an essential issue in the face of antimicrobial resistance) – all of which should be essential considerations in emerging water treatment technologies.

Novel environmentally friendly inorganic red pigments based on calcium bismuth oxides

Novel environmentally friendly inorganic red pigments based on calcium bismuth oxide Ca3(Bi1-xREx)8O15(0≤x≤0.09;RE=Sc^(3+),Er^(3+),Y^(3+),Ho^(3+)and Dy^(3+)),were successfully synthesized and the color properties were characterized.The color of these pigments depended on the composition and the synthesis condition,and the most vivid red color was obtained for the Ca3(Bi0.93Y0.07)8O15 sample calcined thrice at 800℃for 2 h.The L*and a*values corresponding to brightness and red chromaticity for this pigment were 45.6 and+30.6,respectively,which were greater than those of a commercially available Fe2O3 pigment(L^(*)=38.4,a^(*)=+29.5).Since the present pigment is composed of nontoxic and safe elements,it should be an attractive alternative to the conventional Fe2O3 pigment.

Oxygen-deficient bismuth tungstate and bismuth oxide composite photoanode with improved photostability

A homogeneous layer of Bi_2O_3-Bi_(14)WO_(24) composite(BWO/Bi_2O_3) thin film was fabricated using a combination of electrodeposition and thermal treatment. The evenly distributed Bi14 WO24 component within the Bi_2O_3 layer was found to be important in stabilising the photoelectrochemical performances of Bi_2O_3 photoanode by promoting the photoelectron transport. The unmodified Bi_2O_3 suffered from severe photocorrosion as proven by X-ray diffraction(XRD) and inductively coupled plasma(ICP) analyses while the composite thin film was active without noticeable activity decay for at least 3 h of illumination. This strategy might be applicable to other photocatalysts with stability issues.

Research Progress on the Bismuth Containing Complex Oxide in Photocatalystic Technology

The photocatalytic degradation on the bismuth containing complex oxide was revised in detail including the synthesis and classification of photocatalyts, and then the photocatalytic reaction, scavenger, and the mechanism of reaction. In particular, the perspectives of photocatalytic degradation on the bismuth containing oxide were analyzed in detail.

Composite Cathode Bi_(1.14)Sr_(0.43)O_(2.14)-Ag for Intermediate-temperature Solid Oxide Fuel Cells

Composites consisting of strontium stabilized bismuth oxide （Bi1.14Sr0.43O2.14, SSB） and silver were investigated as cathodes for intermediate-temperature solid oxide fuel cells with doped ceria electrolyte. There were no chemical reactions between the two components. The microstructure of the interfaces between composite cathodes and Ce0.8Sm0.2O1.9 （SDC） electrolytes was examined by scanning electron microscopy （SEM）. Impedance spectroscopy measurements show that the performance of cathode fired at 700 ℃ is the best. When the content of Ag2O is 70 wt%, polarization resistance values for the SSB-Ag cathodes are as low as 0.2 Ωcm^2 at 700℃ and 0.29 Ωcm^2 at 650℃. These results are much smaller than some of other reported composite cathodes on doped ceria electrolyte and indicate that SSB-Ag composite is a potential cathode material for intermediate temperature SOFCs.

Metal-organic-frameworks passivated CuBi_(2)O_(4)photocathodes boost CO_(2)reduction kinetics

Photoelectrochemical reduction of CO_(2)to produce CO with metal-organic frameworks(MOFs)is recognized as a desirable technology to mitigate CO_(2)emission and generate sustainable energy.To achieve highly efficient electrocatalyst,it is essential to design a new material interface and uncover new reaction mechanisms or kinetics.Herein,we developed two metal-organic Cu-MOF and Bi-MOF layers using benzene tricarboxylic acid(H_(3)BTC)ligands on CuBi_(2)O_(4) photocathodes.Both MOF layers drastically improved the photoelectrochemical stability by suppressing the photo-corrosion through conformal surface passivation.The Cu-MOF modified CuBi_(2)O_(4) showed more significant charge separation and transfer efficiencies than the Bi-MOF modified control.Based on the transient photocurrent curves under the applied potential of 0.6 V vs.RHE,the rate-law analysis showed the CO_(2)photoreduction took place through a first-order reaction.Further,the photoelectrochemical impedance spectra(PEIS)revealed this reaction order,representing an“operando”analysis.Moreover,the reaction rate constant on Cu-MOF modified sample was higher than that on Bi-MOF modified one and bare CuBi_(2)O_(4).Combined with the density functional theory calculation,the surface absorption of CO_(2)and CO molecules and the higher energy barrier for*COOH intermediates could significantly determine the first order reaction.

A Decisive Study on Dielectric Response of Bi2O3/Polystyrene &Bi2O3/PVDF Composite as Flexible Electrodes for Energy Storage

In this manuscript a comparative study on Bi2O3/polystyrene and Bi2O3/PVDF composites has been executed via analysis of structural, bonding, surface morphology and dielectric response of composites for energy storage. The composites have been synthesized using solution cast method by varying concentrations of Bi2O3 (BO = 1 - 5 mw%) into polystyrene (PS) and polyvinylidene fluoride (PVDF) polymers respectively. X-ray diffraction confirms the generation of crystallinity, Fourier transform infrared (FT-IR) spectroscopy confirms bonding behavior and scanning electron microscopy (SEM) confirms uniform distribution of Bi2O3 (BO) in PS and PVDF polymers. Impedance spectroscopy has been employed for determination of dielectric response of the fabricated composites. The dielectric constant has been found to be increased as 1.4 times of pristine PS to BO5%PS95% composites and 1.8 times of pristine PVDF to BO5%PVDF95% composites respectively. These high dielectric composite electrodes are useful for flexible energy storage devices.

High-capacity Bi_(2)O_(3) anode for 2.4 V neutral aqueous sodium-ion battery-supercapacitor hybrid device through phase conversion mechanism

Aqueous battery-supercapacitor hybrid devices(BSHs)are of great importance to enrich electrochemical energy storage systems with both high energy and power densities.However,further improvement of BSHs in aqueous electrolytes is greatly hampered by operating voltage and capacity limits.Different from the conventional intercalation/de-intercalation mechanism,Bi_(2)O_(3) implements charge storage by a reversible phase conversion mechanism.Herein,taking Bi_(2)O_(3) electrode with wide potential window(from-1.2 to 1 V vs.saturated calomel electrode)and high capacity as battery-type anode,we propose that the overall performance of aqueous BSHs can be greatly upgraded under neutral condition.By paring with stable layer-structuredδ-MnO_(2) cathode,a sodium-ion Bi_(2)O_(3)//MnO_(2) BSH with an ultrahigh voltage of 2.4 V in neutral sodium sulfate electrolyte is developed for the first time.This hybrid device exhibits high capacity(~215 C g^(-1) at 1 mA cm^(-2)),relatively long lifespan(~77.2%capacity retention after 1500 cycles),remarkable energy density(71.7 Wh kg^(-1)@400.5 W kg^(-1))and power density(3204.3 W kg^(-1)@18.8 Wh kg^(-1)).Electrochemical measurements combining a set of spectroscopic techniques reveal the reversible phase conversion between bismuth oxide and metallic bismuth(Bi_(2)O_(3)?Bi0)through Bi^(2+) transition phase in neutral sodium sulfate solution,which can deliver multielectron transfer up to 6,leading to the high-energy BSHs.Our work sheds light on the feasibility of using Bi_(2)O_(3) electrode under neutral condition to address the issue of narrow voltage and low capacity for aqueous BSHs.

Point-defect engineering of nanoporous CuBi_(2)O_(4) photocathode via rapid thermal processing for enhanced photoelectrochemical activity

Engineering point defects such as metal and oxygen vacancies play a crucial role in manipulating the electrical,optical,and catalytic properties of oxide semiconductors for solar water splitting.Herein,we synthesized nanoporous CuBi_(2)O_(4)(np-CBO)photocathodes and engineered their surface point defects via rapid thermal processing(RTP)in controlled atmospheres(O_(2),N_(2),and vacuum).We found that the O_(2)-RTP treatment of np-CBO increased the charge carrier density effectively without hampering the nanoporous morphology,which was attributed to the formation of copper vacancies(VCu).Further analyses revealed that the amounts of oxygen vacancies(Vo)and Cu^(1+)were reduced simultaneously,and the relative electrochemical active surface area increased after the O_(2)-RTP treatment.Notably,the point defects(VC_(u),Cu^(1+),and Vo)regulated np-CBO achieved a superb water-splitting photocurrent density of-1.81 m A cm^(-2) under simulated sunlight illumination,which is attributed to the enhanced charge transport and transfer properties resulting from the regulated surface point defects.Finally,the reversibility of the formation of the point defects was checked by sequential RTP treatments(O_(2)-N_(2)-O_(2)-N_(2)),demonstrating the strong dependence of photocurrent response on the RTP cycles.Conclusively,the surface point defect engineering via RTP treatment in a controlled atmosphere is a rapid and facile strategy to promote charge transport and transfer properties of photoelectrodes for efficient solar water-splitting.

Nonlinear Optical Properties in Bi_2O_3-B_2O_3-SiO_2 Glasses

A series of bismuth borate silica glasses were prepared and their densities, linear refractive indices and transmission spectra were measured. The optical gaps Eopt were obtained from the extrapolation of the linear portions to zero absorption. A decrease in the value of Eopt with increasing bismuth content may be explained by suggesting that the non-bridging oxygen ion content increases .It was found that high refractive index and narrow bandgap could lead into high third-order optical nonlinearity.

Pressureless reactive sintering mechanism of nanocrystalline Bi_2O_3-Y_2O_3 solid electrolyte

The nanocrystalline Bi2O3-Y2O3 solid electrolyte material was synthesized by pressureless reactive sintering process with Bi2O3 and Y2O3 nano mixed powder as raw materials, which was prepared by a chemical coprecipitation process. The study on the behavior of nano δ-Bi2O3 formation and its grain growth showed that the solid solution reaction of Y2O3 and δ-Bi2O3 to form δ-Bi2O3 occurs mainly in the initial stage of sintering process, and nano δ-Bi2O3 crystal grains grow approximately following the rule of paracurve （（D-D0）^2=K.t） during sintering process. After sintered at 600℃ for 2 h, the samples could reach above 96% in relative density and have dense microstructure with few remaining pores, the δ-Bi2O3 grains are less than 100 nm in size.

Synthesis of butterfly-like BiVO4/RGO nanocomposites and their photocatalytic activities

A simple and high efficient method was proposed for the synthesis of uniform three dimensional （3D） BiVO4/reduced graphene oxide （RGO） nanocomposite photocatalyst by adopting the microwave assistant and using Bi （NO3）3·5H2O, graphene oxide （GO） and NH4VO3 as precursor. The as-obtained composites were well characterized with the aid of various techniques to study the morphology, structure, composition, optimal and electrical property. In the as-obtained composites, the GO sheets were fully reduced into RGO, and monoclinic structure BiVO4 crystallized completely into butterfly-like BiVO4 lamellas and well bonded with the RGO lamellas. The length and the width of the butterfly-like BiVO4 particle were about 1.5 μm, and the thickness of the flake was about 20 nm. Photocatalytic performances of BiVO4/RGO composite and pure BiVO4 particle have been evaluated by investigating the reduction of Cr（VI） ion-contained wastewater under simulated solar light irradiation, where the BiVO4/RGO composite displayed enhanced photocatalytic activity. It is found that the pseudo-first-order rate constants （k） for the photocatalytic reduction of Cr （VI） by BiVO4/RGO composite was about 4 times as high as that of the pure BiVO4. The present work suggested that the combination of BiVO4 and RGO displayed a remarkable synergistic effect, which led to enhanced photo-catalytic activity on Cr（VI） reduction.

Syntheses，Structures and Properties of Some New Composition Perovskite Compounds：Sr0．6Bi0．4FeO2．7，Sr1－xBixFeO3－y and Ba1．5Pt0．5Mn2O6

New composition perovskite-type compounds with formula Sr0.6Bi0.4FeO2.7,Sr1-xBixFeO3-y(x=0.1 to 0. 9 in interveral of 0.1),and Ba1.5Pt0.5Mn2O6 have been synthsized and structurally characterized.The crystal structure of Sr0.6Bi0.4FeO2.7has been determined by X-ray single crystal diffraction,and the data of neutron powder diffraction collected at both room temperature and elevated temperature(380℃).The compound Sr0.6Bi0.4FeO2.7 crystallizes in the cubic space group of Pm3m with Z=1,a=3.9330(6) at room temperature,a=3.9498(6)A at 380℃.The magnetic structure from the neutron powder diffraction data collected at room temperature is consistent with a simple G-type antiferromagnetism and has a magnetic moment of 4.98 μB per Fe atom.The structures of Sr1-xBixFeO3-y with x other than 0.4 were also refined from the X-ray powder diffraction data.The data were consistent with a tetragonal cell when x=0.1,a rhombohedral cell when x= 0.9,and a cubic cell for x=0.2～0.8.From single crystal X-ray diffraction data,Ba1.5Pt0.5Mn2O6 crystallizes in hexagonal space group of P63mc with a= 5.7722 (6),c=4.4504(9),V=128.42(2),Z=1.The Sr(1-x)BixFeO(3-y)are found to be a good electronic and ionic conductor.