稀土La3+掺杂Bi2WO6光催化降解活性艳红X-3B的研究

采用水热合成法制备稀土元素La3+掺杂Bi2WO6光催化剂并考察其对染料废水中活性艳红X-3B的光催化活性.通过X射线衍射、场发射扫描电镜、紫外-可见漫反射光谱、N2物理吸附-脱附等手段对合成材料的结构、形貌、光吸收等物理化学性能进行表征.结果表明,La3+掺杂量为5%时,其结晶度好、颗粒均匀、具有较强的可见光吸收性能,且比表面积比纯Bi2WO6提高30%以上,对X-3B的去除效果最好.另外,催化剂投加量、X-3B初始浓度、反应溶液pH等因素对La3+掺杂Bi2WO6光催化降解X-3B均有重要影响.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

稀土Ce3+掺杂Bi2WO6光催化降解罗丹明B的研究

采用水热合成法制备稀土元素Ce3+掺杂Bi2WO6光催剂,通过X射线衍射、场发射电镜扫描、紫外-可见漫反射光谱、N2物理吸附-脱附等手段对合成材料的结构、形貌、光吸收等物理化学性能进行表征,并以染料废水中罗丹明B的降解考察其光催化活性.结果表明,Ce3+掺杂量为0.05%时,其结晶度好、颗粒较均匀、具有较强的可见光吸收性能,且比表面积比纯Bi2WO6提高近10%以上,对罗丹明B的去除效果最好;催化剂用量越高、罗丹明B的初始浓度越低、反应溶液pH值越低、H2O2的浓度越高越有利于Ce/Bi2WO6对罗丹明B的吸附和降解;而阴阳离子的影响各不相同:NO3-、SO42-没有太大的影响; Na+、K+、Ca2+、Mg2+、Cl-的加入均促使的染料的去除;HCO3-抑制了罗丹明B的吸附,但是却促进了光降解.另外,经重复使用3次,光催化降解速率常数并没有降低,表明稀土Ce3+改性Bi2WO6是一种有效稳定的光催化剂.     

铋铁配比对铁酸铋合成及其光催化性能的影响

采用溶胶凝胶法通过改变原料中铋铁配比合成了以铁酸铋为主相的催化剂粉体。利用定量X射线法分析了不同铋铁配比对铁酸铋合成过程中物相组成的影响。采用紫外-可见光谱表征了粉体的光吸收特性。研究了催化剂组成、光照时间以及催化剂用量对催化降解甲基橙性能的影响。结果表明:九水硝酸铁与五水硝酸铋热分解速率相差较大是引起铁酸铋粉体合成过程中产生杂相的原因。降低铋铁配比有利于铁酸铋相的形成,其中铋铁配比为0.90∶1的原料合成的复合催化剂粉体紫外光降解甲基橙效率最高。     

Ferroelectric polarization effect on the photocatalytic activity of Bi0.9Ca0.1FeO3/CdS S-scheme nanocomposites

BiFeO₃ (BFO), as a kind of narrow band-gap semiconductor material, has gradually emerged advantages in the application of photocatalysis. In this paper, Ca doped BFO nanoparticles Bi_0.9Ca_0.1FeO₃ (BCFO) were prepared by sol-gel method. And BCFO and CdS nanocomposites with two morphologies were obtained by controlling the time of loading CdS under a low temperature liquid phase process. It is found that the band gap becomes narrower after doping Ca into BFO, which is conducive to the absorption of visible light. Among all the samples, the composite of CdS nanowires and BCFO nanoparticles obtained by reaction time of 10 min has the best photocatalytic performance. The degradation rate of Methyl Orange solution was 94% after 90 min under visible light irradiation, which was much higher than that of pure BCFO and CdS. Furthermore, significant enhancement in the degradation rate (100% degradation in 60 min) can be achieved in poled samples after electric polarization process. The highest degradation rate is due to the promoted separation of photogenerated carriers induced by the internal polarization field and the formation of S-scheme heterostructure between BCFO and CdS. Such BCFO-CdS nanocomposites may bring new insights into designing highly efficient photocatalyst.     

La/Ce-codoped Bi2O3 composite photocatalysts with high photocatalytic performance in removal of high concentration dye

A series of La/Ce-codoped Bi_2O_3 composite photocatalysts were fabricated via hydrothermal–calcination process. The as-prepared products were intensively characterized by some physicochemical characterizations like N_2 physical adsorption, X-ray powder diffraction(XRD), scanning electron microscope(SEM), transmission electron microscope(TEM), UV–Vis diffuse reflectance(UV–Vis DRS), Fourier transform infrared spectroscopy(FT-IR),photoelectrochemical measurements, and photoluminescence(PL) spectroscopy. The characterization results indicated that La and Ce doping induced obvious crystal phase transformation in Bi_2O_3, from monoclinic to tetragonal phase. La and Ce codoping also gave rise to the obvious synergetic effects, e.g., the lattice contraction of Bi_2O_3, the decrease of crystal size and the increase of surface area. The photocatalytic performance of the prepared catalysts was evaluated by removal of dye acid orange II with high concentration under visible light irradiation. Results showed that La/Ce-codoped Bi_2O_3 displayed much higher photocatalytic performance than that of bare Bi_2O_3, single La or Ce doped Bi_2O_3 samples. The superior photocatalytic activity was mainly attributed to the improved texture and surface properties and the synergistic effects of La and Ce codoping on suppressing the recombination of photo-generated electrons(e~-) and holes(h~+).     

Bi2WO6可见光催化降解活性艳红X-3B的研究

采用水热合成法制备Bi2WO6催化剂,并通过XRD,UV-vis DRS等手段对其进行表征;以活性艳红X-3B为目标污染物,研究催化剂量、X-3B初始浓度、反应溶液pH值以及H2O2等因素在可见光辐射下对其光催化降解效果的影响.结果表明,所制备的Bi2WO6催化剂结晶度好,具有较强的可见光吸收能力;最佳催化反应条件为: X-3B初始浓度20mg/L,Bi2WO6用量2g/L, pH5.18(原始pH值).在此条件下,光照60min,对X-3B的去除率可达到86%;加入2mL/L 30%的H2O2,光照30min,降解率可达到96%以上,降解反应符合一级反应动力学.光催化反应可以有效地破坏X-3B的发色基团偶氮结构使其脱色,但在所设定的反应时间(80 min)内X-3B不能被完全矿化,反应过程中有中间产物生成.     

Three-dimensional biogenic C-doped Bi2MoO6/In2O3-ZnO Z-scheme heterojunctions derived from a layered precursor

Novel 3D biogenic C-doped Bi_2 MoO_6/In_2O_3-ZnO Z-scheme heterojunctions were synthesized for the first time, using cotton fiber as template. The as-prepared samples showed excellent adsorption and photodegradation performance toward the hazardous antibiotic doxycycline under simulated sunlight irradiation. The morphology, phase composition and in situ carbon doping could be precisely controlled by adjusting processing parameters. The carbon doping in Bi_2 MoO_6/In_2O_3-ZnO was derived from the cotton template, and the carbon content could be varied in the range 0.9–4.4 wt.% via controlling the heat treatment temperature. The sample with Bi_2 MoO_6/In_2O_3-ZnO molar ratio of 1:2 and carbon content of1.1 wt.% exhibited the highest photocatalytic activity toward doxycycline degradation,which was 3.6 and 4.3 times higher than those of pure Bi_2 MoO_6 and Zn In Al-CLDH(calcined layered double hydroxides), respectively. It is believed that the Z-scheme heterojunction with C-doping, the 3D hierarchically micro–meso–macro porous structure, as well as the high adsorption capacity, contributed significantly to the enhanced photocatalytic activity.     

Preparation and photocatalytic performance study of dual Z-scheme Bi2Zr2O7/g-C3N4/Ag3PO4 for removal of antibiotics by visible-light

At present, the high re-combination rate of photogenerated carriers and the low redox capability of the photocatalyst are two factors that severely limit the improvement of photocatalytic performance. Herein, a dual Z-scheme photocatalyst bismuthzirconate/graphitic carbon nitride/silver phosphate (Bi₂Zr₂O₇/g-C₃N₄/Ag₃PO₄ (BCA)) was synthesized using a co-precipitation method, and a dual Z-scheme heterojunction photocatalytic system was established to decrease the high re-combination rate of photogenerated carriers and consequently improve the photocatalytic performance. The re-combination of electron-hole pairs (e⁻ and h⁺) in the valence band (VB) of g-C₃N₄ increases the redox potential of e⁻ and h⁺, leading to significant improvements in the redox capability of the photocatalyst and the efficiency of e⁻-h⁺ separation. As a photosensitizer, Ag₃PO₄ can enhance the visible light absorption capacity of the photocatalyst. The prepared photocatalyst showed strong stability, which was attributed to the efficient suppression of photo-corrosion of Ag₃PO₄ by transferring the e⁻ to the VB of g-C₃N₄. Tetracycline was degraded efficiently by BCA-10% (the BCA with 10 wt.% of AgPO₄) under visible light, and the degradation efficiency was up to 86.2%. This study experimentally suggested that the BCA photocatalyst has broad application prospects in removing antibiotic pollution.     

Construction of dual Z-scheme Bi2WO6/g-C3N4/black phosphorus quantum dots composites for effective bisphenol A degradation

In this work, a novel dual Z-scheme Bi₂WO₆/g-C₃N₄/black phosphorus quantum dots (Bi₂WO₆/g-C₃N₄/BPQDs) composites were fabricated and utilized towards photocatalytic degradation of bisphenol A (BPA) under visible-light irradiation. Optimizing the content of g-C₃N₄ and BPQDs in Bi₂WO₆/g-C₃N₄/BPQDs composites to a suitable mass ratio can enhance the visible-light harvesting capacity and increase the charge separation efficiency and the transfer rate of excited-state electrons and holes, resulting in much higher photocatalytic activity for BPA degradation (95.6%, at 20 mg/L in 120 min) than that of Bi₂WO₆ (63.7%), g-C₃N₄ (25.0%), BPQDs (8.5%), and Bi₂WO₆/g-C₃N₄ (79.6%), respectively. Radical trapping experiments indicated that photogenerated holes (h⁺) and superoxide radicals (•O₂⁻) played crucial roles in photocatalytic BPA degradation. Further, the possible degradation pathway and photocatalytic mechanism was proposed by analyzing the BPA intermediates. This work also demonstrated that the Bi₂WO₆/g-C₃N₄/BPQDs as effective photocatalysts was stable and have promising potential to remove environmental contaminants from real water samples.     

Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.     

水热合成纳米Bi2WO6 粉末及其可见光催化活性

以Bi(NO₃)_3⋅5H₂O 和Na₂WO_4⋅2H₂O 为原料,水热合成纳米光催化剂Bi₂WO₆ 粉末.以偶氮染料直接耐酸大红4BS 为目标污染物,通过XRD、TEM、BET 和UV-vis DRS 等表征手段,考察了水热温度、反应物Ph 值以及煅烧对催化剂的可见光催化活性、晶型、粒径和比表面积等方面的影响.结果表明,140℃和原始Ph 值为0.57 时水热合成的催化剂颗粒分散均匀,光催化效果最好,在光照150min 后,对4BS 的去除率为99.9%,其吸收边带达到470nm 左右,带隙能约为2.7eV.     

Enhancement of solar-driven photocatalytic activity of oxygen vacancy-rich Bi/BiOBr/Sr2LaF7:Yb3+,Er3+ composites through synergetic strategy of upconversion function and plasmonic effect

For better use of solar energy,the development of efficient broadband photocatalyst has attracted extraordinary attention.In this study,a ternary composite consisting of Sr₂ LaF₇:Yb³⁺,Er³⁺ upconversion(UC) nanocrystals and Bi nanoparticles loaded BiOBr nanosheets with oxygen vacancies(OVs,SLFBB) was designed and synthesized by multistep solvent-thermal method.Mechanisms of in-situ formation of Bi nanoparticles and OVs in BiOBr/Sr₂ LaF_7<...     

微波辅助Bi_2WO_6光催化降解四氯酚研究

采用水热法制备了纳米Bi2WO6,并用X射线衍射仪XRD、透射电镜TEM和比表面积分析仪BET表征其晶相结构、形貌及比表面积;然后以2,3,4,6-四氯酚(TeCP)为目标物考察了Bi2WO6在微波场中的光催化活性;最后探讨了TeCP在微波光催化反应体系中的降解机理。结果表明,微波辅助Bi2WO6光催化能够有效降解TeCP,反应20minTeCP(30mg/L)的去除率为94%,相应的动力学常数为0.191min-1;用GC/MS分析检测了此反应中TeCP的7种降解中间产物:2,3,4-三氯酚、2,3,5-三氯酚、2,3,6-三氯酚、2,4,5-三氯酚、2,4,6-三氯酚、3,4,5-三氯酚和2,3,5,6-四氯酚;推断在微波辅助Bi2WO6光催化反应体系TeCP的降解机理为TeCP异构化、脱氯、三氯酚异构化和矿化。     

In situ preparation of g-C3N4/Bi4O5I2 complex and its elevated photoactivity in Methyl Orange degradation under visible light

A graphite carbon nitride(g-C_3N_4) modified Bi_4O_5I_2 composite was successfully prepared insitu via the thermal treatment of a g-C_3N_4/Bi OI precursor at 400°C for 3 hr.The as-prepared g-C_3N_4/Bi_4O_5I_2 showed high photocatalytic performance in Methyl Orange(MO) degradation under visible light.The best sample presented a degradation rate of 0.164 min~(-1),which is 3.2 and 82 times as high as that of Bi_4O_5I_2 and g-C_3N_4,respectively.The g-C_3N_4/Bi_4O_5I_2 was characterized by X-ray powder diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Raman,X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectra(DRS),electrochemical impedance spectroscopy(EIS) and transient photocurrent response in order to explain the enhanced photoactivity.Results indicated that the decoration with a small amount of g-C_3N_4 influenced the specific surface area only slightly.Nevertheless,the capability for absorbing visible light was improved measurably,which was beneficial to the MO degradation.On top of that,a strong interaction between g-C_3N_4 and Bi_4O_5I_2 was detected.This interplay promoted the formation of a favorable heterojunction structure and thereby enhanced the charge separation.Thus,the g-C_3N_4/Bi_4O_5I_2 composite presented greater charge separation efficiency and much better photocatalytic performance than Bi_4O_5I_2.Additionally,g-C_3N_4/Bi_4O_5I_2 also presented high stability.·O_2~-and holes were verified to be the main reactive species.     

Sr10Bi6024-y的制备及其光催化活性研究

以Sr(NO3)2和Bi2O3为原料,采用高温固相法在900℃煅烧2h合成了纯度较高、钙钛矿型Sr10Bi6O24-y.使用X射线衍射、扫描电子显微镜和X射线光电子能谱对Sr10Bi6O24-y进行了表征.实验结果表明,Sr10Bi6O24-y光催化具有较强的光催化活性,其降解酸性红G的反应动力学符合一级反应.     

Bi/BiVO4/NiFe-LDH heterostructures with enhanced photoelectrochemical performance for streptomycin detection

Streptomycin (STR) plays an essential role in bacterial infection treatments. Selectivity and sensitivity of photoelectrochemical (PEC) sensors are the two most important parameters, which can be measured using the photosensitivity of its active material. We prepared a novel PEC sensor to detect STR using Bi/BiVO₄/LDH (layered double hydroxides) heterostructures as an active material, which is photoactive in the visible light wavelength range. The simultaneous presence of LDH and Bi/BiVO₄ enhanced the material photocurrent response, which was linear to the STR concentrations in the 0.01–500 nmol/L range. The STR detection limit by this sensor was 0.0042 nmol/L. Our novel PEC-based sensing strategy includes using an ultra-sensitive and highly selective sensor for STR detection. Additionally, the two-pot synthesis of Bi/BiVO₄/LDH developed in this work is environmentally friendly.