WO2020042125A1 - Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation - Google Patents

Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation Download PDF

Info

Publication number
WO2020042125A1
WO2020042125A1 PCT/CN2018/103369 CN2018103369W WO2020042125A1 WO 2020042125 A1 WO2020042125 A1 WO 2020042125A1 CN 2018103369 W CN2018103369 W CN 2018103369W WO 2020042125 A1 WO2020042125 A1 WO 2020042125A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
bismuth oxide
bismuth
libio
solution
Prior art date
Application number
PCT/CN2018/103369
Other languages
English (en)
Chinese (zh)
Inventor
黄彦林
刘宣宣
秦杰
魏东磊
Original Assignee
南通纺织丝绸产业技术研究院
苏州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南通纺织丝绸产业技术研究院, 苏州大学 filed Critical 南通纺织丝绸产业技术研究院
Priority to PCT/CN2018/103369 priority Critical patent/WO2020042125A1/fr
Publication of WO2020042125A1 publication Critical patent/WO2020042125A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation

Definitions

  • Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof
  • the present invention relates to an inorganic photocatalyst material and a preparation method thereof, and particularly to a heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 for degrading organic pollutants and a preparation method thereof.
  • the invention belongs to the technical field of semiconductor material preparation.
  • Bismuth oxide (Bi 2 0 3 ) is widely used in gas sensors, solid oxide fuel cells, optical films, and ceramics because of its excellent properties such as high refractive index, high dielectric constant, and obvious photoluminescence characteristics. Glass manufacturing and other fields.
  • the bismuth oxide Bi 2 0 3 has five isomers of a (monoclinic), (3 (square), Y (body-centered cubic), 6 (face-centered cubic), and e (triclinic) phases. These five isomers Bulk properties vary, especially a-Bi 2 0 3 is a low-temperature phase with a wide absorption wavelength in the visible region (band gap 2.8 eV), and the valence band (VB) of Bi 2 0 3 has strong oxidizing properties. (Compared to the standard hydrogen electrode is 3.13 eV) and is non-toxic and harmless, so it has become a promising photocatalytic material, which can be used for photocatalytic decomposition of water and pollutants.
  • the main disadvantage of the single bismuth oxide Bi 2 0 3 is that the recombination rate of photo-generated electrons and holes is high, and the photocatalytic activity is low. Therefore, more and more researchers are working on the modification of Bi 2 0 3 to reduce the recombination of electrons and holes. In these modification studies, the emphasis is on establishing a heterojunction structure between Bi 2 0 3 and other semiconductors with similar band structures. In recent years, BiOCl / Bi 2 0 3 , BiOBr / Bi 2 0 3 , NaBiO 3 Heterojunction photocatalysts such as / Bi 2 0 3 and NaBiO 3 / BiOCl were synthesized.
  • the present invention provides a simple and easy preparation method, short synthesis period, good photocatalytic activity, and good performance in the visible light region.
  • Heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 which can effectively degrade organic pollutants and its preparation method.
  • the technical solution adopted by the present invention is to provide a lithium bismuth oxide-bismuth oxide photocatalytic material, and bismuth oxide Bi 2 0 3 is supported on lithium bismuth oxide LiBiO 2
  • the technical solution of the present invention also provides a method for preparing a lithium bismuthate-bismuth oxide photocatalytic material, which adopts a hydrothermal method and includes the following steps:
  • the lithium ion Li + containing compound is lithium carbonate Li 2 C0 3, Li 2 lithium sulfate
  • the compound containing bismuth ion Bi 3+ is one of bismuth nitrate Bi (NO 3 ) r 5H 2 0 and bismuth chloride BiCl 3 ; the one containing bismuth ion Bi 3+
  • the molar amount of the compound is 2.2 to 2.6 times the molar amount of the compound containing lithium ion Li + .
  • a preferred solution of step (2) of the present invention is: the reaction temperature is 140 ⁇ 180 ° C, and the reaction time is 10 ⁇ 16 hours.
  • the prepared LiBi0 2 / Bi 2 0 3 photocatalyst has a pure phase, fine particles and uniform distribution, a heterojunction structure promotes the separation of photogenerated electrons and holes, broadens the spectral response range, and has good photocatalytic activity. .
  • the LiBi0 2 / Bi 2 0 3 photocatalyst is prepared from a wide range of raw materials, the preparation process is simple and easy to operate, the preparation conditions are mild and risk-free, the synthesis cycle is short, energy consumption and costs can be reduced, and the chemical properties of the samples prepared And stable optical performance.
  • the present invention is easy for industrial production and is environmentally friendly.
  • the LiBiO 2 / Bi 2 0 3 photocatalyst is a green and safe inorganic photocatalytic material.
  • FIG. 1 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 2 shows the SEN / ® of the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 3 is an ultraviolet-visible absorption spectrum of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 4 is LiBiO 2 / Bi prepared in Example 1 of the present invention 203 samples degradation profile of organic dyes methylene blue in the light;
  • FIG. 5 is a kinetic curve diagram of the degradation of methylene blue dye by the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 6 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention.
  • Example 7 is a SEN / ® of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • FIG. 1 is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment.
  • XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places.
  • the diffraction peaks corresponding to the LiBiO 2 standard PDF card are shown, indicating the formation of the main crystal phase LiBiO 2 , and the incorporation of Bi 2 0 3 does not cause a significant shift of the diffraction peaks of LiBiO 2 , indicating that the Bi 2 0 3 phase exists alone. Without entering the LiBiO 2 lattice, the two form a heterostructure.
  • FIG. 2 it is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment.
  • the obtained sample exhibits a lamellar distribution, and The sheet is thin and has good dispersion, which is beneficial to the separation of photo-generated carriers.
  • FIG. 3 it is an ultraviolet-visible absorption spectrum diagram of a sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the sample has absorption in the ultraviolet and visible light regions. This shows that the heterostructure broadens the spectral response range.
  • the sample LiBi0 2 / Bi 2 0 3 prepared in this example was used as a catalyst for photocatalytic degradation of methylene blue, and its activity was evaluated.
  • the light source lamp is a 500-watt cylindrical xenon lamp
  • the reaction tank uses a cylindrical photocatalytic reaction instrument made of borosilicate glass
  • the light source lamp is inserted into the reaction tank, and the condensed water is passed to cool down.
  • the temperature during the reaction was room temperature.
  • the dosage of the catalyst was 100 mg, the solution volume was 250 ml, and the concentration of methylene blue was 10 mg / liter.
  • the catalyst was placed in the reaction solution, and the catalytic time was set to 2400 minutes.
  • FIG. 4 it is a degradation curve of the organic dye methylene blue prepared by the sample LiBiO 2 / Bi 2 0 3 and a blank sample according to the technical solution of this embodiment.
  • the sample photocatalytically degrades methylene blue
  • the degradation rate reached 90% in 120 minutes, indicating that the prepared LiBiO 2 / Bi 2 0 3 material has good photocatalytic activity.
  • FIG. 5 it is a kinetic curve diagram of the degradation of methylene blue by the sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. It can be seen from the figure that the sample photocatalytically degrades methylene blue. The kinetic rate constant is 0.02268 minutes- 1 .
  • Lithium sulfate Li 2 SO 4 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it was completely transparent. It was recorded as solution A.
  • Bismuth nitrate Bi ( NO 3 ) 3 -5H 2 0 was dissolved in 20 ml of nitric acid by magnetic stirring at 90 ° C until it was completely transparent and recorded as solution B.
  • phase structure, SEM spectrum, ultraviolet-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
  • Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until completely penetrated. Ming, referred to as A solution, bismuth chloride (: 13 to 80 ° (: were dissolved under magnetic stirring in 20 ml of nitric acid, until completely transparent, as B solution.
  • phase structure, SEM spectrum, UV-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until it was completely transparent. Recorded as A solution.
  • Bismuth nitrate Bi (N0 3 ) R 5H 2 0 was dissolved in 20 ml of nitric acid with magnetic stirring at 60 ° C until it was completely transparent and recorded as solution B.
  • FIG. 6 is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment.
  • XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places.
  • a diffraction peak corresponding to 2 LiBiO standard PDF card described main crystalline phase formed LiBiO 2 while, Bi incorporated 203 did not cause significant diffraction peaks shift LiBiO 2, 203 Description of Bi phase alone Without entering the LiBiO 2 lattice, the two form a heterostructure.
  • Example 7 is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the obtained sample exhibits a lamellar distribution. Moreover, the sheet is thin and has good dispersibility, which is beneficial to the separation of photo-generated carriers. [0047] The UV-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation of the prepared sample were similar to those of Example 1.
  • lithium sulfate Li 2 SO 4 was weighed : 0.003 mol (0.3298 g), and bismuth chloride BiCl 3 was 4 mol of lithium sulfate Li 2 SO The amount is 2.48 times: 0.00744 mol (2.3461 g); Lithium sulfate Li 2 SO 4 is magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it is completely transparent. It is recorded as solution A, and bismuth chloride (: 1 3 Dissolve in 20 ml of nitric acid with magnetic stirring at 60 ° (:) until it is completely transparent, and record it as solution B.
  • phase structure and SEM spectrum of the sample prepared in this example are similar to those in Example 4.
  • the ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the phase structure and SEM spectrum of the sample provided in this example are similar to those in Example 4.
  • the ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1.
  • the LiBi0 2 / Bi 2 0 3 heterojunction powder is prepared by a hydrothermal method. The preparation method is simple and easy, and the synthesis period is short. Using the product as a photocatalyst, broadens the spectral response range through a heterostructure, reduces the photo-generated electron-hole recombination rate, has good light absorption in the visible light region, can effectively degrade organic pollutants, and has broad application prospects .

Abstract

L'invention concerne un matériau photocatalytique à base d'oxyde de bismuth-bismuthate de lithium et son procédé de préparation, se rapportant au domaine technique des matériaux photocatalytiques inorganiques. La surface du bismuthate de lithium (LiBiO2) est chargée avec de l'oxyde de bismuth (Bi2O3), et une interface de deux phases forment une hétérostructure; un rapport molaire du LiBiO2 au Bi2O3 étant de 1:(0,05-0,15). La poudre d'hétérojonction LiBiO2/Bi2O3 est préparée au moyen d'un procédé hydrothermique. Le procédé de préparation est simple, faisable et court en période synthétique et le matériau préparé est uniforme en distribution de taille de particule, de pureté élevée et de bonne stabilité chimique. Le produit est utilisé comme photocatalyseur, peut élargir une plage de réponse spectrale au moyen de l'hétérostructure, réduit le taux de recombinaison des électrons et des trous photoproduits, présente une bonne capacité d'absorption de la lumière dans une zone de lumière visible, peut dégrader efficacement les polluants organiques, et présente une large perspective d'application.
PCT/CN2018/103369 2018-08-30 2018-08-30 Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation WO2020042125A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/103369 WO2020042125A1 (fr) 2018-08-30 2018-08-30 Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/103369 WO2020042125A1 (fr) 2018-08-30 2018-08-30 Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation

Publications (1)

Publication Number Publication Date
WO2020042125A1 true WO2020042125A1 (fr) 2020-03-05

Family

ID=69643367

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/103369 WO2020042125A1 (fr) 2018-08-30 2018-08-30 Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2020042125A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115845902A (zh) * 2022-12-08 2023-03-28 上海交通大学深圳研究院 一种石墨相氮化碳光催化材料及其制备方法
CN117696079B (zh) * 2024-02-05 2024-05-14 浙江师范大学杭州校区 一种氧化镍复合PbBiO2Br的S型异质结催化剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1526475A (zh) * 2003-09-19 2004-09-08 �Ϻ���ͨ��ѧ 碱金属和Ag的铋系复合氧化物可见光响应的光催化剂及其应用
CN101711988A (zh) * 2009-08-14 2010-05-26 清华大学 NaBiO3/BiOCl异质结光催化剂及其制备方法
US20160207028A1 (en) * 2015-01-21 2016-07-21 Umm Al-Qura University Metal oxide supported palladium catalyst for hydrocarbon oxidation
CN106944074A (zh) * 2017-03-17 2017-07-14 佛山科学技术学院 一种可见光响应型复合光催化剂及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1526475A (zh) * 2003-09-19 2004-09-08 �Ϻ���ͨ��ѧ 碱金属和Ag的铋系复合氧化物可见光响应的光催化剂及其应用
CN101711988A (zh) * 2009-08-14 2010-05-26 清华大学 NaBiO3/BiOCl异质结光催化剂及其制备方法
US20160207028A1 (en) * 2015-01-21 2016-07-21 Umm Al-Qura University Metal oxide supported palladium catalyst for hydrocarbon oxidation
CN106944074A (zh) * 2017-03-17 2017-07-14 佛山科学技术学院 一种可见光响应型复合光催化剂及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHENG, LIJUN: "Synthesis of NaBiO3/Bi2O3 Heterojunction-structured Photocatalyst and Its Photocatalytic Mechanism", MATERIALS LETTERS, vol. 117, 6 December 2013 (2013-12-06), XP028810625, DOI: 20190306090435A *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115845902A (zh) * 2022-12-08 2023-03-28 上海交通大学深圳研究院 一种石墨相氮化碳光催化材料及其制备方法
CN115845902B (zh) * 2022-12-08 2024-04-19 上海交通大学深圳研究院 一种石墨相氮化碳光催化材料及其制备方法
CN117696079B (zh) * 2024-02-05 2024-05-14 浙江师范大学杭州校区 一种氧化镍复合PbBiO2Br的S型异质结催化剂及其制备方法和应用

Similar Documents

Publication Publication Date Title
Yu et al. Constructing SrTiO3-T/CdZnS heterostructure with tunable oxygen vacancies for solar-light-driven photocatalytic hydrogen evolution
CN100411730C (zh) 一种沸石基纳米二氧化钛双功能材料及其制备方法
Yang et al. Constructing 2D/1D heterostructural BiOBr/CdS composites to promote CO2 photoreduction
CN103894177B (zh) 一种具有光催化活性的稀土掺杂钛酸钾粉末的合成方法
Wu et al. Assembled and isolated Bi 5 O 7 I nanowires with good photocatalytic activities
CN108355669B (zh) 一种磁性纳米洋葱碳负载Bi2WO6的光催化剂及其制备方法和应用
CN112958061B (zh) 一种氧空位促进直接Z机制介孔Cu2O/TiO2光催化剂及其制备方法
CN114618537B (zh) 一种红磷/钛酸锶异质结光催化剂及制备方法及应用
CN111604053A (zh) 三元水滑石光催化剂及其制备方法与应用
Yang et al. 2D/2D Ti3C2/Bi4O5Br2 nanosheet heterojunction with enhanced visible light photocatalytic activity for NO removal
Qu et al. A new visible-light-induced Z-scheme photocatalytic system: Er3+: Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS) for refractory pollutant degradation with simultaneous hydrogen evolution
CN109012653B (zh) 一种铋酸锂-氧化铋光催化材料及其制备方法
WO2020042125A1 (fr) Matériau photocatalytique à base d'oxyde de bismuth-bismuthate lithium et son procédé de préparation
CN113578368B (zh) 一种g-C3N4/Ag3PO4/BiFeO3复合可见光催化剂制备方法及其应用
CN113426461B (zh) 银掺杂多晶面铁酸锌光催化纳米材料的制备方法
CN116196944A (zh) 一种生物质氮掺杂碳量子点耦合超薄BiOBr纳米片复合材料光催化剂的制备方法及应用
CN107812519B (zh) 一种粉末催化材料、含SiO2气凝胶复合多孔纳米催化材料的制备及应用
CN103566952B (zh) CdS/Cd2Ge2O6复合光催化剂的制备方法
CN113877556B (zh) 羟基氧化铟/改性凹凸棒石光催化复合材料及其制备方法和应用
Xue et al. Construction of Cu 2+-doped CeO 2 nanocrystals hierarchical hollow structure and its enhanced photocatalytic performance
CN110624532B (zh) 一种TiO2-BiVO4-石墨烯三元复合光催化材料及其制备方法
CN109967065B (zh) 一种Sn3O4/Sn2O3/SnO2层状纳米光催化材料的制备方法
CN114377693A (zh) 一种具有光氧化活性的空位诱导钌负载的硫铟化锌纳米管及制备与应用
CN113856668A (zh) 一种Bi/BiVO4复合异质结光催化材料的制备方法
Wang et al. Sisal-like Sn 2+ doped ZnO hierarchical structures: synthesis, growth mechanism, and their application in photocatalysis

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18932014

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18932014

Country of ref document: EP

Kind code of ref document: A1