CN115417487A - Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA - Google Patents

Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA Download PDF

Info

Publication number
CN115417487A
CN115417487A CN202211029326.8A CN202211029326A CN115417487A CN 115417487 A CN115417487 A CN 115417487A CN 202211029326 A CN202211029326 A CN 202211029326A CN 115417487 A CN115417487 A CN 115417487A
Authority
CN
China
Prior art keywords
mno
bpa
catalyst
peroxymonosulfate
degradation
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN202211029326.8A
Other languages
Chinese (zh)
Inventor
李园园
蒋明珠
冉若愚
伊远学
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing Precision Medical Industrial Technology Research Institute Co ltd
Chongqing University of Education
Original Assignee
Chongqing Precision Medical Industrial Technology Research Institute Co ltd
Chongqing University of Education
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 Chongqing Precision Medical Industrial Technology Research Institute Co ltd, Chongqing University of Education filed Critical Chongqing Precision Medical Industrial Technology Research Institute Co ltd
Priority to CN202211029326.8A priority Critical patent/CN115417487A/en
Publication of CN115417487A publication Critical patent/CN115417487A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst Li 2 MnO 3 Application of activating peroxymonosulfate to degrade BPA, and catalyst Li 2 MnO 3 The preparation method comprises the step of preparing Li by adopting a solid-phase sintering method 2 MnO 3 Sintering the mixture in a muffle furnace at the constant temperature of 900 ℃ for 10 hours, and naturally cooling the mixture to room temperature to obtain the product. The catalyst Li 2 MnO 3 The catalyst has good catalytic effect on the aspect of activating peroxymonosulfate to degrade BPA, and has stable catalytic property.

Description

Li 2 MnO 3 Application of catalytic activation of peroxymonosulfate to degradation of BPA
Technical Field
The invention belongs to the technical field of environmental protection and pollutant degradation, and particularly relates to a catalyst Li 2 MnO 3 Application for catalyzing and activating peroxymonosulfate to degrade BPA and a preparation method thereof.
Background
In recent years, water pollutionThe pollution problem is increasingly serious, and especially the concentration of residual antibiotics in the water body is excessive and exceeds the standard, which causes serious harm to the life of people. To overcome these challenges, in the past decades, peroxymonosulfate (PMS) based, because of its good stability, low cost and ease of transportation, has become a promising oxidant whose activation to generate Reactive Oxygen Species (ROS) is of increasing interest for degrading or mineralizing recalcitrant organic pollutants in various industrial and consumer applications. A number of supported and unsupported metals or metal oxides have been developed as PMS activators, including MnO 2 、CuO-Fe 3 O 4 、Pd/Al 2 O 3 And the like. Magnetic metal nanoparticles are easily aggregated, thereby reducing their catalytic activity. The release of metal ions based on cobalt oxide and the like can also lead to secondary water contamination. The synthesis of supported metal catalysts typically involves complex processes and multiple reagents, often requiring long preparation times. Therefore, it remains necessary to expand the scope of heterogeneous catalysts for activating PMS by developing other metal/metal oxide materials. The search and preparation of highly efficient and stable catalysts for activating PMS is the hot spot of current research.
Bisphenol A (BPA) is one of the most widely used industrial compounds in the world, and is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenylene oxide resin, unsaturated polyester resin and the like. Can also be used for producing fine chemical products such as plasticizer, flame retardant, antioxidant, heat stabilizer, rubber antioxidant, pesticide, coating and the like.
In the manufacturing process of plastic products, the addition of bisphenol A can make the plastic products have the characteristics of colorless transparency, durability, lightness, outstanding impact resistance and the like, and particularly can prevent acidic vegetables and fruits from corroding metal containers from the inside, so the bisphenol A is widely used in the manufacturing process of packages of canned foods and beverages, sealing glue for feeding bottles, water bottles and tooth fillers, spectacle lenses and other hundreds of daily necessities. Thus, BPA is ubiquitous, ranging from mineral water bottles, medical devices, and the interior of food packaging, all of which have their silhouettes. It can be seen that BPA residues are relatively common and cause environmental pollution, and particularly BPA residues are easy to remain in water and need to be treated in an environment-friendly way.
Li 2 MnO 3 The method is mainly used for electrochemical application, in particular to the preparation of a positive electrode material for a lithium battery. However, the present inventors have unexpectedly found that Li synthesized by a solid phase sintering method 2 MnO 3 Research shows that Li 2 MnO 3 The PMS system has higher and stable catalytic activity, and is very effective in activating peroxymonosulfate to degrade residual BPA, especially residual BPA in water.
Disclosure of Invention
The invention aims to provide Li 2 MnO 3 Use of peroxomonosulfate as catalyst for degrading BPA (bisphenol A), preparation method thereof, and Li 2 MnO 3 A preparation method. The catalyst is mainly applied to the field of environmental protection restoration, and is particularly used for degrading residual BPA in water.
In one embodiment, the present invention provides a catalyst, li 2 MnO 3 Use for catalytically activating peroxymonosulfate to degrade BPA.
In the above-mentioned use of the present invention, the peroxymonosulfate is oxone (also known as "potassium monopersulfate" or "potassium peroxymonosulfate").
The use of the invention, the catalyst Li 2 MnO 3 Has the characteristic peak shown in figure 1.
In another embodiment, the present invention also provides a catalyst, li 2 MnO 3 The preparation method comprises the following steps:
(1) Mixing Li 2 CO 3 And MnCO 3 According to the mol ratio of 1:1, grinding after mixing;
(2) After being uniformly ground, the mixture is placed in a muffle furnace to be heated to 900 ℃ for constant-temperature sintering reaction;
(3) After the reaction is finished, naturally cooling to room temperature to obtain red powdery Li 2 MnO 3 。
In the method of the present invention, in the step (1), the grinding time is 40min, and in the step (2), the temperature is raised at a rate of 5 ℃/min. The sintering time is 10h.
In particular embodiments, a catalyst of the present invention, li 2 MnO 3 The preparation method comprises the following steps:
(1) Mixing Li 2 CO 3 And MnCO 3 According to a certain molar ratio of 3:3, after weighing, placing the mixture in an agate mortar for uniform mixing and grinding;
(2) Placing the uniformly ground mixture in a crucible, and then placing the crucible in a muffle furnace to heat to 900 ℃ for constant-temperature sintering reaction for 10 hours;
(3) After the reaction is finished, naturally cooling to room temperature to obtain red powdery Li 2 MnO 3 。
In the above embodiment, the method of the present invention, the grinding time in the step (1) is 40min, and the temperature in the step (2) is increased at a rate of 5 ℃/min.
On the other hand, catalyst Li 2 MnO 3 Use of the catalyst Li in the catalytic degradation of BPA by activated PMS (peroxymonosulfate) 2 MnO 3 Is prepared by the method of the invention.
Preferably, the use according to the invention is a catalyst Li 2 MnO 3 The application of the catalyst in activating PMS (potassium hydrogen persulfate) to catalytically degrade alkylphenol BPA.
The invention utilizes the catalyst Li prepared by a solid-phase sintering method 2 MnO 3 The application of the activated PMS in catalytic degradation of BPA, particularly in degradation of residual pollutants in environmental water, preferably BPA.
In another embodiment, a catalyst of the present invention, li 2 MnO 3 The preparation method comprises the following steps:
(1) 3mmol of Li were weighed out separately 2 CO 3 、3mmol MnCO 3 Mixing and grinding for 40min, and transferring to a corundum crucible;
(2) Putting the corundum crucible into a high-temperature muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, sintering for 10 hours, naturally cooling to room temperature, and finally obtaining Li 2 MnO 3 ；
The invention has the beneficial effects that:catalyst Li obtained by solid-phase sintering 2 MnO 3 The catalyst has good catalytic degradation effect on antibiotics, particularly BPA, is particularly used for degrading BPA medicines in water pollutants, is beneficial to environmental protection treatment, can be recycled, and has stable catalytic property.
Drawings
FIG. 1 Li prepared in example 1 2 MnO 3 XRD pattern of (a);
FIG. 2 catalyst Li 2 MnO 3 ，MnCO 3 A catalytic degradation diagram of activating PMS to degrade BPA;
FIG. 3Li 2 MnO 3 XRD contrast patterns before and after PMS activation degradation BPA reaction, wherein the upper pattern is Li before catalytic reaction 2 MnO 3 The lower spectrum is Li after catalytic reaction 2 MnO 3 XRD pattern of (a).
Detailed Description
The following examples are exemplary and are included to aid in understanding and further illustrate the spirit of the invention, but are not intended to limit the scope of the invention.
It should be noted that the experimental methods used in the following examples are all conventional methods unless otherwise specified; materials, reagents, equipment and the like used in the following examples are commercially available unless otherwise specified.
Li used in the examples 2 CO 3 99.90% pure from alatin; mnCO 3 99.90% pure from alatin; the purity of the potassium hydrogen persulfate is 42 to 46 percent 5 basis, from alatin; bisphenol A with a purity of 99.0% from alatin; the methanol has purity of AR 99.5% and is from chemical industry of Chuandong.
Example 1 solid phase method for preparing Li 2 MnO 3
The preparation process comprises the following steps:
(1) 3mmol of Li were weighed out separately 2 CO 3 、3mmol MnCO 3 Mixing and grinding for 40min, and transferring to a corundum crucible;
(2) Putting the corundum crucible into a high-temperature muffle furnace, and keeping the temperature rise at 5 ℃Heating to 900 ℃ in min, sintering and reacting for 10h, naturally cooling to room temperature after the reaction is finished, and finally obtaining the product catalyst Li 2 MnO 3 。
XRD test: taking the obtained product Li 2 MnO 3 After a small amount of the product was sufficiently ground in an agate mortar, the sample was subjected to phase characterization on a Shimadzu 7000-X-ray diffractometer, and the XRD (X-ray powder diffraction pattern) result thereof is shown in FIG. 1.
Example 2 application Effect test
1. By implementing the experiment of activating PMS to catalytically degrade BPA, li prepared by solid-phase sintering can be known 2 MnO 3 the/PMS (potassium hydrogen persulfate) system has good degradation effect on BPA. Originally using Li 2 MnO 3 PMS and MnCO 3 PMS, li only 2 MnO 3 The results of the comparative experiment with PMS alone are shown in FIG. 2, and Li can be seen within 90min 2 MnO 3 The degradation rate of (70 mg)/PMS (potassium hydrogen persulfate) (6 mg) system to BPA (20 mg/L) can reach 80%. The cycle experiment shows that Li 2 MnO 3 Has stable catalytic oxidation degradation efficiency. Compared with MnCO 3 The catalytic oxidation degradation efficiency is greatly improved.
2. The experiment comprises the following specific steps:
taking 70mg of the prepared catalyst Li 2 MnO 3 Adding into 100ml BPA solution with concentration of 20mg/L, dark adsorbing for 60min to establish adsorption-desorption equilibrium. Adding 6mg PMS (potassium hydrogen persulfate) after dark adsorption for reacting for 90min, taking 2mL of supernatant every 15min for the first 60min and 30min for the last one, placing the supernatant in a centrifuge tube prepared with 2mL of methanol, centrifuging, filtering with a 0.22um filter membrane, and measuring the peak area by a high performance liquid chromatograph (Agilent 1260). The result shows that the degradation efficiency reaches 80% within 90min, and the degradation effect is good.
Taking 70mg of MnCO 3 (i.e. preparation of catalyst Li) 2 MnO 3 Raw material (b) was added to 100ml of BPA solution having a concentration of 20mg/L, and adsorption-desorption equilibrium was established for 60min by dark adsorption. Adding 6mg PMS (potassium hydrogen persulfate) after dark adsorption for reaction for 90min, taking 2mL supernatant every 15min for the first 60min, and taking the supernatant at 30min intervals for the last one, and placing the supernatant in the place where the supernatant has been removedCentrifuging in a centrifuge tube containing 2mL of methanol, filtering with 0.22um filter membrane, and measuring its peak area with high performance liquid chromatograph (Agilent 1260). The result shows that the catalytic degradation-oxidation decomposition efficiency is only 20 percent in 90min relative to Li 2 MnO 3 The catalytic oxidation degradation efficiency is reduced by 60 percent. Illustrating the Li prepared 2 MnO 3 The catalyst can greatly improve the degradation effect of BPA.
The circulation experiment proves Li 2 MnO 3 Reproducibility and stability of catalytic activity of PMS for degradation of BPA.
Further, catalyst Li was investigated 2 MnO 3 Phase stability after cyclic reaction of activated PMS (potassium hydrogen persulfate) degradation experiment. FIG. 3 shows the catalyst Li 2 MnO 3 XRD patterns before and after catalytic reaction show that the catalyst Li 2 MnO 3 The crystal form structure remains unchanged after the cyclic catalysis test, and the crystal form structure has good phase stability and cyclic usability. Thus, the catalyst Li prepared by the solid-phase sintering method 2 MnO 3 Can be recycled to treat and remove the residual antibiotic BPA pollutants in the water body, thereby continuously protecting the environment.

Claims (7)

1. Catalyst Li 2 MnO 3 Use for catalytically activating peroxymonosulfate to degrade BPA.
2. The use according to claim 1, wherein the peroxymonosulfate is oxone.
3. The use according to claim 1, said Li 2 MnO 3 Has the characteristic peaks shown in figure 1.
4. Preparation of the catalyst Li according to claim 1 2 MnO 3 The method comprises the following steps:
(1) Mixing Li 2 CO 3 And MnCO 3 According to the mol ratio of 1:1, grinding after mixing;
(2) After being uniformly ground, the mixture is placed in a muffle furnace to be heated to 900 ℃ for constant-temperature sintering reaction;
(3) After the reaction is finished, naturally cooling to room temperature to obtain red powdery Li 2 MnO 3 。
5. The method of claim 4, wherein in step (1), the milling time is 40min.
6. The method of claim 4, wherein in step (2), the sintering time is 10 hours.
7. The method according to claim 4, wherein in the step (2), the temperature is increased at a rate of 5 ℃/min.
CN202211029326.8A 2022-08-24 2022-08-24 Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA Pending CN115417487A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211029326.8A CN115417487A (en) 2022-08-24 2022-08-24 Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211029326.8A CN115417487A (en) 2022-08-24 2022-08-24 Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA

Publications (1)

Publication Number Publication Date
CN115417487A true CN115417487A (en) 2022-12-02

Family

ID=84200686

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211029326.8A Pending CN115417487A (en) 2022-08-24 2022-08-24 Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA

Country Status (1)

Country Link
CN (1) CN115417487A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582497A (en) * 2009-06-18 2009-11-18 中南大学 Method for preparing composite anode material of high-capacity lithium ion battery
CN101593829A (en) * 2009-06-26 2009-12-02 湖南化工研究院 A kind of preparation method of lithium cell anode material lithium manganate
CN101964428A (en) * 2010-08-05 2011-02-02 深圳市贝特瑞新能源材料股份有限公司 Preparation method of lamellar lithium manganese battery
CN107634196A (en) * 2017-08-31 2018-01-26 福建师范大学 Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc
CN109999811A (en) * 2019-05-07 2019-07-12 鲁东大学 It a kind of preparation of biomass iron carbon composite and degrades bisphenol-A for catalytic activation sodium peroxydisulfate
CN111530466A (en) * 2020-05-11 2020-08-14 湖南大学 Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries
CN111905720A (en) * 2020-08-17 2020-11-10 中国环境科学研究院 Application of waste battery anode material in catalyst, catalyst and preparation method thereof
CN114054019A (en) * 2021-10-27 2022-02-18 重庆第二师范学院 Lithium, manganese and titanium composite oxide photocatalyst, preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582497A (en) * 2009-06-18 2009-11-18 中南大学 Method for preparing composite anode material of high-capacity lithium ion battery
CN101593829A (en) * 2009-06-26 2009-12-02 湖南化工研究院 A kind of preparation method of lithium cell anode material lithium manganate
CN101964428A (en) * 2010-08-05 2011-02-02 深圳市贝特瑞新能源材料股份有限公司 Preparation method of lamellar lithium manganese battery
CN107634196A (en) * 2017-08-31 2018-01-26 福建师范大学 Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc
CN109999811A (en) * 2019-05-07 2019-07-12 鲁东大学 It a kind of preparation of biomass iron carbon composite and degrades bisphenol-A for catalytic activation sodium peroxydisulfate
CN111530466A (en) * 2020-05-11 2020-08-14 湖南大学 Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries
CN111905720A (en) * 2020-08-17 2020-11-10 中国环境科学研究院 Application of waste battery anode material in catalyst, catalyst and preparation method thereof
CN114054019A (en) * 2021-10-27 2022-02-18 重庆第二师范学院 Lithium, manganese and titanium composite oxide photocatalyst, preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘昊林;: "废旧钴酸锂电池资源化回收研究", 低碳世界, no. 01 *
马世闯: ""锂离子电池锰酸锂正极材料的制备与废旧锰酸锂正极材料的回收利用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》, no. 2009, pages 042 - 497 *
马鹏;: "锂离子电池用锰酸锂(LiMn_2O_4)的研究与发展", 热处理, no. 04 *

Similar Documents

Publication Publication Date Title
Ranjit et al. Photocatalytic reduction of nitrite and nitrate ions over doped TiO2 catalysts
Gao et al. Titania supported Pd-Cu bimetallic catalyst for the reduction of nitrate in drinking water
CN110368924B (en) Bismuth titanate/bismuth vanadate composite photocatalyst and application thereof in photothermal catalytic purification of organic gas pollutants
CN105107505B (en) A kind of magnetic TiO2Porous carbon Fe3O4Composite visible light catalyst and preparation method thereof
CN113457711B (en) Graphite-phase carbon nitride-loaded magnesium monoatomic composite material, preparation method thereof and method for preparing hydrogen peroxide through photocatalysis
CN106975481A (en) The preparation method of alkaline earth metal doping MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs
Amadelli et al. Preparation, Characterisation, and Photocatalytic Behaviour of C o-T i O 2 with Visible Light Response
EP1724014B1 (en) Use of a composite oxide as a visible light responsive photocatalyst and method for decomposition and removal of harmful chemical material using the same
Tao et al. Enhanced activity of microwave-activated CoOx/MOR catalyst for the epoxidation of α-pinene with air
CN105854867A (en) Preparation method of zinc oxide/antimony tin oxide composite nano-material
CN115417487A (en) Li 2 MnO 3 Application of BPA in catalytic activation of peroxymonosulfate to degradation of BPA
Asadi et al. Construction of Mg-doped ZnO/g-C3N4@ ZIF-8 multi-component catalyst with superior catalytic performance for the degradation of illicit drug under visible light
CN112844410B (en) Preparation method and application of nickel ion modified bismuth oxysulfide photocatalyst
CN111774067B (en) Z-shaped CoO/WO 3 Synthesis method of nanosheet and application of nanosheet in degradation of environmental pollutants
CN111229200B (en) Bismuth oxide modified Ti 3+ Self-doping TiO 2 Preparation method of heterojunction photocatalyst
JP2004137087A (en) Novel titanium suboxide and its production method
Poormohammadi-Ahandani et al. Microwave-assisted preparation of Zn1− xCuxS nanoparticles by a fast, green, and template-free method and photocatalytic activity
Wang et al. Highly efficient degradation of rhodamine B by α-MnO2 nanorods
CN105056962B (en) A kind of preparation method of support type rare earth double-perovskite compound oxide photocatalyst
CN107803196B (en) Synthesis of photocatalyst Zn with visible light response2SnO4/Bi2WO6Preparation method of nanosheet
CN107597098B (en) One-pot synthesis of visible-light-responsive photocatalyst LaVO4/WO3Preparation method of nanosheet
CN115779944A (en) Modified carbon nitride based on alkali metal ions, preparation method thereof and photocatalytic H production 2 O 2 In (1)
JP2008279407A (en) Visible light response type titanium dioxide photocatalyst powder and its manufacturing method and device
CN100493698C (en) Composite oxide photocatalyst containing lithium and preparation method
CN112661192A (en) Synthesis of lanthanum manganate/cobaltosic oxide and purification treatment of toluene under full spectrum

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination