CN108579681B - CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof - Google Patents

CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof Download PDF

Info

Publication number
CN108579681B
CN108579681B CN201810219311.5A CN201810219311A CN108579681B CN 108579681 B CN108579681 B CN 108579681B CN 201810219311 A CN201810219311 A CN 201810219311A CN 108579681 B CN108579681 B CN 108579681B
Authority
CN
China
Prior art keywords
ctab
preparation
doped
repairing material
fecl
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.)
Active
Application number
CN201810219311.5A
Other languages
Chinese (zh)
Other versions
CN108579681A (en
Inventor
王小治
周颜霞
尹微琴
王圣森
侯建华
封克
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.)
Yangzhou University
Original Assignee
Yangzhou University
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 Yangzhou University filed Critical Yangzhou University
Priority to CN201810219311.5A priority Critical patent/CN108579681B/en
Publication of CN108579681A publication Critical patent/CN108579681A/en
Application granted granted Critical
Publication of CN108579681B publication Critical patent/CN108579681B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Compounds Of Iron (AREA)

Abstract

The invention discloses a CTAB doped Fe3S4The magnetic environment repairing material and the preparation method and the application thereof comprise the following steps: FeCl is added3·6H2Dissolving O and thiourea in a certain volume of ethylene glycol according to a certain molar ratio, and magnetically stirring until a carmine solution is formed; adding 0.6-2.4 mmol CTAB into the solution, and stirring and ultrasonically treating for 10-30 min; carrying out hydrothermal reaction on the reaction system at 160-200 ℃; and cooling to room temperature, cleaning the obtained product, drying and grinding under a vacuum condition to obtain the magnetic environment repairing material. The magnetic environment restoration material prepared by the invention has good magnetic property and strong adsorption capacity, and can adsorb heavy metals in water which are difficult to remove by other methods.

Description

CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof
Technical Field
The invention relates to an environment restoration material for removing heavy metals in a water body environment, and a preparation method and application thereof, and belongs to the field of environment restoration.
Background
At present, the synthesis and application of ferroferric sulfide are mainly researched in the aspects of electrochemical performance, biomedicine, feed additive degradation and the like in the environmental fieldThe research is rare and still in the preliminary research stage. Kong et al use beta-cyclodextrin for magnetic Fe3S4The nanoparticles are stabilized and applied to the removal of the heavy metal Pb by chemical precipitation (galena formation) and surface adsorption (Kong L, Yan L, Qu Z, et al. beta. -Cyclodextrin stabilized surfactant Fe)3S4nanoparticles for efficient removal of Pb(II)[J]Journal of materials Chemistry A, 2015, 3(30): 15755-15763); preparation of Fe by Mahamudur Islam et al by hydrothermal method3S4Polypyrrole (GPPy) nanocomposites and their application for arsenious acid and arsenate removal (Islam M, Patel r. Solvothermal synthesis of greigite (Fe)3S4)– Conducting polypyrrolenanocomposite and its application towards arsenic removal[J]. SeparationScience&Technology, 2017.); feng Mei et al used beta-CD and PEG for Fe control3S4And the application of the prepared magnetic nanocrystals (GMNCs) in the biomedical field (Feng M, Lu Y, Yang Y, et. biological crystalline nanocrystals: chemical synthesis and biological amplification applications [ J]Scientific Reports, 2013, 3(10): 2994.). In recent years, the application of cationic surfactants in the removal of anionic heavy metals is increasing, and suitable surfactants can improve Fe3S4Purity and stability of (b).
However, Fe is added3S4The reduction and adsorption of hexavalent chromium are discussed, and no CTAB doped Fe exists at present3S4Report of hexavalent chromium removal.
Disclosure of Invention
The invention aims to provide a CTAB doped Fe3S4The magnetic environment restoration material and the preparation method thereof are used for adsorbing heavy metals in the environment as the environment restoration material, and have large removal capacity, thereby having wide application prospect.
The technical solution for realizing the purpose of the invention is as follows: CTAB doped Fe3S4The magnetic environment repairing material and the preparation method thereof comprise the following steps:
the first step is as follows: FeCl is added3·6H2Mixing O and thiourea, and dissolving the mixture in glycol to form a mixed solution;
the second step is that: adding cetyltrimethylammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
the third step: carrying out hydrothermal reaction on the second-step reaction system at 160-200 ℃;
the fourth step: and cooling to room temperature, cleaning the obtained product, drying and grinding under a vacuum condition to obtain the magnetic environment repairing material.
Further, in the first step, FeCl in the mixed solution3·6H2The molar ratio of O to thiourea is 0.5-1.0.
Further, in the second step, the amount of CTAB added and FeCl3·6H2The molar ratio of O is 0.20-0.80, and the ultrasonic stirring time is 10-30 min.
Further, in the third step, the hydrothermal reaction time is 12-15 hours.
Further, in the fourth step, cleaning the obtained product for 3-5 times by using ethanol and deionized water; the drying temperature was 60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention has simple synthesis process and low production cost, and is beneficial to large-scale production with low cost.
(2) Using magnetic Fe3S4As an adsorbent for heavy metals in the solution, the adsorbent has larger adsorption capacity, is easy to separate, and is beneficial to the treatment of high-concentration heavy metal polluted wastewater.
(3) CTAB is adopted as a doping agent in the synthesis process of the repair material, which is beneficial to improving Fe3S4Purity and stability of (b).
Drawings
FIG. 1 shows Fe prepared in comparative example 1 and examples 1 to 4 of the present invention3S4And Fe3S4-CTAB0.6~2.4Field emission scanning electron micrograph (a is Fe)3S4B is Fe3S4-CTAB0.6C is Fe3S4-CTAB1.2D is Fe3S4-CTAB1.8E is Fe3S4-CTAB2.4）。
FIG. 2 shows Fe prepared in comparative example 1 and examples 1 to 4 of the present invention3S4And Fe3S4-CTAB0.6~2.4Magnetic hysteresis loop diagram of (1).
FIG. 3 is a graph showing the removal efficiency of Cr (VI) from the materials prepared in comparative example 1 and examples 1 to 4 of the present invention.
Detailed Description
Comparative example 1
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, transferring the reaction system in the first step into a closed reaction container (high-pressure kettle);
thirdly, placing the high-pressure reaction kettle in the second step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
step four, cooling the reaction system in the step three to room temperature, washing the obtained product with ethanol and deionized water, drying under a vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4FIG. 1(a) shows a scanning electron micrograph, and FIG. 2 shows a hysteresis loop.
Taking 15mg of Fe3S4And 50mL of hexavalent chromium solution were added to a 150mL Erlenmeyer flask, and shaken at room temperature for 1.0 h. Concentration of hexavalent chromium solution: 100 mg/L. As shown in fig. 3, the removal rate of hexavalent chromium was experimentally measured to be about 70%.
Example 1
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, adding 0.6mmol of cetyltrimethylammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
step three, transferring the reaction system in the step two into a closed reaction container (high-pressure kettle);
fourthly, placing the high-pressure reaction kettle in the third step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
fifthly, cooling the reaction system in the fourth step to room temperature, washing the obtained product with ethanol and deionized water, drying under vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4-CTAB0.6FIG. 1(b) shows a scanning electron micrograph, and FIG. 2 shows a hysteresis loop.
Taking 15mg of Fe3S4-CTAB0.6And 50mL of hexavalent chromium solution were added to a 150mL Erlenmeyer flask, and shaken at room temperature for 1.0 h. Concentration of hexavalent chromium solution: 100 mg/L. As shown in fig. 2, the removal rate of hexavalent chromium was measured by an experiment to be about 84%.
Example 2
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, adding 1.2mmol of cetyltrimethylammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
step three, transferring the reaction system in the step two into a closed reaction container (high-pressure kettle);
fourthly, placing the high-pressure reaction kettle in the third step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
fifthly, cooling the reaction system in the fourth step to room temperature, washing the obtained product with ethanol and deionized water, drying under vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4-CTAB1.2FIG. 1(c) shows a scanning electron micrograph, and FIG. 2 shows a hysteresis loop.
Taking 15mg of Fe3S4-CTAB1.2And 50mL sixThe chromium solution was added to a 150mL Erlenmeyer flask and shaken at room temperature for 1.0 h. Concentration of hexavalent chromium solution: 100 mg/L. As shown in fig. 3, the removal rate of hexavalent chromium was found to be about 91% by experiment.
Example 3
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, adding 1.8mmol of cetyltrimethylammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
step three, transferring the reaction system in the step two into a closed reaction container (high-pressure kettle);
fourthly, placing the high-pressure reaction kettle in the third step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
fifthly, cooling the reaction system in the fourth step to room temperature, washing the obtained product with ethanol and deionized water, drying under vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4-CTAB1.8FIG. 1(d) shows a scanning electron micrograph, and FIG. 2 shows a hysteresis loop.
Taking 15mg of Fe3S4-CTAB1.8And 50mL of hexavalent chromium solution were added to a 150mL Erlenmeyer flask, and shaken at room temperature for 1.0 h. Concentration of hexavalent chromium solution: 100 mg/L. As shown in fig. 3, the removal rate of hexavalent chromium was found to be about 94% by experiment.
Example 4
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, adding 2.4mmol of hexadecyl trimethyl ammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
step three, transferring the reaction system in the step two into a closed reaction container (high-pressure kettle);
fourthly, placing the high-pressure reaction kettle in the third step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
fifthly, cooling the reaction system in the fourth step to room temperature, washing the obtained product with ethanol and deionized water, drying under vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4-CTAB2.4FIG. 1(e) shows a scanning electron micrograph, and FIG. 2 shows a hysteresis loop.
Taking 15mg of Fe3S4-CTAB2.4And 50mL of hexavalent chromium solution were added to a 150mL Erlenmeyer flask, and shaken at room temperature for 1.0 h. Concentration of hexavalent chromium solution: 100 mg/L. As shown in fig. 3, the removal rate of hexavalent chromium was measured by an experiment to be about 84%.
Example 5
First, FeCl is added3·6H2O and thiourea according to a ratio of 1: dissolving the mixture in a certain volume of ethylene glycol according to the molar ratio of 2, and magnetically stirring for 20-30 min until a carmine solution is formed;
secondly, adding 1.8mmol of cetyltrimethylammonium bromide (CTAB) into the mixed solution, and ultrasonically stirring for a period of time;
step three, transferring the reaction system in the step two into a closed reaction container (high-pressure kettle);
fourthly, placing the high-pressure reaction kettle in the third step into an oven, heating the oven to the reaction temperature of 180 ℃, creating a high-temperature and high-pressure reaction environment, and maintaining the constant temperature for 12 hours;
fifthly, cooling the reaction system in the fourth step to room temperature, washing the obtained product with ethanol and deionized water, drying under vacuum condition, and grinding to obtain the magnetic environment repairing material Fe3S4-CTAB1.8。
Taking 15mg of Fe3S4-CTAB1.8And 50mL of hexavalent chromium solution were added to a 150mL Erlenmeyer flask, and shaken at room temperature for 1.0 h. The initial concentrations of the prepared hexavalent chromium solutions are respectively as follows: 100, 125, 150, 200, 250 and 300 mg/L. The experimental result is in accordance with Langmuir adsorption isotherm, and the maximum adsorption capacity is 330.03 mg/g.

Claims (8)

  1. CTAB-doped Fe3S4The preparation method of the magnetic environment repairing material is characterized by comprising the following steps:
    the first step is as follows: FeCl is added3·6H2Mixing O and thiourea, and dissolving the mixture in glycol to form a mixed solution;
    the second step is that: adding CTAB into the mixed solution, and ultrasonically stirring for a period of time;
    the third step: carrying out hydrothermal reaction on the second-step reaction system at 160-200 ℃;
    the fourth step: cooling to room temperature, cleaning the obtained product, drying and grinding under a vacuum condition to obtain the magnetic environment repairing material;
    wherein, the input amount of CTAB and FeCl3·6H2The molar ratio of O is 0.20 to 0.80.
  2. 2. The method of claim 1, wherein in the first step, FeCl in the mixed solution3·6H2The molar ratio of O to thiourea is 0.5-1.0.
  3. 3. The method of claim 1, wherein the ultrasonic stirring time in the second step is 10 to 30 min.
  4. 4. The method according to claim 1, wherein the hydrothermal reaction time in the third step is 12 to 15 hours.
  5. 5. The preparation method according to claim 1, wherein in the fourth step, the obtained product is washed with ethanol and deionized water for 3-5 times; the drying temperature was 60 ℃.
  6. 6. The CTAB-doped Fe prepared by the preparation method of any one of claims 1 to 53S4The magnetic environmental remediation material of (1).
  7. 7. The CTAB-doped Fe prepared by the preparation method of any one of claims 1 to 53S4The magnetic environment restoration material is applied to removing heavy metals in water body environment.
  8. 8. The use according to claim 7, wherein the heavy metal is hexavalent chromium.
CN201810219311.5A 2018-03-16 2018-03-16 CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof Active CN108579681B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810219311.5A CN108579681B (en) 2018-03-16 2018-03-16 CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810219311.5A CN108579681B (en) 2018-03-16 2018-03-16 CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108579681A CN108579681A (en) 2018-09-28
CN108579681B true CN108579681B (en) 2020-10-27

Family

ID=63626502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810219311.5A Active CN108579681B (en) 2018-03-16 2018-03-16 CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108579681B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114870870B (en) * 2022-04-29 2023-04-11 成都理工大学 Magnetic environment purifying material for co-processing MO and Cr (VI) pollution and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102874879A (en) * 2012-10-12 2013-01-16 中国科学技术大学 Preparation method for Fe3S4 nanocrystalline material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014059323A1 (en) * 2012-10-12 2014-04-17 Advantageous Systems Llc Immobilization of particles on a matrix

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102874879A (en) * 2012-10-12 2013-01-16 中国科学技术大学 Preparation method for Fe3S4 nanocrystalline material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Solvothermal synthesis of greigite (Fe3S4)-Conducting polypyrrole nanocomposite and its application towards arsenic removal;Mahamudur Islam et al.;《Separation Science and Technology》;20170911;第1-18页 *
羧甲基纤维素钠辅助磁性Fe3S4纳米复合物的合成及其吸附与吸波性质研究;凌丹 等;《化学通报》;20141231;第77卷(第12期);第1202-1207页 *

Also Published As

Publication number Publication date
CN108579681A (en) 2018-09-28

Similar Documents

Publication Publication Date Title
CN110813251B (en) Modified nano material and application thereof in antimony-containing wastewater treatment
Wei et al. Scalable low temperature in air solid phase synthesis of porous flower-like hierarchical nanostructure SnS2 with superior performance in the adsorption and photocatalytic reduction of aqueous Cr (VI)
CN110894084B (en) Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage
CN104437390A (en) Preparation method of graphene oxide/amino acid composite material with adsorption effect on heavy metal ions
CN101599335B (en) Oxidation resistant dimethyl silicon oil based magnetic fluid and preparation method thereof
CN103007887B (en) Carbon-nanotube-loaded multi-stage nanometer ferroferric oxide adsorbent and preparation method and application thereof
CN108483613B (en) Hydrophilic material doped blending membrane loaded nano zero-valent iron composite material and preparation method and application thereof
CN102963938B (en) Spinel ferrite/CNx nanocomposite and preparation method thereof
CN107308929A (en) A kind of preparation method of graphene nano titanium dioxide compound photochemical catalyst
Tong et al. Facile synthesis of highly crystalline α-Fe2O3 nanostructures with different shapes as photocatalysts for waste dye treatment
CN108579681B (en) CTAB doped Fe3S4Magnetic environment repairing material and preparation method and application thereof
CN114225897B (en) Modified attapulgite loaded nano zero-valent iron composite material and preparation method and application thereof
CN107619045B (en) Method for in-situ preparation of small-size metal oxide on graphene
CN112547018A (en) Magnetic nano composite material and preparation method thereof
CN104046652A (en) Biosynthesis method of magnetic graphene composite material
CN111875025A (en) Graphene type nitrogen carbide loaded nano zero-valent iron composite material and preparation method and application thereof
JP5909125B2 (en) Method for producing metal particles using solvothermal reaction
CN107899541B (en) preparation method of magnetic carbon nanocomposite for adsorbing hexavalent chromium ions in wastewater
WO2021101394A4 (en) Modified nanostructured silica materials for heavy metal removal from contaminated water and the methods of production thereof
CN1299578C (en) Nano antiseptic silver powder preparation method using metallic silver
KR101135446B1 (en) Manufacturing method of hollow spheral iron oxide particles
CN110559935A (en) Preparation method of one-dimensional nano magnetons with stable solution dispersibility
CN112958780B (en) Flake nano metal nickel and preparation method and application thereof
Xu et al. Sonocatalytic Degradation of Tetracycline by Biobr/Fewo4 Nanomaterials in Collaboration with Potassium Persulfate
CN115007183B (en) Preparation method of monoatomic transition metal/nitrogen doped mesoporous carbon material for producing nitrogen by electrocatalytic reduction of nitrate

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
GR01 Patent grant
GR01 Patent grant