CN113877516A - Preparation method of germanium selenide nano material and application of germanium selenide nano material - Google Patents
Preparation method of germanium selenide nano material and application of germanium selenide nano material Download PDFInfo
- Publication number
- CN113877516A CN113877516A CN202111316172.6A CN202111316172A CN113877516A CN 113877516 A CN113877516 A CN 113877516A CN 202111316172 A CN202111316172 A CN 202111316172A CN 113877516 A CN113877516 A CN 113877516A
- Authority
- CN
- China
- Prior art keywords
- germanium selenide
- germanium
- selenide nano
- oleylamine
- gei
- 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
Links
- QIHHYQWNYKOHEV-UHFFFAOYSA-N 4-tert-butyl-3-nitrobenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O QIHHYQWNYKOHEV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910006149 GeI4 Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- 239000002135 nanosheet Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000003115 biocidal effect Effects 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 4
- 239000004098 Tetracycline Substances 0.000 description 12
- 229960002180 tetracycline Drugs 0.000 description 12
- 229930101283 tetracycline Natural products 0.000 description 12
- 235000019364 tetracycline Nutrition 0.000 description 12
- 150000003522 tetracyclines Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003090 WSe2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- -1 cyclic tetracycline Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
-
- 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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
-
- 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
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- 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
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a germanium selenide nano material and application of the germanium selenide nano material. The preparation method of the germanium selenide nanometer material comprises the step of mixing GeI4Mixing with oleylamine, and sequentially carrying out magnetic stirring, vacuumizing, heating and heat preservation; to GeI4And injecting selenourea into the mixture of the selenium and the oleylamine, refluxing the reaction mixture at high temperature and under an inert gas environment, cooling to room temperature, sequentially washing with acetone, alcohol and deionized water, and drying to obtain the germanium selenide nano-particles. The preparation method of the germanium selenide nano material comprises the steps of mixing selenourea and GeI4The germanium selenide nano-particle material is prepared by carrying out redox reaction at high temperature in an oleylamine solvent to synthesize germanium selenide nano-particles, cooling to room temperature, washing with three solvents of acetone, alcohol and deionized water, and drying. The germanium selenide nanometer material is applied to degrading organic pollutants.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method of a germanium selenide nanometer material and application of the germanium selenide nanometer material.
Background
In recent years, with the increasing development of industry, a large amount of pollutants such as waste water and the like are increased, the quality of water, soil and air is gradually deteriorated, particularly organic dyes which are difficult to degrade are adopted, the types of the organic dyes are tens of thousands, particularly tetracycline in antibiotics has the characteristics of difficult degradability and durability, if the organic dyes are discharged without being completely degraded, the dyes can enter human bodies through other ways, and finally the human health is harmed and the environmental pollution is caused. The current methods for degrading organic dyes are: adsorption filtration, photocatalytic methods, and the like. In order to meet the urgent requirements of people on green and environment-friendly living environment, the technology which is high in efficiency, mild in reaction condition, low in cost and recyclable is developed to degrade antibiotic organic pollutants is urgent.
Researches show that the two-dimensional piezoelectric material can effectively remove rhodamine B organic pollutants through piezoelectric catalysis, and various two-dimensional piezoelectric materials are reported, such as MoS2, WS2, WSe2, C3N4 and the like. However, two-dimensional piezoelectric materials have been less investigated for antibiotic removal. Therefore, there is a need to find a method for degrading antibiotic organic pollutants by using an effective piezoelectric catalytic technology.
Germanium selenide (GeSe) is a novel two-dimensional material, is a direct band gap semiconductor material with a wide-band photoluminescence spectrum, a complex energy band structure and excellent photoelectric characteristics, and has a good application prospect in the development of the photoelectric field at present. However, the teaching of Yang indicates that germanium selenide has higher piezoelectric properties, GeSe: d11 is 212.13pm/V (appl. Phys. Lett.107, 173104(2015)), so the selected germanium selenide nano material has bright prospect in the aspect of dye wastewater degradation, but the existing preparation method of the germanium selenide nano material is troublesome to operate and is not suitable for industrial production.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a germanium selenide nanometer material and application of the germanium selenide nanometer material, wherein the preparation method has the characteristics of simple operation, easy industrial production and the like.
A preparation method of a germanium selenide nanometer material comprises the following steps:
GeI will be mixed4Mixing with oleylamine, and sequentially carrying out magnetic stirring, vacuumizing, heating and heat preservation;
to GeI4And injecting selenourea into the mixture of the selenium and the oleylamine, refluxing the reaction mixture at high temperature and under an inert gas environment, cooling to room temperature, sequentially washing with acetone, alcohol and deionized water, and drying to obtain the germanium selenide nano-particles.
The invention relates to a preparation method of a germanium selenide nano material, which comprises the steps of mixing selenourea and GeI4In the presence of oleylamineUnder the action of the agent, carrying out redox reaction at high temperature to synthesize germanium selenide nano-particles, cooling to room temperature, washing by three solvents of acetone, alcohol and deionized water, and drying to obtain the germanium selenide nano-particle material.
Further preferably, the step of GeI4Mixing with oleylamine, and sequentially performing magnetic stirring, vacuumizing, heating and heat preservation, wherein the steps of:
0.4g of GeI4And 20mL of oleylamine are added into a three-neck flask in 25mL of air, magnetic stirring is carried out sequentially at the rotating speed of 250r/min, vacuum pumping is carried out until the pressure is minus 0.2MPa, then heating is carried out until the temperature is 120 ℃, and heat preservation is carried out for 30 min;
the direction GeI4And injecting selenourea into the oleylamine mixture, and then refluxing the reaction mixture at an elevated temperature and under an inert gas atmosphere, comprising:
into the three-necked flask was charged 120. mu.L selenourea, and the reaction mixture was heated at 240 ℃ and under N2The mixture was refluxed for 12 hours.
Wherein, the oleylamine can protect the hydrophobicity of the nano material, and is also used as a reducing agent and a surfactant in the preparation. The magnetic stirring speed is 250r/min, and the stirring is carried out at a low speed. Because the stirring speed is higher, the amount of air blended is increased, the synthetic materials are affected, and the low-speed stirring is mainly used for dispersing, so that the powder and oleylamine thereof are attached to the inner side of the three-neck flask, and the solution is uneven and wasted.
The inert gas is introduced to prevent the synthetic material from being oxidized, and the reaction can be carried out smoothly.
Further preferably, the preparation method of the germanium selenide nanometer material further comprises the following steps:
and grinding the germanium selenide nano particles into powder, sieving, adding the powder into ethanol, carrying out ice bath ultrasonic treatment, centrifuging the obtained product, taking supernate, and carrying out centrifugal drying to obtain the germanium selenide nanosheet.
Further preferably, the germanium selenide nanoparticle material is ground into powder, sieved and added into ethanol for ice bath ultrasonic treatment, and the centrifugation of the obtained product comprises the following steps:
grinding the germanium selenide nano-particle material into powder, sieving the powder by a 600-mesh sieve, adding the powder into ethanol, carrying out ice bath and ultrasonic treatment for 2 hours, and centrifuging the obtained product at 8000rpm for 2 min.
Further preferably, the germanium selenide nanoparticles have a thickness of 1-2 μm.
Further preferably, the length of the germanium selenide nanosheets is 300-900 nm.
Compared with the prior art, the preparation method of the germanium selenide nano material comprises the steps of mixing selenourea and GeI4Carrying out redox reaction at high temperature in an oleylamine solvent to synthesize germanium selenide nano particles, cooling to room temperature, washing with three solvents of acetone, alcohol and deionized water, and drying to obtain a germanium selenide nano particle material, wherein the whole preparation method is simple to operate, environment-friendly and pollution-free, and easy for industrial production; the germanium selenide nanosheet material is prepared by a simple liquid phase stripping method, has excellent piezoelectric performance, can better respond to ultrasonic vibration, and is beneficial to enrichment and conversion of sound waves, so that the removal efficiency of organic pollutants is improved. The preparation method of the germanium selenide nanometer material has the characteristics of simple operation, suitability for industrial production and the like.
The invention further provides an application of the germanium selenide nanometer material prepared by the preparation method of the germanium selenide nanometer material, and the application is the degradation of organic pollutants.
The germanium selenide nano material is used for efficiently degrading antibiotic organic pollutants, has the advantages of environmental protection, high efficiency, high stability, high performance and recyclability, and has important significance in promoting the environmental engineering application of piezoelectric materials.
Further preferably, the application method is as follows:
dispersing the germanium selenide nano material in an aqueous solution of organic pollutants, magnetically stirring under a dark condition to achieve adsorption-desorption balance, then carrying out piezoelectric catalytic degradation reaction under the action of ultrasonic vibration, and taking supernatant to determine the concentration of the target pollutants.
Further preferably, the mass of the germanium selenide nanometer material is 50-100 mg;
the organic pollutant is antibiotic with concentration of 0.001-0.01 mol/L.
Further preferably, the power of the ultrasonic vibration is 20-100W, and the frequency is 20-100 KHz.
Compared with the prior art, the germanium selenide nano material provided by the invention is applied, the germanium selenide nano sheet and the organic pollutant are used as a reaction system, water is decomposed under the condition of ultrasonic treatment, and the removal effect is finally achieved. Specifically, in 45kHz ultrasonic wave, the 120min degradation efficiency can reach 95%.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
Fig. 1 is an SEM image of germanium selenide nanoparticles obtained by the present invention.
Fig. 2 is an SEM image of germanium selenide nanosheets obtained in the present invention.
FIG. 3 is a graph comparing the tetracycline removal results of examples 3 and 4 of the present invention.
Fig. 4 is a performance stability test of germanium selenide nanosheets in the cyclic tetracycline removal process of example 4 of the present invention.
Detailed Description
The terms of orientation of up, down, left, right, front, back, top, bottom, and the like, referred to or may be referred to in this specification, are defined relative to their configuration, and are relative concepts. Therefore, it may be changed according to different positions and different use states. Therefore, these and other directional terms should not be construed as limiting terms.
The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of implementations consistent with certain aspects of the present disclosure.
The terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
The germanium selenide nanomaterial can be in the form of particles or flakes, but is not limited thereto. Preferably, the germanium selenide nanometer material is sheet-shaped, and the sheet-shaped germanium selenide nanometer material can better respond to ultrasonic vibration and is beneficial to enrichment and conversion of sound waves, so that the hydrogen production efficiency is improved. Specifically, the length of the sheet-shaped nano germanium selenide is 300-900nm, and exemplary lengths are 300nm, 500nm, 700nm, 800nm and 900nm, but the invention is not limited thereto.
Example 1
The embodiment provides a preparation method of germanium selenide nanoparticles, which comprises the following steps:
0.4g of GeI4And 20mL of Oleylamine (OLA) are added into a three-neck flask in 25mL of air, magnetic stirring is carried out at the rotating speed of 250r/min, then the vacuum pumping is carried out to-0.2 MPa, and the mixture is heated to 120 ℃ and kept for 30 min;
then 120. mu.L of selenourea was injected and the reaction mixture was heated at 240 ℃ and under N2And (3) refluxing for 12h under the flow, cooling to room temperature, washing with acetone, alcohol and deionized water in sequence, and drying to obtain germanium selenide nanoparticles, wherein the thickness of the germanium selenide nanoparticles is 1-2 microns.
Example 2
The embodiment provides a preparation method of germanium selenide nanosheets, which comprises the following steps:
grinding the germanium selenide nano-particle material into powder, sieving the powder by a 600-mesh sieve, adding the powder into ethanol, carrying out ice bath and ultrasonic treatment for 2 hours, centrifuging the obtained product at 8000rpm for 2min, and carrying out centrifugal drying to obtain the germanium selenide nanosheet. The length of the germanium selenide nanosheet is 300-900, and according to specific implementation conditions, the germanium selenide nanosheet can be implemented as 300nm, 500nm, 700nm, 800nm and 900 nm.
Scanning Electron Microscope (SEM) analysis is performed on the germanium selenide nanoparticles and the germanium selenide nanosheets in examples 1 and 2, and as shown in fig. 1 and 2, it can be seen that the germanium selenide obtained in example 1 is granular, and the germanium selenide obtained in example 2 is flaky.
The invention also provides an application of the germanium selenide nanosheet, wherein the application is used for degrading organic pollutants, and the degradation method of the organic pollutants comprises the following steps:
dispersing the germanium selenide nano material in an aqueous solution of organic pollutants, magnetically stirring under a dark condition to achieve adsorption-desorption balance, then carrying out piezoelectric catalytic degradation reaction under the action of ultrasonic vibration, and taking supernatant to determine the concentration of the target pollutants. The specific embodiment is as follows, wherein the organic contaminant is tetracycline selected from antibiotics.
Example 3
50mg of germanium selenide nanoparticles of example 1 were put into 100mL of deionized water containing 0.005mol/L of antibiotic, magnetically stirred in the dark to achieve adsorption-desorption equilibrium, and subjected to ultrasonic waves of 45kHz and 100W for 0h, 1h, 2h, 3h, 4h and 5h, respectively, and a High Performance Liquid Chromatograph (HPLC) with a UV detector to measure antibiotic concentration.
Example 4
50mg of germanium selenide nanosheets obtained in example 2 were placed in 100mL of deionized water containing 0.005mol/L of antibiotic, magnetically stirred in the dark to achieve adsorption-desorption equilibrium, and subjected to ultrasonic waves of 45kHz and 100W for 0h, 1h, 2h, 3h, 4h and 5h, respectively, and a High Performance Liquid Chromatograph (HPLC) with a UV detector was used to determine the antibiotic concentration.
Example 5
75mg of germanium selenide nanosheets obtained in example 2 were placed in 100mL of deionized water containing 0.001mol/L of antibiotic, magnetically stirred in the dark to achieve adsorption-desorption equilibrium, and subjected to ultrasonic waves of 20kHz and 20W for 0h, 1h, 2h, 3h, 4h and 5h, respectively, and a High Performance Liquid Chromatograph (HPLC) with a UV detector was used to determine the antibiotic concentration.
Example 6
100mg of germanium selenide nanoparticles of example 1 were put into 100mL of deionized water containing 0.01mol/L of antibiotic, magnetically stirred in the dark to reach adsorption-desorption equilibrium, and subjected to ultrasonic waves of 80kHz and 60W for 0h, 1h, 2h, 3h, 4h and 5h, respectively, and a High Performance Liquid Chromatograph (HPLC) with a UV detector was used to measure the antibiotic concentration.
Examples 3-6 the removal rates for tetracycline are shown in the following table:
| examples | Rate of tetracycline removal |
| 3 | 28％ |
| 4 | 95％ |
| 5 | 98％ |
| 6 | 35％ |
As can be seen from the above table, under the ultrasonic condition, the tetracycline removal rates of the germanium selenide nanoparticle material in the present invention are respectively 28% and 35%, and under the ultrasonic condition, the tetracycline removal rates of the germanium selenide nanoparticle material are respectively 95% and 98%, so that the germanium selenide nanoparticle material has a higher tetracycline removal rate under the ultrasonic condition. As can be seen from fig. 4, the germanium selenide nanosheet material is more stable in tetracycline degradation.
The mechanism of action in this example is:
the germanium selenide material and the organic pollutant tetracycline are mixed to obtain a reaction system, and the reaction system is subjected to ultrasonic treatment to finally achieve the removal effect. Specifically, when the ultrasonic wave acts on the germanium selenide nanometer material, an electric field is generated, under the action of the electric field, electron holes migrate in opposite directions, the local electron density on the surface of the germanium selenide nanometer material is increased, the redox reaction at a solid-liquid interface is promoted, and therefore tetracycline is removed.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A preparation method of germanium selenide nanometer material is characterized in that: the method comprises the following steps:
GeI will be mixed4Mixing with oleylamine, and sequentially carrying out magnetic stirring, vacuumizing, heating and heat preservation;
to GeI4And injecting selenourea into the mixture of the selenium and the oleylamine, refluxing the reaction mixture at high temperature and under an inert gas environment, cooling to room temperature, sequentially washing with acetone, alcohol and deionized water, and drying to obtain the germanium selenide nano-particles.
2. The method for preparing germanium selenide nanometer material according to claim 1, wherein: said will GeI4Mixing with oleylamine, and sequentially performing magnetic stirring, vacuumizing, heating and heat preservation, wherein the steps of:
0.4g of GeI4And 20mL of oleylamine are added into a 25mL three-necked flask placed in the air, magnetic stirring is carried out sequentially at the rotating speed of 250r/min, vacuum pumping is carried out until the pressure is minus 0.2MPa, then heating is carried out until the temperature is 120 ℃, and heat preservation is carried out for 30 min;
the direction GeI4And injecting selenourea into the oleylamine mixture, and then refluxing the reaction mixture at an elevated temperature and under an inert gas atmosphere, comprising:
into the three-necked flask was charged 120. mu.L selenourea, and the reaction mixture was heated at 240 ℃ and under N2The mixture was refluxed for 12 hours.
3. The method for preparing germanium selenide nanometer material according to claim 1, wherein: the preparation method of the germanium selenide nanometer material also comprises the following steps:
and grinding the germanium selenide nano particles into powder, sieving, adding the powder into ethanol, carrying out ice bath ultrasonic treatment, centrifuging the obtained product, taking supernate, and carrying out centrifugal drying to obtain the germanium selenide nanosheet.
4. The method for preparing germanium selenide nanometer material according to claim 3, wherein: grinding the germanium selenide nano-particle material into powder, sieving, adding the powder into ethanol, carrying out ice bath ultrasonic treatment, and centrifuging the obtained product, wherein the method comprises the following steps:
grinding the germanium selenide nano-particle material into powder, sieving the powder by a 600-mesh sieve, adding the powder into ethanol, carrying out ice bath and ultrasonic treatment for 2 hours, and centrifuging the obtained product at 8000rpm for 2 min.
5. The method for preparing germanium selenide nano-material according to any one of claims 1-4, wherein: the thickness of the germanium selenide nano-particles is 1-2 mu m.
6. The method for preparing germanium selenide nano-material according to any one of claims 1-4, wherein: the length of the germanium selenide nanosheet is 300-900 nm.
7. Use of a germanium selenide nanomaterial prepared by the method of any one of claims 1-6, wherein: the application is the degradation of organic pollutants.
8. The use of germanium selenide nanomaterial according to claim 7, wherein: the application method comprises the following steps:
dispersing the germanium selenide nano material in an aqueous solution of organic pollutants, magnetically stirring under a dark condition to achieve adsorption-desorption balance, then carrying out piezoelectric catalytic degradation reaction under the action of ultrasonic vibration, and taking supernatant to determine the concentration of the target pollutants.
9. The use of germanium selenide nanomaterial according to claim 8, wherein the mass of the germanium selenide nanomaterial is 50-100 mg;
the organic pollutant is antibiotic with concentration of 0.001-0.01 mol/L.
10. The use of germanium selenide nanomaterial according to claim 8, wherein: the power of the ultrasonic vibration is 20-100W, and the frequency is 20-100 KHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111316172.6A CN113877516A (en) | 2021-11-08 | 2021-11-08 | Preparation method of germanium selenide nano material and application of germanium selenide nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111316172.6A CN113877516A (en) | 2021-11-08 | 2021-11-08 | Preparation method of germanium selenide nano material and application of germanium selenide nano material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113877516A true CN113877516A (en) | 2022-01-04 |
Family
ID=79017530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111316172.6A Pending CN113877516A (en) | 2021-11-08 | 2021-11-08 | Preparation method of germanium selenide nano material and application of germanium selenide nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113877516A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159474A (en) * | 2022-07-20 | 2022-10-11 | 湘潭大学 | Germanium selenide nanosheet and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887562A (en) * | 2012-11-01 | 2013-01-23 | 浙江师范大学 | Method for ultrasonically degrading dye wastewater by adopting nano piezoelectric material |
| CN104445104A (en) * | 2014-11-17 | 2015-03-25 | 南京师范大学 | GeSe2 nanocrystalline as well as preparation method and application thereof |
-
2021
- 2021-11-08 CN CN202111316172.6A patent/CN113877516A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887562A (en) * | 2012-11-01 | 2013-01-23 | 浙江师范大学 | Method for ultrasonically degrading dye wastewater by adopting nano piezoelectric material |
| CN104445104A (en) * | 2014-11-17 | 2015-03-25 | 南京师范大学 | GeSe2 nanocrystalline as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JING LI等: "Synthesis and Photocatalytic Properties of SnSe2/Se Heterojunction Films", 《NANO: BRIEF REPORTS AND REVIEWS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159474A (en) * | 2022-07-20 | 2022-10-11 | 湘潭大学 | Germanium selenide nanosheet and preparation method thereof |
| CN115159474B (en) * | 2022-07-20 | 2024-02-02 | 湘潭大学 | Germanium selenide nano-sheet and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Construction of direct Z-scheme SnS2@ ZnIn2S4@ kaolinite heterostructure photocatalyst for efficient photocatalytic degradation of tetracycline hydrochloride | |
| Sun et al. | Facile synthesis of two clay minerals supported graphitic carbon nitride composites as highly efficient visible-light-driven photocatalysts | |
| CN104941674B (en) | Catalyst of phosphatization cobalt and its preparation method and application is loaded on a kind of activated carbon | |
| Liu et al. | A magnetically separable photocatalyst based on nest-like γ-Fe 2 O 3/ZnO double-shelled hollow structures with enhanced photocatalytic activity | |
| CN105056985B (en) | g‑C3N4The visible light-responded catalytic membrane of/graphene oxide/Nanoscale Iron | |
| Li et al. | Facile synthesis of ZnO/g-C3N4 composites with honeycomb-like structure by H2 bubble templates and their enhanced visible light photocatalytic performance | |
| Yu et al. | In situ preparation of g-C3N4/polyaniline hybrid composites with enhanced visible-light photocatalytic performance | |
| Wei et al. | Three-dimensional flower heterojunction g-C3N4/Ag/ZnO composed of ultrathin nanosheets with enhanced photocatalytic performance | |
| CN104353469A (en) | Method for preparing nanocomposite photocatalyst and application of nanocomposite photocatalyst | |
| CN101613537A (en) | A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide | |
| Liu et al. | Improved photocatalytic activity of MWCNT/BiOBr composite synthesized via interfacial covalent bonding linkage | |
| CN108654607B (en) | Preparation method of silver nanoparticle/carbon/titanium dioxide nano composite with core-shell structure | |
| CN109433229A (en) | A kind of preparation method of CdS/CoO nano-heterogeneous structure | |
| CN113877516A (en) | Preparation method of germanium selenide nano material and application of germanium selenide nano material | |
| CN109317183A (en) | A kind of boron nitride quantum dot/ultra-thin porous carbonitride composite photocatalyst material and its preparation method and application | |
| Wang et al. | Target preparation of multicomponent composites Au@ CdS/g-C3N4 as efficient visible light photocatalysts with the assistance of biomolecules | |
| CN102502771B (en) | Method for preparing cuprous oxide (Cu2O) with hierarchical flower-like structure | |
| CN108654671B (en) | Composite photocatalyst and preparation method and application thereof | |
| Kang et al. | Preparation of Zn2GeO4 nanosheets with MIL-125 (Ti) hybrid photocatalyst for improved photodegradation of organic pollutants | |
| Sun et al. | Microwave in-situ liquid-phase deposition of Cu2O/Tg-C3N4 heterojunction for enhancing visible light photocatalytic degradation of tetracycline | |
| CN110193362A (en) | A kind of zinc oxide/carbon composite photocatalyst and preparation method thereof | |
| Zhang et al. | Electrostatic self-assembly of 2D/2D Bi2WO6/ZnIn2S4 heterojunction with enhanced photocatalytic degradation of tetracycline hydrochloride | |
| CN107790183B (en) | Conjugated polymer nanoparticle photocatalyst, preparation method and application thereof | |
| CN112209476A (en) | Method for degrading organic dye by applying low-dimensional zinc oxide nano material through piezoelectric catalysis | |
| CN103752329B (en) | A kind of photochemical method for preparation of CuS photocatalyst |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230512 Address after: 528000 Room 208, 2nd Floor, Building A, No. 92 Suiyan West Road, Yanbu, Dali Town, Nanhai District, Foshan City, Guangdong Province (Residence Declaration) Applicant after: Guangdong Qingfo Industry Investment and Development Co.,Ltd. Applicant after: Li Shun Address before: Room 1101, 14th Floor, No. 8, Zone A, Hantian Science and Technology City, No. 17 Shenhai Road, Guicheng Street, Nanhai District, Foshan City, Guangdong Province, 528000 Applicant before: Foshan (South China) New Material Research Institute |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230803 Address after: 528000 Room 601, 6th floor, building B, No. 92, Hexi Road, Suiyan Road, Yanbu Town, Dali Town, Nanhai District, Foshan City, Guangdong Province (residence declaration) Applicant after: Guangdong Yina New Material Technology Co.,Ltd. Address before: 528000 Room 208, 2nd Floor, Building A, No. 92 Suiyan West Road, Yanbu, Dali Town, Nanhai District, Foshan City, Guangdong Province (Residence Declaration) Applicant before: Guangdong Qingfo Industry Investment and Development Co.,Ltd. Applicant before: Li Shun |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220104 |
|
| RJ01 | Rejection of invention patent application after publication |