CN111137942A - Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof - Google Patents

Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof Download PDF

Info

Publication number
CN111137942A
CN111137942A CN201911268998.2A CN201911268998A CN111137942A CN 111137942 A CN111137942 A CN 111137942A CN 201911268998 A CN201911268998 A CN 201911268998A CN 111137942 A CN111137942 A CN 111137942A
Authority
CN
China
Prior art keywords
graphene quantum
composite material
quantum dot
precursor
quantum dots
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.)
Granted
Application number
CN201911268998.2A
Other languages
Chinese (zh)
Other versions
CN111137942B (en
Inventor
田静琦
付正
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 CN201911268998.2A priority Critical patent/CN111137942B/en
Publication of CN111137942A publication Critical patent/CN111137942A/en
Application granted granted Critical
Publication of CN111137942B publication Critical patent/CN111137942B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Abstract

The invention discloses a flaky porous graphene quantum dot/copper phosphide composite material and a preparation method thereof, and the preparation method comprises the following steps: taking a mixed aqueous solution containing graphene quantum dots and copper acetate as a precursor solution for self-assembly, freeze-drying to obtain the graphene quantum dots/metal ion precursor with a sheet structure, and then using NaH2PO2As a phosphorus source, the precursor is converted into a flaky porous graphene quantum dot/copper phosphide composite material by a low-temperature phosphating method. The method has the advantages of diverse raw material selection and wide source, simple and easy operation and high cost performance; the prepared sheet-shaped porous graphene quantum dot/copper phosphide composite material has important practical value and good application prospect in the field of photo-thermal seawater desalination.

Description

Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof
Technical Field
The invention relates to the field of energy materials, in particular to a preparation method of a flaky porous graphene quantum dot/copper phosphide composite material.
Background
The zero-dimensional structure of the graphene quantum dot endows the graphene quantum dot with unique physicochemical properties such as optical characteristics, high modifiability, good water solubility and dispersibility and the like, and is widely applied to the fields of photoelectrocatalysis and sensing, and energy utilization and conversion. The composite material constructed by the graphene quantum dots can take the advantages of all components into consideration, so that the material performance is improved. The reported graphene quantum dot/transition metal phosphide composite material is limited to a graphene quantum dot/nickel cobalt phosphide array structure (NanoEnergy, 2018, 48, 284) and cobalt phosphide/graphene quantum dot/graphene (ChemSusChem, 2017, 10, 1014) only, and the adopted method is that the graphene quantum dot and a precursor solution are mixed and then subjected to hydrothermal and phosphorization reactions to obtain a product, so that the large-scale preparation is difficult, and the product with adjustable morphology and size cannot be obtained. To date, there has been no report on graphene quantum dot/copper phosphide composite materials.
Disclosure of Invention
The invention aims to provide a preparation method of a flaky porous graphene quantum dot/copper phosphide composite material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a sheet-shaped porous graphene quantum dot/copper phosphide composite material and a preparation method thereof comprise the following steps: the method comprises the steps of self-assembling by taking a mixed aqueous solution of graphene quantum dots and copper acetate as a precursor solution, and freeze-drying to obtain the graphene quantum dots/metal ions (GQD/Cu) with a sheet structure2+) Precursor, then NaH2PO2As a phosphorus source, GQD/Cu is subjected to a low-temperature phosphating method2+Graphene quantum dot/copper phosphide composite material (GQD/Cu) converted into flaky porous material3P）。
Further, the graphene quantum dot is prepared by a chemical stripping method, and the method comprises the following steps: dispersing carbon black in a mixed solution of water and concentrated nitric acid, wherein the volume ratio is 1:1.5, refluxing for 20-40 hours at 120-180 ℃, and after the reaction is finished, centrifuging, dialyzing and drying to obtain the graphene quantum dot, wherein the temperature and the time are adjusted to control the size and the functional group concentration of the graphene quantum dot.
Further, the self-assembly is to stir the precursor solution for 5-8 hours at room temperature.
Further, in the precursor solution, the mass ratio of the graphene quantum dots to the copper acetate is controlled to be 10: 1-10: 5 GQD/Cu for the purpose of controlling precursor sheet shape2+The horizontal dimension and the thickness of (c).
Further, in the precursor solution, the concentration of the graphene quantum dots in the precursor solution is controlled to be 0.5-5 mg/mL, and the aim is to controlGQD/Cu for preparing precursor sheet2+The horizontal dimension and the thickness of (c).
Further, the low-temperature phosphorization is to convert GQD/Cu into2+Precursor and NaH2PO2Respectively arranged at the upstream and the downstream of carrier gas in the tube furnace, heated to 300-350 ℃ in argon atmosphere and kept for 2h, and the purpose of regulating and controlling the temperature is to control the flaky porous GQD/Cu3Pore size and composition of P.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a graphene quantum dot/copper phosphide composite material (GQD/Cu)3P), the technological process is simple and easy to implement, the raw material sources are wide, the cost performance is high, the morphology and the components of the formed sheet-shaped porous composite material are highly controllable, and the sheet-shaped porous composite material has excellent performance in the application of photo-thermal seawater desalination.
Drawings
Fig. 1 is a transmission electron microscope image of a graphene quantum dot used in the present invention.
FIG. 2 shows the graphene quantum dots/metal ions (GQD/Cu) prepared in example 1 of the present invention2+) Scanning electron micrographs of the precursor.
FIG. 3 is a scanning electron micrograph of the material prepared in example 1 of the present invention.
FIG. 4 shows the graphene quantum dots/metal ions (GQD/Cu) prepared in example 2 of the present invention2+) Scanning electron micrographs of the precursor.
FIG. 5 is a scanning electron micrograph of the material prepared in example 2 of the present invention.
FIG. 6 shows the graphene quantum dots/metal ions (GQD/Cu) prepared in example 3 of the present invention2+) Scanning electron micrographs of the precursor.
FIG. 7 is a scanning electron micrograph of the material prepared in example 3 of the present invention.
FIG. 8 shows the graphene quantum dots/metal ions (GQD/Cu) prepared in example 4 of the present invention2+) Scanning electron micrographs of the precursor.
FIG. 9 is a scanning electron micrograph of the material prepared in example 4 of the present invention.
Fig. 10 is a transmission electron micrograph of the graphene quantum dot used in example 5 of the present invention.
FIG. 11 shows the graphene quantum dots/metal ions (GQD/Cu) prepared in example 5 of the present invention2+) Scanning electron micrographs of the precursor.
FIG. 12 is a graph showing the photothermal seawater desalination performance of the material prepared in example 1 of the present invention (a: simulation of temperature profile with time under solar illumination; b: seawater evaporation rate under illumination).
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
Example 1
A preparation method of a flaky porous graphene quantum dot/copper phosphide composite material comprises the following steps:
weighing 10 mg of graphene quantum dots (the shape is shown in figure 1), 3.0 mg of copper acetate, adding 10 ml of deionized water, uniformly stirring, taking the mixed aqueous solution as a precursor solution, stirring at room temperature for 6 h, and performing freeze drying treatment to obtain the graphene quantum dots/metal ions (GQD/Cu) with the sheet structure2+) Precursor (the morphology is shown in figure 2). Graphene quantum dots/metal ions (GQD/Cu)2+) Precursor and NaH2PO2Respectively placing the materials at the upstream and downstream of carrier gas in a tubular furnace, heating to 320 ℃ in Ar atmosphere and keeping for 2 hours to obtain the flaky porous graphene quantum dot/copper phosphide composite material (GQD/Cu)3P）。
FIG. 3 is a scanning electron microscope image of the material prepared in example 1 of the present invention, from which it can be seen that the graphene quantum dot/copper phosphide composite material has a sheet structure with a horizontal size of 10 to 20 μm and a thickness of 50 to 80 nm.
Example 2
A preparation method of a flaky porous graphene quantum dot/copper phosphide composite material comprises the following steps:
weighing 10 mg of graphene quantum dots (the appearance is shown in figure 1), 1.5 mg of copper acetate, adding 10 ml of deionized water, stirring uniformly, taking the mixed water solution as a precursor solution, stirring at room temperature for 6 h, and performing freeze drying treatment to obtain the graphene quantum dotsTo graphene quantum dots/metal ions (GQD/Cu) having a lamellar structure2+) Precursor (the morphology is shown in fig. 4). Graphene quantum dots/metal ions (GQD/Cu)2+) Precursor and NaH2PO2Respectively placing the materials at the upstream and downstream of carrier gas in a tubular furnace, heating to 320 ℃ in Ar atmosphere and keeping for 2 hours to obtain the flaky porous graphene quantum dot/copper phosphide composite material (GQD/Cu)3P）。
FIG. 5 is a scanning electron microscope image of the material prepared in example 2 of the present invention, from which it can be seen that the graphene quantum dot/copper phosphide composite material is composed of a sheet structure with a horizontal size of 10 to 20 microns and a thickness of 30 to 60 nm, and a strip structure with a length of 5 to 10 microns.
Example 3
A preparation method of a flaky porous graphene quantum dot/copper phosphide composite material comprises the following steps:
weighing 10 mg of graphene quantum dots (the shape is shown in figure 1), 5.0 mg of copper acetate, adding 10 ml of deionized water, uniformly stirring, taking the mixed aqueous solution as a precursor solution, stirring at room temperature for 6 h, and performing freeze drying treatment to obtain the graphene quantum dots/metal ions (GQD/Cu) with the sheet structure2+) Precursor (its morphology is shown in fig. 6). Graphene quantum dots/metal ions (GQD/Cu)2+) Precursor and NaH2PO2Respectively placing the materials at the upstream and downstream of carrier gas in a tubular furnace, heating to 320 ℃ in Ar atmosphere and keeping for 2 hours to obtain the flaky porous graphene quantum dot/copper phosphide composite material (GQD/Cu)3P）。
FIG. 7 is a scanning electron microscope image of the material prepared in example 3 of the present invention, from which it can be seen that the graphene quantum dot/copper phosphide composite material has a sheet structure with a horizontal dimension of 5 to 10 μm and a thickness of 150 to 200 nm.
Example 4
A preparation method of a flaky porous graphene quantum dot/copper phosphide composite material comprises the following steps:
weighing 10 mg of graphene quantum dots (the morphology is shown in figure 1)) Adding 3.0 mg of copper acetate into 2 ml of deionized water, uniformly stirring, taking the mixed aqueous solution as a precursor solution, stirring at room temperature for 6 hours, and carrying out freeze drying treatment to obtain the graphene quantum dots/metal ions (GQD/Cu) with the sheet structure2+) Precursor (its morphology is shown in fig. 8). Graphene quantum dots/metal ions (GQD/Cu)2+) Precursor and NaH2PO2Respectively placing the materials at the upstream and downstream of carrier gas in a tubular furnace, heating to 320 ℃ in Ar atmosphere and keeping for 2 hours to obtain the flaky porous graphene quantum dot/copper phosphide composite material (GQD/Cu)3P）。
Fig. 9 is a scanning electron microscope image of the material prepared in example 4 of the present invention, from which it can be seen that the graphene quantum dot/copper phosphide composite material is a micron-sized bulk structure.
Example 5
A preparation method of a flaky porous graphene quantum dot/copper phosphide composite material comprises the following steps:
weighing 10 mg of graphene quantum dots (the shape is shown in figure 10), 3.0 mg of copper acetate, adding 10 ml of deionized water, uniformly stirring, taking the mixed aqueous solution as a precursor solution, stirring at room temperature for 6 h, and performing freeze drying treatment to obtain the graphene quantum dots/metal ions (GQD/Cu) with the sheet structure2+) Precursor (its morphology is shown in fig. 11). Graphene quantum dots/metal ions (GQD/Cu)2+) Precursor and NaH2PO2Respectively placing the materials at the upstream and downstream of carrier gas in a tubular furnace, heating to 320 ℃ in Ar atmosphere and keeping for 2 hours to obtain the flaky porous graphene quantum dot/copper phosphide composite material (GQD/Cu)3P）。
FIG. 12 is a graph showing the photothermal seawater desalination performance of the material prepared in example 1 of the present invention, and it can be seen from the graph that the material prepared in example 1 has high efficiency photothermal conversion performance, the temperature rises to 58.5 ℃ within 20 minutes, and the seawater evaporation rate is 1.57 kg m-2h-1。

Claims (8)

1. Flaky porous graphene quantum dot/copper phosphide compositeThe preparation method of the composite material is characterized by comprising the following steps: the method comprises the steps of carrying out self-assembly by taking a mixed aqueous solution of graphene quantum dots and copper acetate as a precursor solution, carrying out freeze drying to obtain graphene quantum dots/metal ion precursors with sheet structures, and then using NaH2PO2As a phosphorus source, the precursor is converted into a flaky porous graphene quantum dot/copper phosphide composite material by a low-temperature phosphating method.
2. The method of claim 1, wherein the graphene quantum dots are prepared by a chemical exfoliation method comprising the steps of: dispersing carbon black in a mixed solution of water and concentrated nitric acid, wherein the volume ratio is 1:1.5, refluxing for 20-40 hours at 120-180 ℃, and centrifuging, dialyzing and drying after the reaction is finished to obtain the carbon black.
3. The method according to claim 1, wherein the self-assembly is carried out by stirring the precursor solution at room temperature for 5-8 h.
4. The method according to claim 1, wherein in the precursor solution, the mass ratio of the graphene quantum dots to the copper acetate is controlled to be 10: 1-10: 5.
5. the method according to claim 1, wherein the concentration of the graphene quantum dots in the precursor solution is controlled to be 0.5-5 mg/mL.
6. The method of claim 1, wherein the low temperature phosphating is performed with GQD/Cu2+Precursor and NaH2PO2Respectively placing the carrier gas upstream and downstream in the tube furnace, heating to 300-350 ℃ under argon atmosphere and keeping for 2 h.
7. The sheet-like porous graphene quantum dot/copper phosphide composite material prepared by the method of any one of claims 1 to 6.
8. The application of the sheet-like porous graphene quantum dot/copper phosphide composite material prepared by the method as described in any one of claims 1 to 6 in photothermal seawater desalination.
CN201911268998.2A 2019-12-11 2019-12-11 Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof Active CN111137942B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911268998.2A CN111137942B (en) 2019-12-11 2019-12-11 Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911268998.2A CN111137942B (en) 2019-12-11 2019-12-11 Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111137942A true CN111137942A (en) 2020-05-12
CN111137942B CN111137942B (en) 2022-03-15

Family

ID=70518075

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911268998.2A Active CN111137942B (en) 2019-12-11 2019-12-11 Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111137942B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552902A (en) * 2020-11-20 2021-03-26 扬州大学 Graphene quantum dot assembly with foam structure and preparation method thereof
CN113488650A (en) * 2020-08-28 2021-10-08 中南大学 Cu3P @ P-doped mesoporous carbon composite framework and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107403911A (en) * 2017-06-20 2017-11-28 江苏大学 Graphene/transition metal phosphide/C-base composte material, preparation method and lithium ion battery negative electrode
CN109433030A (en) * 2018-11-23 2019-03-08 山东大学 A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107403911A (en) * 2017-06-20 2017-11-28 江苏大学 Graphene/transition metal phosphide/C-base composte material, preparation method and lithium ion battery negative electrode
CN109433030A (en) * 2018-11-23 2019-03-08 山东大学 A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JINGQI TIAN ET AL.: "Graphene quantum dot engineered nickel-cobalt phosphide as highly efficient bifunctional catalyst for overall water splitting", 《NANO ENERGY》 *
马海燕: "半导体/碳材料的制备及其光热性能研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113488650A (en) * 2020-08-28 2021-10-08 中南大学 Cu3P @ P-doped mesoporous carbon composite framework and preparation method and application thereof
CN112552902A (en) * 2020-11-20 2021-03-26 扬州大学 Graphene quantum dot assembly with foam structure and preparation method thereof

Also Published As

Publication number Publication date
CN111137942B (en) 2022-03-15

Similar Documents

Publication Publication Date Title
CN109046408B (en) Composite hydrogen evolution electro-catalytic material and preparation method and application thereof
CN109956463B (en) Carbon nano tube and preparation method thereof
CN108837838B (en) Ultra-small vanadium carbide embedded carbon nanotube material, preparation method and application thereof in aspect of hydrogen production by water splitting
CN109437156B (en) Preparation method of nitrogen-doped carbon nanotube
CN110148760B (en) Porous carbon-carbon nanotube composite material and preparation method and application thereof
CN110342477B (en) Oxygen-doped porous carbon nitride nanosheet and preparation method thereof
CN111437846B (en) Porous CoO/CoP nanotube and preparation method and application thereof
CN110479271B (en) Preparation method of two-dimensional nickel-carbon nanosheet catalyst for hydrogen production through water electrolysis
CN103613093B (en) A kind of hydrogen reducing prepares the method for Graphene
CN111137942B (en) Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof
CN111203262B (en) Method for rapidly preparing carbon nitride nanosheet loaded nano-copper, product and application thereof
CN104986742A (en) Bead-chain-like graphitized carbon nitride nano material and preparation method thereof
CN108126728B (en) Preparation method of g-C3N4/g-C3N4 metal-free isomeric structure, obtained product and application
CN105329883A (en) Porous graphene preparation method
CN111013619B (en) Molybdenum carbide nanorod for catalyst and preparation method and application thereof
CN103787324B (en) A kind of method based on template synthesis Graphene porous membrane
CN108117064B (en) Preparation method of folded graphene
Cai et al. Recent advances in metal-free electrocatalysts for the hydrogen evolution reaction
CN110015651B (en) Preparation method of layered carbon material
CN112725830B (en) Preparation method of multistage pore cobalt phosphide/nitrogen-doped carbon network electrocatalyst
CN110721723B (en) Interpenetrating network structure conductive carbon-based alloy material and preparation method thereof
CN112552902A (en) Graphene quantum dot assembly with foam structure and preparation method thereof
CN111359637A (en) Hydrogen production catalyst nickel diselenide nanoparticle @ carbon nanosheet composite material and preparation method and application thereof
CN112520727B (en) Carbon nanotube prepared by taking graphene quantum dots as template and method thereof
CN110902672A (en) Photothermal effect multi-stage structure microspherical graphene aerogel and preparation method thereof

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