CN111330620A - Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof - Google Patents
Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000009830 intercalation Methods 0.000 title claims abstract description 23
- 230000002687 intercalation Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003624 transition metals Chemical group 0.000 claims abstract description 30
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 8
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002815 nickel Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- WNTSKRMFHPIFOI-UHFFFAOYSA-K trichloroiron nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.Cl[Fe](Cl)Cl WNTSKRMFHPIFOI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a preparation method of an intercalation type graphite-like carbon nitride composite material, which comprises the following steps: mixing the graphite-like carbon nitride g-C3N5 intercalated by alkali metal ions with transition metal salt, and stirring to obtain the intercalated graphite-like carbon nitride composite material. The application also provides an intercalated graphite-like carbon nitride composite material which consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N 5. The intercalation graphite-like carbon nitride composite material has huge application prospects in the aspects of photoelectrocatalysis, electrocatalysis, energy storage, composite materials and the like, and compared with the existing transition metal single atom, the composite material is simple in synthesis method, large in loading capacity and easy for large-scale production.
Description
Technical Field
The invention relates to the technical field of novel composite materials, in particular to an intercalation type graphite-like carbon nitride composite material, and a preparation method and application thereof.
Background
Transition metal monatomics have the highest atomic utilization and specific activity, however, synthesis of transition metal monatomics still has difficulties, such as low yield and expensive cost of atomic layer deposition methods, and general strategies for large scale synthesis also have certain challenges.
The graphite-like carbon nitride (g-C3N5) is an important conjugated polymer semiconductor, has an excellent electronic energy band structure (the band gap width is 1.76eV), chemical stability and environmental friendliness, and has such characteristics that the g-C3N5 is widely applied, including the aspects of visible light photocatalytic decomposition of water, photodegradation of organic pollutants and the like.
Disclosure of Invention
The invention aims to provide an intercalation type graphite-like carbon nitride composite material and a preparation method thereof, and the intercalation type graphite-like carbon nitride composite material provided by the application can be used as an excellent catalyst for water decomposition oxygen analysis reaction.
In view of the above, the present application provides a method for preparing an intercalated graphite-like carbon nitride composite material, including:
mixing the graphite-like carbon nitride g-C3N5 intercalated by alkali metal ions with transition metal salt, and stirring to obtain the intercalated graphite-like carbon nitride composite material.
Preferably, the preparation method of the alkali metal ion intercalated graphite-like carbon nitride g-C3N5 specifically comprises the following steps:
mixing alkali metal bromide, 3-amino-1, 2, 4-triazole and water, evaporating and grinding to obtain mixed powder;
primarily calcining the mixed powder to obtain initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5;
and calcining the initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5 again to obtain the alkali metal ion intercalated graphite-like carbon nitride g-C3N 5.
Preferably, the primary calcination temperature is 500-600 ℃, and the secondary calcination temperature is 400-500 ℃.
Preferably, the stirring temperature is 50-100 ℃ and the stirring time is 24-48 h.
Preferably, the transition metal salt is selected from iron nitrate nonahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, manganese sulfate monohydrate, or iridium chloride trihydrate.
The application also provides an intercalation type graphite-like carbon nitride composite material which consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N 5.
Preferably, the transition metal atom is selected from a nickel atom, a cobalt atom, an iron atom, a manganese atom or an iridium atom.
The application also provides the intercalation graphite-like carbon nitride composite material prepared by the preparation method or the application of the intercalation graphite-like carbon nitride composite material in water decomposition oxygen analysis reaction.
The application provides a preparation method of an intercalation type graphite-like carbon nitride composite material, which is prepared by mixing alkali metal ion intercalated graphite-like carbon nitride g-C3N5 with transition metal salt and stirring; the intercalation type graphite-like carbon nitride composite material consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N5; the pyridine nitrogen atoms rich in electrons in the composite material provide rich coordination sites for transition metal atoms, and van der Waals force between adjacent layers of g-C3N5 can stabilize the transition metal atoms and can prevent the transition metal atoms from aggregating into particles, so that the composite material can be stably stored; furthermore, the electronic structure of transition metal atoms can be changed due to the interaction between adjacent layers, so that the energy barrier of the reaction is reduced, and the composite material can be used as a catalyst in the water decomposition oxygen analysis reaction.
Drawings
FIG. 1 is a SEM of Ni/g-C3N5 prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of Ni/g-C3N5 prepared in example 1 of the present invention;
FIG. 3 is a digital photograph of a K/g-C3N5 real object prepared in example 1 of the present invention;
FIG. 4 is a digital photograph of a Ni/g-C3N5 real object prepared in example 1 of the present invention;
FIG. 5 is an EXAFS plot of Ir/g-C3N5 prepared in example 4 of the present invention;
FIG. 6 is an LSV curve of the hydrolytic oxygen evolution reaction of Ni/g-C3N5 prepared in example 1 of the present invention under alkaline conditions.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Based on some problems still existing in the existing large-scale monoatomic synthesis method, the application provides an intercalation type graphite-like carbon nitride composite material and a preparation method thereof, and particularly, the embodiment of the invention discloses a preparation method of the intercalation type graphite-like carbon nitride composite material, which comprises the following steps:
mixing the graphite-like carbon nitride g-C3N5 intercalated by alkali metal ions with transition metal salt, and stirring to obtain the intercalated graphite-like carbon nitride composite material.
In the process of preparing the intercalation type graphite-like carbon nitride composite material (M/g-C3N5, M represents transition metal atoms), the intercalation type graphite-like carbon nitride composite material is obtained by mixing and stirring the alkali metal ion intercalated graphite-like carbon nitride g-C3N5 and transition metal salt; in the process, alkali metal ions and transition metal atoms are subjected to electrostatic ion exchange; namely, the graphite-like carbon nitride intercalated by alkali metal ions can promote cations in a transition metal salt solution to be adsorbed to the surface of the material, and through the ion exchange effect, transition metal single atoms are stabilized through the limited area between adjacent layers of the graphite-like carbon nitride. The alkali metal ion is selected from K in specific embodiments, and can also be selected from alkali metals such as Li or Na; taking potassium ion intercalated graphite-like carbon nitride as an example, it can be expressed as K/g-C3N 5.
In the application, raw materials are firstly prepared, wherein one of the raw materials, namely the graphite-like carbon nitride intercalated by alkali metal ions, can be prepared; the preparation method of the alkali metal ion intercalated graphite-like carbon nitride specifically comprises the following steps:
mixing alkali metal bromide, 3-amino-1, 2, 4-triazole and water, evaporating and grinding to obtain mixed powder;
primarily calcining the mixed powder to obtain initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5;
and calcining the initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5 again to obtain the alkali metal ion intercalated graphite-like carbon nitride g-C3N 5.
In the above step of preparing the mixed powder, the raw materials are all chemically pure; the mass ratio of the bromide of the alkali metal to the 3-amino-1, 2, 4-triazole is (8-10) to 100. In the process, the mixing temperature is 50-100 ℃.
Primarily calcining the mixed powder to obtain initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5; the temperature rise rate of the calcination is 10-15 ℃/min, and the temperature of the calcination is 500-600 ℃. This process yields microscopically blocky alkali metal ion intercalated graphite-like carbon nitride g-C3N 5.
And finally calcining the initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5 again to realize the stripping of the graphite-like carbon nitride so as to obtain the nano-sheet structure alkali metal ion intercalated graphite-like carbon nitride g-C3N 5.
For the other starting material, the transition metal salt is a transition metal salt well known to those skilled in the art and may be selected in particular from iron nitrate nonahydrate, cobalt nitrate hexahydrate, manganese sulfate monohydrate, iridium chloride trihydrate or nickel nitrate hexahydrate. The mass ratio of the graphite-like carbon nitride g-C3N5 intercalated by the alkali metal ions to the transition metal salt is 2: 1. And mixing the two raw materials, and then stirring at the temperature of 50-100 ℃ for 24-48 hours. If the stirring time is too short, the transition metal monoatomic group cannot completely replace the alkali metal ion.
The application also provides an intercalated graphite-like carbon nitride composite material which consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N 5.
In the above composite material, the transition metal atom is all known to those skilled in the art, and may be selected from a nickel atom, a cobalt atom, a manganese atom, an iridium atom, or an iron atom, for example. The transition metal atoms are stabilized by confinement between adjacent layers of graphite-like carbon nitride g-C3N 5.
The application also provides application of the intercalation type graphite-like carbon nitride composite material in water decomposition oxygen analysis reaction, in particular to water decomposition oxygen analysis reaction in an alkaline environment, and the intercalation type graphite-like carbon nitride composite material is used as a catalyst.
The intercalation type graphite-like carbon nitride composite material provided by the application consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N5; the composite material provides rich coordination sites for transition metal atoms due to the pyridine nitrogen atoms rich in electrons, and van der Waals force between adjacent layers of g-C3N5 can stabilize the transition metal atoms and can prevent the transition metal atoms from aggregating into particles, so that the composite material can be stably stored; furthermore, the electronic structure of transition metal atoms can be changed due to the interaction between adjacent layers, so that the energy barrier of the reaction is reduced, and the composite material can be used as a catalyst in the water decomposition oxygen analysis reaction.
The intercalation graphite-like carbon nitride composite material has huge application prospects in the aspects of photoelectrocatalysis, energy storage, composite materials and the like, and compared with the existing transition metal single atom, the composite material is simple in synthesis method, large in loading capacity and easy for large-scale production.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method and applications of the intercalated graphite-like carbon nitride composite material, and the scope of the present invention is not limited by the following examples.
Example 1
a. Dissolving 0.45g of potassium bromide powder and 5g of 3-amino-1, 2, 4-triazole in 30ml of deionized water, magnetically stirring and evaporating to remove water, and grinding the obtained solid into powder;
b. putting the obtained powder into an alumina crucible and covering, putting the alumina crucible into a muffle furnace, calcining for two hours at 550 ℃ at the heating rate of 15 ℃/min, and grinding the obtained solid into powder to obtain brown yellow powder bulk K/g-C3N 5;
c. the synthesized powder is formed into a nano-sheet structure by adopting a thermal stripping method, namely, the nano-sheet structure is placed in a corundum ark and calcined in a tube furnace at 450 ℃ at the heating rate of 15 ℃/min to form K/g-C3N5nanosheet (as shown in figure 3);
d. obtaining 50mg of K/g-C3N5nanosheet and 20mg of nickel nitrate hexahydrate, mixing, dissolving in 20mL of aqueous solution, and continuously stirring;
e. and d, centrifuging the suspension obtained in the step d, collecting precipitates, alternately washing the precipitates for 6 times by using deionized water and ethanol, and cleaning the product to be neutral to obtain the catalyst of the transition metal Ni monoatomic intercalation g-C3N5 (shown in figure 4).
FIG. 1 is a scanning electron micrograph of the Ni atom intercalated g-C3N5 composite material prepared in this example; FIG. 2 shows XRD patterns of g-C3N5, K/g-C3N5 and Ni/g-C3N 5. from FIGS. 1 and 2, this example successfully produced a transition metal intercalated graphite-like carbon nitride material.
Dissolving 4mg of Ni atom intercalated g-C3N5 powder in 1mL of solution, wherein the solution consists of 500uL of deionized water, 460uL of absolute ethyl alcohol solution and 40uL of nafion solution, and carrying out ultrasonic treatment on the solution and the powder for 30min to uniformly mix the solution and the powder; dripping 5uL of mixed solution on a glassy carbon electrode (GC), naturally drying the glassy carbon electrode, taking the glassy carbon electrode as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a carbon rod as a counter electrode to form a three-electrode system, and taking 1M KOH solution as electrolyte solution; when an electrochemical LSV (linear sweep voltammetry) test is carried out, the applied voltage range is 0-0.8V (VS RHE), the sweep rate is 5mV/s, and bubbles are separated out on the surface of an observation electrode; therefore, the Ni atoms are intercalated into the g-C3N5 composite material to catalyze the water decomposition to generate oxygen under the alkaline condition. FIG. 6 is an LSV curve of the hydrolytic oxygen evolution reaction of Ni/g-C3N5 under alkaline conditions, and it can be known from FIG. 6 that the transition metal monoatomic intercalated graphite-like carbon nitride composite material can be applied to the field of electrocatalysis.
Example 2
This example differs from example 1 in that: the amount of potassium bromide in step a was 0.75g, and the rest was the same as in example 1.
Example 3
This example differs from example 1 in that: the mass of potassium bromide in step a was 1.5g, and the rest was the same as in example 1.
Example 4
This example differs from example 1 in that: the transition metal salt in the step d is iridium chloride trihydrate, so that the Ir atom intercalated g-C3N5 composite material is obtained; the rest is the same as in example 1. FIG. 5 is an EXAFS plot of Ir/g-C3N5 prepared in this example, from which it can be seen that the intercalated transition metal is in the monatomic form.
Example 5
This example differs from example 1 in that: the transition metal salt in the step d is ferric chloride nonahydrate, so that the Fe atom intercalated g-C3N5 composite material is obtained; the rest is the same as in example 1.
Example 6
This example differs from example 1 in that: the transition metal salt in the step d is cobalt chloride hexahydrate, so that a Co atom intercalated g-C3N5 composite material is obtained; the rest is the same as in example 1.
Example 7
This example differs from example 1 in that: the reactant in step a is thiourea, and the rest is the same as the example 1.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of an intercalation type graphite-like carbon nitride composite material comprises the following steps:
mixing the graphite-like carbon nitride g-C3N5 intercalated by alkali metal ions with transition metal salt, and stirring to obtain the intercalated graphite-like carbon nitride composite material.
2. The preparation method according to claim 1, wherein the preparation method of the alkali metal ion intercalated graphite-like carbon nitride g-C3N5 specifically comprises the following steps:
mixing alkali metal bromide, 3-amino-1, 2, 4-triazole and water, evaporating and grinding to obtain mixed powder;
primarily calcining the mixed powder to obtain initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5;
and calcining the initial alkali metal ion intercalated graphite-like carbon nitride g-C3N5 again to obtain the alkali metal ion intercalated graphite-like carbon nitride g-C3N 5.
3. The method according to claim 2, wherein the temperature of the primary calcination is 500 to 600 ℃ and the temperature of the secondary calcination is 400 to 500 ℃.
4. The preparation method according to claim 1 or 2, wherein the stirring temperature is 50-100 ℃ and the stirring time is 24-48 h.
5. The method according to claim 1 or 2, wherein the transition metal salt is selected from the group consisting of iron nitrate nonahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, manganese sulfate monohydrate, and iridium chloride trihydrate.
6. An intercalation type graphite-like carbon nitride composite material consists of graphite-like carbon nitride g-C3N5 and transition metal atoms intercalated in the graphite-like carbon nitride g-C3N 5.
7. The intercalated graphite-like carbon nitride composite material according to claim 1, wherein the transition metal atoms are selected from nickel atoms, cobalt atoms, iron atoms, manganese atoms or iridium atoms.
8. Use of the intercalated graphite-like carbon nitride composite material prepared by the preparation method according to any one of claims 1 to 5 or the intercalated graphite-like carbon nitride composite material according to any one of claims 6 to 7 in a water-splitting oxygen-analyzing reaction.
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