CN108993563A - A kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride - Google Patents

A kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride Download PDF

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CN108993563A
CN108993563A CN201810705483.3A CN201810705483A CN108993563A CN 108993563 A CN108993563 A CN 108993563A CN 201810705483 A CN201810705483 A CN 201810705483A CN 108993563 A CN108993563 A CN 108993563A
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montmorillonite
carbon nitride
phase carbon
dimensional network
graphite phase
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仪德启
秦培凡
郝建薇
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/39
    • B01J35/647
    • B01J35/651

Abstract

The invention discloses the preparation methods of a kind of montmorillonite and the three-dimensional network frame of graphite phase carbon nitride, belong to the preparation field of porous material.Montmorillonite, cyanuric acid and melamine are added in the reaction kettle taken water as a solvent for invention, stir under fixed temperature and are dried to obtain presoma.Presoma is placed in have and is passed through in the furnace body of gas function, gas flow rate is controlled and heating rate is calcined, obtain montmorillonite and graphite phase carbon nitride three-dimensional network frame material compound layer by layer.The invention has the advantages that: melamine cyanurate is self-assembly of in the solution with melamine and cyanuric acid, and it is intercalation between montmorillonite layer, then as the carbon source of graphite phase carbon nitride and nitrogen source, thermal polycondensation reaction is generated by calcining in inert gas, prepare montmorillonite and graphite phase carbon nitride composite material layer by layer, and the method for the mass ratio of changeable raw material controls three-dimensional network frame aperture, process is simple.

Description

A kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride
Technical field
The present invention relates to the preparation methods of a kind of montmorillonite and the three-dimensional network frame of graphite phase carbon nitride, belong to porous material The preparation field of material can be used for the fields such as photocatalysis field and lithium ion battery negative material.
Background technique
Montmorillonite is the 2:1 structure multilayer silicate clay formed by oxygen-octahedron and alumina octahedral, wherein alumina Part Al atom in octahedron is replaced by Mg, makes lamella with elecrtonegativity, interlayer is usually by Na+、Ca2+Equal metal cations are flat Weigh charge.Each montmorillonite layer has comprising three sub-layers, and upper layer and lower layer are oxygen-octahedron sub-layer, and centre is alumina octahedral Body sub-layer is connected between sub-layer with covalent bond by sharing oxygen atom, and only has faint Van der Waals force between adjacent sheets.It covers De- soil is used as a kind of clay mineral, has the characteristics that cheap and easy to get, cation exchange capacity is big, is easy to intercalation.Graphite-phase nitridation Carbon (graphitic carbon nitride), is abbreviated as g-C3N4, it is nitridation carbon allotrope the most stable, is a kind of Very promising non-metallic catalyst.The fields such as the hydrogen manufacturing of the photodegradation that has been widely used water, photocatalysis.Because it has excellent performance And it receives significant attention.
The lower thermal polycondensation reaction using melamine cyanurate super-molecule assembling body in hot conditions can effectively make at present Obtaining graphite phase carbon nitride, (23 (29): Adv.Funct.Mater.2013 3661-3667.), can induce stronger with its layer structure Light absorption, band gap can effectively increase 0.16eV.Three-dimensional netted frame structure has high-specific surface area and duct abundant, energy More active points are exposed, reactant and product in the performances and heterogeneous reaction of applications such as catalysis reaction are then lifted at Mass transfer diffusion.Framework material of the montmorillonite as three-dimensional network frame, come into full contact with graphite phase carbon nitride can be formed it is heterogeneous Knot, because of the difference of its conduction band and valence band, graphite phase carbon nitride can be transferred to compound due to the electronics of light excitation generation or hole Conduction band or valence band in, electron hole separation, recombination rate reduce, so as to more efficiently utilize light excitation generate active grain Son improves catalytic efficiency (Chemical Reviews, 2016,116 (12): 7159-7329.).
Currently without the patent for imvite modified preparation three-dimensional network frame structure.Now use melamine cyanurate Salt has imvite modified patent: a kind of melamine cyanurate and montmorillonite nano complex and preparation method thereof are (public The number of opening: CN 104829860A, on August 12nd, 2015, Beijing Institute of Technology), it is added using melamine, cyanuric acid and urea Into the reaction kettle containing montmorillonite and solvent, reaction obtains the nano-complex of melamine cyanurate and montmorillonite, uses In polymer material flame retardant area.
The patent of preparation graphite phase carbon nitride has: a kind of method (publication number: CN preparing graphite phase carbon nitride material 106540733A, on March 29th, 2017, Institutes Of Technology Of Taiyuan), it the use of dicyanodiamine and nano silica is presoma, with The graphitic carbon nitride of high specific surface area is prepared in microwave calcining and Muffle furnace roasting.A kind of conjunction of porous graphite phase carbon nitride At method (publication number: CN104843658A, on August 19th, 2015, Changzhou University), with polystyrene or poly-methyl methacrylate Ester microemulsion is hard template, and cyanamide, dicyanodiamine or guanidine hydrochloride are presoma, dry by directly mixing, the gas of inert gas Porous graphite phase carbon nitride can be obtained in roasting under atmosphere.
Summary of the invention
The object of the present invention is to provide the preparation methods of a kind of montmorillonite and the three-dimensional network frame of graphite phase carbon nitride.It should Composite material can be used for the fields such as photocatalysis field and lithium ion battery negative material as porous material.Application prospect is wide It is wealthy, and preparation method process is simple, can be mass-produced.
The present invention is realized by following technological means, a kind of montmorillonite and graphite phase carbon nitride composite wood layer by layer The three-dimensional network frame of material, which is characterized in that the three-dimensional network frame is stratiform montmorillonite-based nano piece and graphite phase carbon nitride layer A kind of three-dimensional network frame structure that layer is compound and is built into, network aperture are 5-300nm, are with the gross mass of compound 100% calculates, and the mass percentage of montmorillonite is 50%-95%, and the mass percentage of graphite phase carbon nitride is 5%- 50%.
The preparation method of the montmorillonite of above structure and graphite phase carbon nitride the three-dimensional network frame of composite material layer by layer, Be characterized in that the following steps are included:
(1) montmorillonite, melamine and cyanuric acid are added in the reaction kettle taken water as a solvent, it is small that 4 is stirred under fixed temperature When, it removes solvent and is dried to obtain presoma.Wherein montmorillonite be unmodified montmorillonite perhaps organic modification montmonrillonite or It is the clay containing montmorillonite structure, which only includes montmorillonite and melamine cyanurate, with the quality of montmorillonite It is calculated for 1, the mass ratio of melamine cyanurate is 0.05~20.Melamine cyanurate by etc. amount of substance trimerization H-bonding self-assembly obtains cyanamide in aqueous solution with cyanuric acid.The fixed temperature range of reaction is room temperature~100 DEG C, Optimal Temperature It is 90 DEG C.
(2) by presoma made from step (1) be placed in tube furnace, Muffle furnace or other have be passed through gas function can heating furnace In vivo, protective gas is passed through with certain gas flow rate into furnace body and started to warm up.The gas flow and heating speed being kept fixed Rate is warming up to fixed temperature, keeps the temperature and calcines 30~200 minutes, it is compound layer by layer with graphite phase carbon nitride to obtain montmorillonite The three-dimensional network frame of material.Protective gas is nitrogen (N2), argon gas (Ar) or helium (He).Gas flow be 100~ 400ml/min, wherein optimal gas flow is 200ml/min.Heating rate is 1~50 DEG C/min, and optimal heating rate value is situated between In 10~30 DEG C/min.Fixed temperature is 300~700 DEG C.
The advantages and positive effects of the present invention are: making melamine and cyanuric acid due to taking above-mentioned technical proposal H-bonding self-assembly forms melamine cyanurate between montmorillonite layer, between achieving the effect that intercalation enters cheating engaging layer.Lead to again Crossing inert gas shielding and temperature control heating makes melamine cyanurate thermal polycondensation graphite phase carbon nitride.It is covered by control de- The pore size of soil and melamine cyanurate mass ratio control three-dimensional network frame.This method is low in cost, reacts Journey is simple, and controllability is strong.
Detailed description of the invention
Fig. 1 is the three-dimensional network frame of the composite material layer by layer of montmorillonite and graphite phase carbon nitride made from present example 3 Electron scanning micrograph.From this view it is apparent that the material three-dimensional network frame structure.
Specific embodiment
Below by example, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.It is (each Raw material is that commercially available analysis is pure)
Embodiment 1
0.556 gram of montmorillonite is weighed, 0.735 gram of melamine, 0.692 gram of cyanuric acid, 1000ml milliliters has been added to and has gone In the reaction kettle of ionized water, 95 DEG C of stirring 3h are warming up to, filter to obtain precursor product, 80 DEG C of vacuum drying 4h.Presoma is set In tube furnace, it is passed through gas flow rate and is the argon gas of 500ml/min, and temperature is warming up to the heating rate of 2.3 DEG C/min 550 DEG C of degree keeps the temperature 1h.It is cooled to room temperature under argon atmosphere protection after reaction, obtains montmorillonite and graphite phase carbon nitride The three-dimensional network frame of composite material layer by layer, measuring product aperture made from the formula is 50nm.
Embodiment 2
0.581 gram of cation-modified montmorillonite is weighed, 1.235 grams of melamine, 1.196 grams of cyanuric acid, has been added to In the reaction kettle of 1000 ml deionized waters, 80 DEG C of stirring 4h are warming up to, rotary evaporation obtains precursor product.Presoma is set In tube furnace, it is passed through the nitrogen gas that gas flow rate is 300ml/min, temperature is warming up to the heating rate of 10 DEG C/min 650 DEG C, keep the temperature 1h.It is cooled to room temperature under nitrogen atmosphere protection after reaction, obtains montmorillonite and graphite phase carbon nitride layer The three-dimensional network frame of layer composite material, measuring product aperture made from the formula is 20nm.
Embodiment 3
Weigh 0.501 gram of montmorillonite, 0.595 gram of melamine, 0.612 gram of cyanuric acid, be added to 1000 milliliters go from In the reaction kettle of sub- water, 70 DEG C of stirring 4h are warming up to, filter to obtain precursor product, 80 DEG C of vacuum drying 4h.Presoma is placed in In tube furnace, it is passed through the helium atmosphere that gas flow rate is 100ml/min, temperature 650 is warming up to the heating rate of 50 DEG C/min DEG C, keep the temperature 1h.It is cooled to room temperature under helium atmosphere protection after reaction, it is multiple layer by layer to obtain montmorillonite and graphite phase carbon nitride The three-dimensional network frame of condensation material, measuring product aperture made from the formula is 100nm.

Claims (12)

1. a kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride, the preparation method include following step It is rapid: (1) montmorillonite, melamine and cyanuric acid to be added in the reaction kettle taken water as a solvent, it is small that 4 are stirred under fixed temperature When, it removes solvent and is dried to obtain presoma.
2. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 1 and graphite phase carbon nitride, Be characterized in that: the montmorillonite that raw material uses is unmodified montmorillonite or organic modification montmonrillonite, or contains montmorillonite The clay of structure.
3. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 1 and graphite phase carbon nitride, Be characterized in that: the presoma includes montmorillonite and melamine cyanurate, is 1 calculating, melamine with the quality of montmorillonite The mass ratio of cyanurate be 0.05~20, wherein melamine cyanurate by etc. amount of substance melamine and cyanuric acid H-bonding self-assembly obtains in aqueous solution.
4. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 1 and graphite phase carbon nitride, Be characterized in that: the range of fixed temperature is room temperature~100 DEG C in reaction process, and Optimal Temperature is 90 DEG C.
5. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 1 and graphite phase carbon nitride, Be characterized in that: removal dissolving agent process includes natural drying, suction filtration or rotary evaporation in vacuo.
6. a kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride, the preparation method include following step It is rapid: (2) by presoma made from step (1) be placed in tube furnace, Muffle furnace or other have be passed through gas function can heating furnace In vivo, protective gas is passed through with certain gas flow rate into furnace body and started to warm up, the gas flow being kept fixed and heating speed Rate is warming up to fixed temperature, keeps the temperature and calcines a period of time, obtains montmorillonite and graphite phase carbon nitride composite wood layer by layer The three-dimensional network frame of material.
7. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: place step (1) presoma furnace body be tube furnace, Muffle furnace or other with controllable heating rate and can lead to Enter the furnace body of gas function.
8. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: the protective gas being passed through into furnace body is nitrogen (N2), argon gas (Ar) or helium (He).
9. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: the gas flow that protective gas is passed through into furnace body is 100~400ml/min, wherein optimal gas flow is 200ml/min。
10. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: heating rate is 1~50 DEG C/min in temperature-rise period, and optimal heating rate value is between 10~30 DEG C/min.
11. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: furnace body is warming up to fixed temperature, which is 300~700 DEG C.
12. the preparation method of the three-dimensional network frame of a kind of montmorillonite according to claim 6 and graphite phase carbon nitride, Be characterized in that: the calcination time under fixed temperature is 30~200min.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN109841818A (en) * 2019-03-05 2019-06-04 电子科技大学 A kind of preparation method and applications of lithium secondary battery cathode material
CN110026221A (en) * 2019-04-26 2019-07-19 沈阳建筑大学 A kind of montmorillonite-base optic catalytic composite material and preparation method thereof
CN110075901A (en) * 2019-05-14 2019-08-02 东南大学 Porous sulphur mixes the preparation of graphite phase carbon nitride-redox graphene nanometer sheet
CN110142057A (en) * 2019-05-17 2019-08-20 浙江工业大学 A kind of Ag/g-C3N4/ bamboo charcoal/montmorillonite composite material and its application
CN110560120A (en) * 2019-08-16 2019-12-13 徐州工程学院 Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof
CN114308101A (en) * 2021-12-22 2022-04-12 华南理工大学 Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109841818A (en) * 2019-03-05 2019-06-04 电子科技大学 A kind of preparation method and applications of lithium secondary battery cathode material
CN109841818B (en) * 2019-03-05 2021-12-03 电子科技大学 Preparation method and application of negative electrode material of lithium secondary battery
CN110026221A (en) * 2019-04-26 2019-07-19 沈阳建筑大学 A kind of montmorillonite-base optic catalytic composite material and preparation method thereof
CN110075901A (en) * 2019-05-14 2019-08-02 东南大学 Porous sulphur mixes the preparation of graphite phase carbon nitride-redox graphene nanometer sheet
CN110075901B (en) * 2019-05-14 2021-10-19 东南大学 Preparation of porous sulfur-doped graphite phase carbon nitride-reduced graphene oxide nanosheet
CN110142057A (en) * 2019-05-17 2019-08-20 浙江工业大学 A kind of Ag/g-C3N4/ bamboo charcoal/montmorillonite composite material and its application
CN110142057B (en) * 2019-05-17 2021-11-23 浙江工业大学 Ag/g-C3N4Bamboo charcoal/montmorillonite composite material and application thereof
CN110560120A (en) * 2019-08-16 2019-12-13 徐州工程学院 Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof
CN114308101A (en) * 2021-12-22 2022-04-12 华南理工大学 Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof

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