A kind of preparation of three-dimensional grapheme/nickel/graphite phase carbon nitride composite photocatalyst materialMethodTechnical field
The invention belongs to photocatalysis technology fields, and in particular to a kind of three-dimensional (3D) graphene/nickel (Ni)/graphite-phase nitridationCarbon (g-C3N4) composite photocatalyst material preparation method.
Background technique
In recent years due to the raising of the quickening of process of industrialization and human living standard, consumption of the mankind to the energyThe fossil energies such as coal, petroleum, the natural gas for increasing year by year, but storing on the earth are extremely limited, therefore pass through photocatalysis technologyThe Hydrogen Energy for converting solar energy into cleanliness without any pollution becomes the most effective means for solving energy crisis at present.
Most study is inorganic semiconductor during photocatalysis technology develops, such as titanium oxide, zinc oxide and cadmium sulfide,But most of oxide, which cannot absorb visible light, sulfide, to be easy to happen photoetch these problems during the reaction and limitsIts application in photocatalysis field.And g-C3N4A kind of organic semiconductor as no metal attracted researcher's note thatg-C3N4Have the advantages that stability height, good environmental adaptability, band gap size suitable (2.7eV or so), visible light can be absorbed.But g-C3N4Smaller, electron hole pair recombination rate that there is also specific surface areas is high, lacks to incomplete absorption of visible light region etc.Point causes its photocatalysis hydrogen production rate lower.
g-C3N4It is light absorption, table/interfacial reaction, electricity applied to play crucial effect to its performance in photocatalysis researchLotus separates three problems, main by improving g-C at present3N4To the absorption of visible light, increase reactivity site, reduction current-carryingThe recombination rate of son improves its catalytic activity.Such as the Au/g-C prepared by one-step method3N4The absorption of composite material visible regionIt is largely increased, and since a characteristic absorption peak also occurs at 550nm in the plasma effect of Au.Pass through templateEither the method preparation of thermal oxide etching removing has the single layer or few layer g-C of bigger serface3N4It is more to exposeActive site.It can also be by g-C3N4It is compound with the progress of other narrow gap semiconductors, promote photoproduction electric by forming hetero-junctionsThe separation of son-hole, or the compound conduction to improve material is carried out with carbon materials such as graphene, carbon quantum dot, carbon nanotubesProperty to improve the separative efficiency of carrier.
Graphene has big specific surface area, excellent conduction and heating conduction, but catalytic performance is weaker, by g-C3N4With graphene carry out it is compound can overcome the disadvantage of two components respectively, and assign composite material superior catalytic performance.
Summary of the invention
In order to solve the problems, such as that graphite phase carbon nitride exists, the object of the present invention is to provide a kind of three-dimensional (3D) graphene/Nickel (Ni)/graphite phase carbon nitride (g-C3N4) composite photocatalyst material preparation method, improve the production hydrogen of graphite phase carbon nitrideEnergy.Technical scheme is as follows:
A kind of preparation method of three-dimensional grapheme/nickel/graphite phase carbon nitride composite photocatalyst material, including the following steps:
1) preparation of the 3D graphene of Ni particulate load: with catalyst, carbon source, alkali metal salt is raw material, catalyst, carbonSource, the mass ratio of alkali metal salt are 1:(10-20): (100-200) is dissolved in a certain amount of water, stirs 1-2h；ThenMove in refrigerator freeze it is blocking；
2) after then freezing blocking material freeze drying, light-blue solid powder is obtained.
3) powder that freeze-drying obtains is put into Noah's ark or crucible, under hydrogen, 600- is warming up to 5-15 DEG C/min750 DEG C, 1-2h is kept the temperature, is then cleaned several times with deionized water, drying obtains the 3D graphene of Ni particulate load；
4) 3D graphene/Ni/g-C3N4Preparation: by the 3D graphene and g-C of a certain amount of Ni particulate load3N4BeforeIt drives body to mix by the way of melting, the solid being mixed to get is put into Noah's ark, under an argon atmosphere, with 5-15 DEG C/min literTemperature arrives 500-600 DEG C, keeps the temperature 2-4h, obtains 3D graphene/Ni/g-C3N4Composite material.
Preferably, carbon source is glucose or sucrose in step 1)；Catalyst is the chloride or nitrate of nickel；Alkali metal saltIt is the chloride of alkali metal, sulfate or carbonate.The g-C3N4Presoma be thiocarbamide or cyanamide or dicyandiamide or threePoly cyanamid or urea.
In conclusion core of the invention is the 3D graphene and fused salt-heat for preparing Ni particulate load by salt templateThe mode of polymerization prepares 3D graphene/Ni/g-C3N4Composite photocatalyst material.Compared with prior art, advantages of the present invention existsIn:
(1) present invention takes full advantage of the limit of alkali metal salt using the 3D graphene of the Ni particulate load of salt template preparationDomain effect forms three-dimensional structure, and the effect that the nickel particle of uniform load not only acts as catalyst also hinders the group of grapheneIt is poly-.
(2) present invention preparation 3D graphene/Ni/g-C3N4Composite material significantly improves the production hydrogen of graphite phase carbon nitridePerformance and good performance is also shown in terms of degradation of contaminant.
(3) Preparation equipment of the present invention is simple, simple process.
(4) high reliablity of the present invention.Use alkali metal salt as template, repeatability is strong, there is good application prospect.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the 3D graphene of Ni particulate load prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM spectrum of the 3D graphene of Ni particulate load prepared by the embodiment of the present invention 1.
Fig. 3 is 3D graphene/Ni/g-C prepared by the embodiment of the present invention 13N4XRD spectrum.
Fig. 4 is 3D graphene/Ni/g-C prepared by the embodiment of the present invention 13N4SEM figure.
Specific embodiment
Embodiment 1
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:10:100, stirred1h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 600 DEG C are warming up to 5 DEG C/min, 1h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedThe 3D graphene of Ni particulate load as shown in Fig. 2.The three-dimensional grapheme and 10g urea that 5mg nickel particle is loaded are at 135 DEG CLower melting simultaneously stirs 1h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 5 DEG C/min literTemperature keeps the temperature 3h, obtained solid is ground to obtain 3D graphene/Ni/g-C to 500 DEG C3N4Composite material.
Embodiment 2
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:15:100, stirred1h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 600 DEG C are warming up to 10 DEG C/min, 1h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedTo the 3D graphene of Ni particulate load as shown in Fig. 2.The three-dimensional grapheme and 10g urea that 5mg nickel particle is loaded are 135It is melted at DEG C and stirs 1h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 5 DEG C/min500 DEG C are warming up to, 3h is kept the temperature, obtained solid is ground to obtain 3D graphene/Ni/g-C3N4Composite material.
Embodiment 3
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:15:200, stirred2h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 700 DEG C are warming up to 10 DEG C/min, 1h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedTo the 3D graphene of Ni particulate load as shown in Fig. 2.The three-dimensional grapheme and 10g urea that 5mg nickel particle is loaded are 135It is melted at DEG C and stirs 1h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 10 DEG C/min550 DEG C are warming up to, 3h is kept the temperature, obtained solid is ground to obtain 3D graphene/Ni/g-C3N4Composite material.
Embodiment 4
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:20:200, stirred2h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 700 DEG C are warming up to 15 DEG C/min, 1h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedTo the 3D graphene of Ni particulate load as shown in Fig. 2.Three-dimensional grapheme and 10g urea that 10mg nickel particle loads are existedAt 135 DEG C melt and stir 2h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 10 DEG C/Min is warming up to 550 DEG C, keeps the temperature 3h, obtained solid is ground to obtain 3D graphene/Ni/g-C3N4Composite material.
Embodiment 5
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:20:200, stirred2h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 700 DEG C are warming up to 15 DEG C/min, 2h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedTo the 3D graphene of Ni particulate load as shown in Fig. 2.Three-dimensional grapheme and 10g urea that 15mg nickel particle loads are existedAt 135 DEG C melt and stir 2h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 10 DEG C/Min is warming up to 550 DEG C, keeps the temperature 4h, obtained solid is ground to obtain 3D graphene/Ni/g-C3N4Composite material.
Embodiment 6
Nickel nitrate, DEXTROSE ANHYDROUS and sodium chloride are dissolved in 125ml deionized water with the ratio of 1:20:200, stirred2h；Then move in refrigerator freeze it is blocking；Then blocking substance will be freezed to be put into freeze drier, when by for 24 hours longBetween be lyophilized after, obtain light-blue solid powder.Then obtained light-blue solid powder is put into Noah's ark, in hydrogen atmosphereUnder, 600 DEG C are warming up to 15 DEG C/min, 1h is kept the temperature, is then cleaned twice with deionized water, be put into vacuum drying oven and dry, obtainedTo the 3D graphene of Ni particulate load as shown in Fig. 2.Three-dimensional grapheme and 10g urea that 15mg nickel particle loads are existedAt 135 DEG C melt and stir 1h at this temperature, then resulting solid is put into Noah's ark, under an argon atmosphere, with 15 DEG C/Min is warming up to 550 DEG C, keeps the temperature 4h, obtained solid is ground to obtain 3D graphene/Ni/g-C3N4Composite material.