A kind of g-C3N4@g-C4N3Composite photo-catalyst and its preparation method and application
Technical field
The invention belongs to semiconducting polymer's field of material technology, and in particular to a kind of g-C3N4@g-C4N3(class graphite nitrogen
Compound g-C3N4And g-C4N3) carbon composite photocatalyst and preparation method thereof.
Background technique
In recent years, as that studies organic semiconducting materials deepens continuously, a kind of high molecular polymer semiconductor material
Material-class graphitic nitralloy carbon (g-C3N4) cause the extensive concern of people.With classical inorganic oxide semiconductor light-catalyst
TiO2, ZnO compare, g-C3N4It is stable, cheap with preferable visible light-responded (the relatively narrow Eg=2.70eV of band gap), chemical property
The advantages that easily processed, it is often more important that its suitable band structure, especially higher conduction band positions and its unique two-dimensional slice
Layer structure makes its theoretically photocatalytic pollutant degradation with higher, photocatalytic water splitting and photocatalysis CO simultaneously2Reduction is lived
Property.In addition, g-C3N4The features such as being also equipped with the chemical composition and band structure easy-regulating of polymer semiconductor, therefore, it has become most
Has one of the novel semi-conductor photochemical catalyst of research potential.However, g-C3N4As conventional high molecular polymer, crystallinity phase
To poor, and exciton binding energy with higher, it is unfavorable for photo-generated carrier and is quickly migrated to catalyst surface, thus its light
The separative efficiency of raw carrier is lower, seriously inhibits g-C3N4Photocatalytic activity, affect its large-scale promotion and application.
In order to further improve g-C3N4Physics and chemical property, by Morphological control, element doping and from different semiconductor materials
It is compound, become g-C in recent years3N4The research hotspot of material.Patent CN103170358A discloses a kind of porous g-C3N4Light is urged
Dicyandiamide and thiocarbamide are carried out ground and mixed by agent and preparation method thereof, this method, and calcining mixt obtains in air atmosphere
Porous g-C3N4.But monophase materials cannot achieve photo-generate electron-hole to efficiently separating, and photocatalytic activity is restricted.Patent
CN 105858730A discloses a kind of carbonitride/tungsten oxide compound hollow microballoon material and preparation method thereof, passes through glucose water
Thermosetting carbon ball and synchronized loading tungsten oxide and carbonitride form carbonitride using high-temperature calcination removal template synchronous, are made
Tiny balloon made of shell is constructed jointly as tungsten oxide, carbonitride.But two kinds of materials for forming the hetero-junctions are physical bond,
Photo-generated carrier transmission, separating capacity are limited.
Recently, g-C4N3It is concerned as a kind of novel semi-metallic, has been reported and be applied to photocatalysis Decomposition
Water hydrogen manufacturing.g-C4N3Have and g-C3N4Similar structure, and the presoma of the two has the function that can be copolymerized
Group's cyano.By g-C4N3With g-C3N4By Covalent bonding together, excellent interface performance will be helpful to quick transporting electronics, so that
Light induced electron and hole can efficiently separate and shift, and then can significantly improve the photoelectric properties of material, make the composite wood
Material produces oxygen, CO in photocatalysis contaminant degradation, decomposition aquatic products hydrogen2The fields such as reduction conversion have larger application potential.
Summary of the invention
It is an object of the present invention to provide a kind of g-C3N4@g-C4N3(class graphitic nitralloy closes object g-C3N4And g-C4N3) complex light
Catalyst and its preparation method and application, the material preparation process is simple, controllable, specific surface area with higher and it is good can
Light-exposed responsiveness, especially its excellent photo-generate electron-hole separating capacity, so that material is in photocatalytic pollutant degradation, water
It decomposes, CO2Application field great potential.
Realizing the technical solution of the object of the invention is: a kind of g-C3N4@g-C4N3Composite photo-catalyst, g-C3N4And g-
C4N3It is coupled and is constituted by covalent bond, there is two-dimension plane structure, wherein g-C4N3Content be 3-25wt%.The material is by three
Cyano methanation imidazole ion liquid and g-C3N4Presoma be prepared by high temperature copolyreaction.The present invention is by macromolecule
Semimetal g-C4N3With semiconducting polymer g-C3N4It is coupled by covalent bond, semimetal property, g-C4N3With g-C3N4Similar knot
Structure and close continuous phase interface be photo-generated carrier migration, is efficiently separated and its efficiently using providing condition.
Above-mentioned g-C3N4@g-C4N3The preparation method of composite photo-catalyst, the specific steps are that:
Step a), by tricyano methanation imidazole ion liquid and g-C3N4Presoma as stock dispersion in water,
It is ultrasonically treated 0.5~1h, water phase is evaporated off, be uniformly mixed body;
Gained homogeneous mixture in step a) is heated to 400 in tube furnace with certain heating rate by step b)~
420 DEG C, 1~2h is maintained, then rise to 500~550 DEG C, heat 2~5h, cooled to room temperature, deionized water is washed, and vacuum is dry
It is dry, obtain g-C3N4@g-C4N3Composite photo-catalyst.
Tricyano methanation imidazole ion liquid described in step a) is tricyano methanation 1- ethyl -3- methyl miaow
One of azoles, tricyano methanation 1- butyl -3- methylimidazole, tricyano methanation 1- hexyl -3- methylimidazole.
G-C described in step a)3N4The presoma of carbonitride is one of dicyanodiamine, cyanamide.
Tricyano methanation imidazole ion liquid and g-C in step a)3N4The molar ratio of presoma is 1:10~1:30.
The g-C3N4@g-C4N3Composite photo-catalyst is in photocatalysis contaminant degradation, water decomposition and CO2In reduction reaction
Application.
Photocatalysis contaminant degradation, water decomposition and CO2Application in reduction reaction.
Beneficial effects of the present invention, the composite photo-catalyst are two-dimensional nano chip architecture, specific surface area with higher, half
Metal g-C4N3Pass through covalent bond and g-C3N4Coupling, interface is close, has efficient carrier transport and photo-generate electron-hole
Separative efficiency can be applied to photocatalysis contaminant degradation, water decomposition and CO2Reduction field.
(1) different from the common hetero-junctions physically combined, the present invention is prepared for g- by high temperature copolyreaction
C3N4@g-C4N3Composite photo-catalyst, which has 2D planar structure, adjustable compound by the change of presoma ratio
G-C in photochemical catalyst3N4With g-C4N3Content, preparation process is simple.
(2)g-C3N4With g-C4N3Structure is similar, and compatibility, binding force are excellent, and interface performance is prominent, can effectively reduce
Transport resistance of the charge between two kinds of materials, promotes the separating capacity of photo-generate electron-hole.The internal electron of two-dimensional material
Material surface can faster be reached and participate in reaction, photon utilization rate is high.
(3) semi-metallic g-C4N3Conductivity is higher, and electron density is big, is conducive to the raising of material adsorption capacity, provides
More catalytic reaction activity sites.
Detailed description of the invention
Fig. 1 is g-C3N4@g-C4N3The preparation flow figure of composite photo-catalyst.
Fig. 2 is 2 gained g-C of embodiment3N4@g-C4N3The SEM photograph of composite photo-catalyst.
Fig. 3 is 2 gained g-C of embodiment3N4@g-C4N3The TEM photo of composite photo-catalyst.
Fig. 4 is 2 gained g-C of embodiment3N4@g-C4N3The AFM photo of composite photo-catalyst.
Fig. 5 is 2 gained g-C of embodiment3N4@g-C4N3The UV-vis spectrogram of composite photo-catalyst and its component.
Fig. 6 is 2 gained g-C of embodiment3N4@g-C4N3The TG curve of composite photo-catalyst and its component.
Fig. 7 is 2 gained g-C of embodiment3N4@g-C4N3The photocatalysis CO of composite photo-catalyst2Restore application efficiency.
Fig. 8 is 3 gained g-C of embodiment3N4@g-C4N3Composite photo-catalyst13C solid-state nuclear magnetic resonance spectrogram.
Specific embodiment
Below in conjunction with attached drawing, present invention is further described in detail.It can make this professional technique by the following examples
The present invention is more fully understood in personnel.
Embodiment 1
By 0.402g (2.0mmol) tricyano methanation 1- ethyl-3-methylimidazole and 3.363g (40mmol) dicyan two
Amine is added in 50ml deionized water, ultrasound, and stirring 30min is uniformly mixed.Water phase is evaporated off in mixed solution, mixture is in tube furnace
In with 2 DEG C/min be heated to 400 DEG C, calcine 1 hour, then heat to 550 DEG C, keep the temperature 4 hours, natural cooling,
Washing, vacuum drying obtain g-C3N4@g-C4N3Composite photo-catalyst.
Embodiment 2
By 0.458g (2.0mmol) tricyano methanation 1- butyl -3- methylimidazole and 3.363g (40mmol) dicyan two
Amine is added in 50ml deionized water, ultrasound, and stirring 30min is uniformly mixed.Water phase is evaporated off in mixed solution, mixture is in tube furnace
In with 2 DEG C/min be heated to 400 DEG C, calcine 1 hour, then heat to 550 DEG C, keep the temperature 4 hours, natural cooling,
Washing, vacuum drying obtain g-C3N4@g-C4N3Composite photo-catalyst.
Fig. 2 is g-C3N4@g-C4N3The SEM photograph of composite photo-catalyst, it can be seen that g-C3N4@g-C4N3Composite photo-catalyst
It is surfacing, smooth for 2D planar structure.
Fig. 3 is g-C3N4@g-C4N3The TEM photo of composite photo-catalyst, it can be seen that composite photo-catalyst is ultrathin nanometer
Piece, structural integrity are uniform.
Fig. 4 a is g-C3N4@g-C4N3The AFM photo of composite photo-catalyst, Fig. 4 b are selection area g-C in Fig. 4 a3N4@g-
C4N3The thickness distribution map of composite photo-catalyst nanometer sheet, nanometer sheet thickness are of uniform size in 4nm or so.
Fig. 5 is g-C3N4@g-C4N3Composite photo-catalyst and its ultraviolet-ray visible absorbing of component diffuse spectrogram, and light is urged
Agent has good visible light absorption capacity, relative to simple g-C3N4, obvious red shift occurs for absorption band, with g-C3N4@g-
C4N3Brown appearance it is consistent.
Fig. 6 is g-C3N4@g-C4N3The thermogravimetric curve of composite photo-catalyst and its component can be calculated in composite material
g-C4N3Mass percentage be 13%.
Fig. 7 is g-C3N4@g-C4N3The photocatalysis CO of composite photo-catalyst2Reducing property characterization, experiment use 300W xenon lamp
As light source.From the figure, it can be seen that g-C3N4@g-C4N3With excellent catalytic activity, through 6 hour illumination, CO yield reaches
To 99.03 μm of ol g-1, average yield is 16.5 μm of ol g-1h-1。
Test learns, the g-C3N4@g-C4N3Composite photo-catalyst is in photocatalysis contaminant degradation, water decomposition and CO2
Reduction reaction application effect is good, especially reduction reaction application.
Embodiment 3
By 0.458g (2.0mmol) tricyano methanation 1- butyl -3- methylimidazole and 0.841g (10mmol) dicyan two
Amine is added in 50ml deionized water, ultrasound, and stirring 30min is uniformly mixed.Water phase is evaporated off in mixed solution, mixture is in tube furnace
In with 2 DEG C/min be heated to 400 DEG C, calcine 1 hour, then heat to 550 DEG C, keep the temperature 4 hours, natural cooling,
Washing, vacuum drying obtain g-C3N4@g-C4N3Composite photo-catalyst.
Fig. 8 is g-C3N4@g-C4N3The solid state nmr carbon of composite photo-catalyst is composed, g-C3N4On seven piperazine rings carbon atom signal with
g-C4N3Carbon atom signal forms the absorption peak of chemical shift 156ppm on triazine ring, and the absorption peak at chemical shift 86ppm is corresponding
In g-C4N3The carbon atom of middle connection triazine ring.
Embodiment 4
By 0.514g (2.0mmol) tricyano methanation 1- hexyl -3- methylimidazole and 3.363g (40mmol) dicyan two
Amine is added in 50ml deionized water, ultrasound, and stirring 30min is uniformly mixed.Water phase is evaporated off in mixed solution, mixture is in tube furnace
In with 2 DEG C/min be heated to 420 DEG C, calcine 1 hour, then heat to 550 DEG C, keep the temperature 3 hours, natural cooling,
Washing, vacuum drying obtain g-C3N4@g-C4N3Composite photo-catalyst.
Embodiment 5
By 0.458g (2.0mmol) tricyano methanation 1- butyl -3- methylimidazole and 2.522g (60mmol) cyanamide
It is added in 50ml deionized water, ultrasound, stirring 30min is uniformly mixed.Water phase is evaporated off in mixed solution, mixture is in tube furnace
420 DEG C are heated to 2 DEG C/min, 2 hours is calcined, then heats to 550 DEG C, keeps the temperature 5 hours, natural cooling, water
It washes, vacuum drying obtains g-C3N4@g-C4N3Composite photo-catalyst.