CN110026219A - A kind of transient metal doped g-C3N4Powder and preparation method thereof - Google Patents
A kind of transient metal doped g-C3N4Powder and preparation method thereof Download PDFInfo
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- CN110026219A CN110026219A CN201910323012.0A CN201910323012A CN110026219A CN 110026219 A CN110026219 A CN 110026219A CN 201910323012 A CN201910323012 A CN 201910323012A CN 110026219 A CN110026219 A CN 110026219A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 77
- 239000002184 metal Substances 0.000 title claims abstract description 77
- 230000001052 transient effect Effects 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 55
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of transient metal doped g-C3N4Powder and preparation method thereof.Its technical solution is: by nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.01~0.05 ingredient, and mixing obtains mixture.It is 16.8~21.0g/L by solid-to-liquid ratio, feeds the mixture into organic solvent I, stir, 60~80h of hydro-thermal process, is then washed with organic solvent II under the conditions of 150~180 DEG C, is filtered, and dry 8~10h, obtains transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.Finally under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by transient metal doped g-C3N4Complex precursors be warming up to 450~600 DEG C, keep the temperature 2~4h, obtain transient metal doped g-C3N4Powder.The organic solvent I is identical as organic solvent II.Low in cost, simple process of the invention and environmental-friendly；Made product has the characteristics that excellent photoresponse ability, good conductivity, structure and morphology are controllable and specific surface area is high.
Description
Technical field
The invention belongs to powder technology fields.More particularly to a kind of transient metal doped g-C3N4Powder and preparation method thereof.
Background technique
Two-dimensional material refers to that electronics only can the free movement (plane motion) on the nanoscale (1-100nm) of two dimensions
Material, because exclusive characteristic be applied to optics and electricity device, energy preparation and storage, environment maintenance, hybrid material and
Chemical sensor etc..Wherein boron nitride, carbon-nitrogen material, graphene and molybdenum sulfide etc. have been used widely.
Graphite phase carbon nitride (g-C3N4) there is the structure for being similar to graphene, band structure is adjustable, stability is good, easy system
It is standby, raw material sources are extensive and environmental-friendly, thus be applied to photocatalytic pollutant degradation, hydrogen manufacturing, carbon dioxide reduction and super
The fields such as grade capacitor.But the problems such as electron hole of there are still specific surface areas small, poorly conductive and excitation is easily compound, limits
Extensive use in terms of photocatalysis.Therefore different method of modifying is put forward one after another, such as doping, carried noble metal, construct it is heterogeneous
Junction structure and design nanostructure etc..Such as Bai is by g-C3N4Surface modification Pd is nanocrystalline, by the hetero-junctions formed between the two
And the electric conductivity that noble metal is high, noble metal energy fast Acquisition g-C3N4On light induced electron, realize photo-generated carrier effectively point
From improving g-C3N4Photocatalytic activity (Bai S, Wang X, Hu C, et al.Two-dimensional g-C3N4:an
ideal platform for examining facet selectivity of metal co-catalysts in
photocatalysis[J].Chemical communications,2014,50(46):6094-6097.).And noble metal is negative
Although carrying has excellent performance, noble metal reserves are low, expensive, limit its scope of application.Yu et al. (Yue,
Q.Y.Li,et a1.Hydrogenproductionusing zinc-doped carbon nitride catalyst
irradiated with visible light[J].Science and Technology of AdvancedMaterials,
2011,12 (3): 034401.) by g-C3N4With ZnCl2The g-C of Zn doping is made through high-temperature calcination for mixing3N4.This method system
Standby g-C3N4, it is difficult to its appearance structure is regulated and controled, it is not easy to synthesize the g-C of special appearance3N4.Chen etc. (Chen X,
Zhang J,Fu X,et al.Fe-g-C3N4-Catalyzed Oxidation ofBenzene to Phenol Using
Hydrogen Peroxide and Visible Light[J].Journal ofthe American Chemical
Society, 2009,131 (33): 11658-11659.) using dicyandiamide and ferric trichloride as raw material, using SBA-15 as template,
N2It is heated to 600 DEG C under protection to be kept for 4 hours, Fe is made and adulterates g-C3N4Porous material.The removal of template, which generally requires, uses by force
Acid etc., environmental pollution is larger.
Summary of the invention
The present invention is directed to overcome prior art defect, it is therefore an objective to provide a kind of low in cost, simple process, environmental-friendly
Transient metal doped g-C3N4Raw powder's production technology, the transient metal doped g-C prepared with this method3N4The photoresponse of powder
Ability is excellent, good conductivity, structure and morphology is controllable and specific surface area is high.
To achieve the above object, the technical solution adopted by the present invention comprises the concrete steps that:
Step 1: transient metal doped g-C3N4The preparation of presoma
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.01~0.05, by the nitrogenous compound and
The transition metal inorganic salts mixing, obtains mixture；It is again 16.8~21.0g/L by solid-to-liquid ratio, the mixture is added
In organic solvent I, 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C are stirred；Then 3 are washed with organic solvent II
It~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 450~600 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is one of melamine, cyanuric acid, urea, thiocarbamide and dicyandiamide.
The transition metal inorganic salts are one of cobalt nitrate, nickel nitrate, copper nitrate and ferric nitrate.
The organic solvent I is one of nitrogen-nitrogen dimethylformamide, dehydrated alcohol and dimethyl sulfoxide；It is described to have
Solvent II is identical as the organic solvent I.
The protective atmosphere is one of argon gas, nitrogen and ammonia.
Due to the adoption of the above technical scheme, compared with prior art, the present invention having following good effect:
1, the organic inorganic hybridization mode that uses in the present invention, simple process can be from using the mode of constructing from bottom to top
Molecular level carries out structure design, the transient metal doped g-C constructed3N4Morphology microstructure is controllable.
2, the present invention is not related to the use of strong acid, and environmental pollution is smaller, and the transition metal that original flavor introduces can be opened up effectively
The transient metal doped g-C of width3N4The light abstraction width of powder promotes the separation of photo-generated carrier, has more excellent photocatalysis
Performance.
3, the present invention with one of cheap melamine, cyanuric acid, urea, thiocarbamide, dicyandiamide for primary raw material,
Using Transition metal substituted noble metal, production cost is effectively reduced.
Transient metal doped g-C prepared by the present invention3N4Powder is through detecting: specific surface area is 59~82m2/g；Total pore volume
For 0.24~0.68cm3/g；Average pore size is 11.32~25.33nm.
Low in cost, simple process of the invention and environmental-friendly；Prepared transient metal doped g-C3N4Powder has excellent
Good photoresponse ability, good conductivity, the feature that structure and morphology is controllable and specific surface area is high.
Detailed description of the invention
Fig. 1 is a kind of transient metal doped g-C prepared by the present invention3N4The SEM shape appearance figure of powder；
Fig. 2 is the transient metal doped g-C of another kind prepared by the present invention3N4The SEM shape appearance figure of powder；
Fig. 3 is another transient metal doped g-C prepared by the present invention3N4The SEM shape appearance figure of powder.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description, not to the scope of the present invention
Limitation.
In present embodiment: the organic solvent II is identical as the organic solvent I.It is repeated no more in embodiment.
Embodiment 1
A kind of transient metal doped g-C3N4Powder and preparation method thereof.The specific steps of preparation method described in the present embodiment
It is:
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.01~0.018, by the nitrogenous compound and
The transition metal inorganic salts mixing, obtains mixture；It is again 16.8~17.8g/L by solid-to-liquid ratio, the mixture is added
In organic solvent I, 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C are stirred；Then 3 are washed with organic solvent II
It~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 450~480 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is melamine.
The transition metal inorganic salts are cobalt nitrate.
The organic solvent I is nitrogen-nitrogen dimethylformamide.
The protective atmosphere is argon gas.
Transient metal doped g-C manufactured in the present embodiment3N4Powder is through detecting: specific surface area is 70~75m2/g；Total hole body
Product is 0.24~0.45cm3/g；Average pore size is 11.32~13.50nm.
Embodiment 2
A kind of transient metal doped g-C3N4Powder and preparation method thereof.The specific steps of preparation method described in the present embodiment
It is:
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.018~0.026, by the nitrogenous compound
It is mixed with the transition metal inorganic salts, obtains mixture；It is again 17.6~18.6g/L by solid-to-liquid ratio, the mixture is added
Enter in organic solvent I, stirs 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C；Then it is washed with organic solvent II
It washs 3~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 480~510 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is cyanuric acid.
The transition metal inorganic salts are ferric nitrate.
The organic solvent I is dehydrated alcohol.
The protective atmosphere is argon gas.
Transient metal doped g-C manufactured in the present embodiment3N4Powder is through detecting: specific surface area is 72~78m2/g；Total hole body
Product is 0.41~0.60cm3/g；Average pore size is 20.21~23.24nm.
Embodiment 3
A kind of transient metal doped g-C3N4Powder and preparation method thereof.The specific steps of preparation method described in the present embodiment
It is:
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.026~0.034, by the nitrogenous compound
It is mixed with the transition metal inorganic salts, obtains mixture；It is again 18.4~19.4g/L by solid-to-liquid ratio, the mixture is added
Enter in organic solvent I, stirs 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C；Then it is washed with organic solvent II
It washs 3~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 510~540 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is urea.
The transition metal inorganic salts are nickel nitrate.
The organic solvent I is dimethyl sulfoxide.
The protective atmosphere is nitrogen.
Transient metal doped g-C manufactured in the present embodiment3N4Powder is through detecting: specific surface area is 75~82m2/g；Total hole body
Product is 0.33~0.57cm3/g；Average pore size is 21.52~24.15nm.
Embodiment 4
A kind of transient metal doped g-C3N4Powder and preparation method thereof.The specific steps of preparation method described in the present embodiment
It is:
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.034~0.042, by the nitrogenous compound
It is mixed with the transition metal inorganic salts, obtains mixture；It is again 19.2~20.2g/L by solid-to-liquid ratio, the mixture is added
Enter in organic solvent I, stirs 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C；Then it is washed with organic solvent II
It washs 3~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 540~570 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is thiocarbamide.
The transition metal inorganic salts are copper nitrate.
The organic solvent I is dimethyl sulfoxide.
The protective atmosphere is ammonia.
Transient metal doped g-C manufactured in the present embodiment3N4Powder is through detecting: specific surface area is 68~74m2/g；Total hole body
Product is 0.41~0.68cm3/g；Average pore size is 22.76~25.33nm.
Embodiment 5
A kind of transient metal doped g-C3N4Powder and preparation method thereof.The specific steps of preparation method described in the present embodiment
It is:
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.042~0.05, by the nitrogenous compound and
The transition metal inorganic salts mixing, obtains mixture；It is again 20.0~21.0g/L by solid-to-liquid ratio, the mixture is added
In organic solvent I, 1~3h, 60~80h of hydro-thermal process under the conditions of 150~180 DEG C are stirred；Then 3 are washed with organic solvent II
It~5 times, filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors.
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex
Presoma is warming up to 570~600 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
The nitrogenous compound is dicyandiamide.
The transition metal inorganic salts are cobalt nitrate.
The organic solvent I is dehydrated alcohol.
The protective atmosphere is nitrogen.
Transient metal doped g-C manufactured in the present embodiment3N4Powder is through detecting: specific surface area is 59~70m2/g；Total hole body
Product is 0.43~0.55cm3/g；Average pore size is 19.10~21.57nm.
Present embodiment compared with prior art, has following good effect:
1, the organic inorganic hybridization mode used in present embodiment, simple process, using constructing from bottom to top
Mode can carry out structure design, the transient metal doped g-C constructed from molecular level3N4Morphology microstructure is controllable.
2, present embodiment is not related to the use of strong acid, and environmental pollution is smaller, the transition metal that original flavor introduces
Transient metal doped g-C can effectively be widened3N4The light abstraction width of powder promotes the separation of photo-generated carrier, has more excellent
Photocatalysis performance.
3, present embodiment is with one of cheap melamine, cyanuric acid, urea, thiocarbamide, dicyandiamide
Primary raw material effectively reduces production cost using Transition metal substituted noble metal.
4, the transient metal doped g-C of present embodiment preparation3N4Powder is as shown in the picture: Fig. 1 is to implement example 1
A kind of transient metal doped g-C of preparation3N4The SEM shape appearance figure of powder；Fig. 2 is to implement a kind of transition metal prepared by example 2 to mix
Miscellaneous g-C3N4The SEM shape appearance figure of powder；Fig. 3 is a kind of transient metal doped g-C for implementing example 3 and preparing3N4The SEM shape of powder
Looks figure.As can be seen from Figure 1: transient metal doped g-C prepared by embodiment 13N4Powder is permitted by laminated structure cladding
Mostly nanotube-shaped structure composition；As can be seen from Figure 2: transient metal doped g-C prepared by embodiment 23N4Powder is by many
The nano tubular structure of sealing end forms；As can be seen from Figure 3: transient metal doped g-C prepared by embodiment 33N4Powder be by
Many micron tubular structure compositions.By attached drawing it can be seen that prepared transient metal doped g-C3N4Morphology microstructure structure can
Control, and there is tubular structure, effectively increase specific surface area.The transient metal doped g-C of present embodiment preparation3N4Powder
Body is through detecting: specific surface area is 59~82m2/g；Total pore volume is 0.24~0.68cm3/g；Average pore size be 11.32~
25.33nm。
Present embodiment is low in cost, simple process and environmental-friendly；Prepared transient metal doped g-C3N4Powder
Body has the characteristics that excellent photoresponse ability, good conductivity, structure and morphology are controllable and specific surface area is high.
Claims (6)
1. a kind of transient metal doped g-C3N4Raw powder's production technology, it is characterised in that the preparation method comprises the concrete steps that:
Step 1: transient metal doped g-C3N4The preparation of presoma
By nitrogenous compound: the mass ratio of transition metal inorganic salts is 1: 0.01~0.05, by the nitrogenous compound and described
The mixing of transition metal inorganic salts, obtains mixture；It is again 16.8~21.0g/L by solid-to-liquid ratio, the mixture is added organic
In solvent I, 1~3h is stirred, 60~80h of hydro-thermal process, then washs 3~5 with organic solvent II under the conditions of 150~180 DEG C
It is secondary, it filters, dry 8~10h, is made transient metal doped g-C under the conditions of 60~80 DEG C3N4Complex precursors；
Step 2: transient metal doped g-C3N4The preparation of powder
Under the conditions of protective atmosphere, with the rate of 5~8 DEG C/min by the transient metal doped g-C3N4Complex forerunner
Body is warming up to 450~600 DEG C, keeps the temperature 2~4h, transient metal doped g-C is made3N4Powder.
2. transient metal doped g-C according to claim 13N4Raw powder's production technology, it is characterised in that the nitrogen
Conjunction object is one of melamine, cyanuric acid, urea, thiocarbamide and dicyandiamide.
3. transient metal doped g-C according to claim 13N4Raw powder's production technology, it is characterised in that the transition gold
Category inorganic salts are one of cobalt nitrate, nickel nitrate, copper nitrate and ferric nitrate.
4. transient metal doped g-C according to claim 13N4Raw powder's production technology, it is characterised in that described organic molten
Agent I is one of nitrogen-nitrogen dimethylformamide, dehydrated alcohol and dimethyl sulfoxide；
The organic solvent II is identical as the organic solvent I.
5. transient metal doped g-C according to claim 13N4Raw powder's production technology, it is characterised in that the protectiveness
Atmosphere is one of argon gas, nitrogen and ammonia.
6. a kind of transient metal doped g-C3N4Powder, it is characterised in that the transient metal doped g-C3N4Powder is according to right
It is required that transient metal doped g-C described in any one of 1~53N4Transient metal doped g- prepared by raw powder's production technology
C3N4Powder.
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