CN110201703A - A kind of preparation method of multi-element metal doping nitridation carbon composite - Google Patents
A kind of preparation method of multi-element metal doping nitridation carbon composite Download PDFInfo
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- CN110201703A CN110201703A CN201910598218.4A CN201910598218A CN110201703A CN 110201703 A CN110201703 A CN 110201703A CN 201910598218 A CN201910598218 A CN 201910598218A CN 110201703 A CN110201703 A CN 110201703A
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- carbonitride
- carbon composite
- transition metal
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 metals salt Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000003115 biocidal effect Effects 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 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 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 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 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention relates to field of inorganic materials, and in particular to a kind of preparation method of multi-element metal doping nitridation carbon composite.The preparation method of the composite material is the following steps are included: S1. mixes various metals salt and carbonitride is scattered in water or ethyl alcohol, 10 ~ 60min of ultrasound under conditions of 200 ~ 1000 W, wherein the metal salt is transition metal salt；S2. obtained suspension after step S1 ultrasound is filtered；S3. filter residue step S2 being obtained by filtration calcines 1 ~ 3h time under the conditions of 200 ~ 400 DEG C.The separation of carrier can be better achieved by the composite material that transition metal salt is obtained as dopant in the present invention, to reach better photocatalysis effect.Further, the photochemical catalyst of the nitridation carbon composite containing above method preparation, has the effect of the degradation of big ring resinae antibiotic excellent.
Description
Technical field
The present invention relates to field of inorganic materials, and in particular to a kind of preparation side of multi-element metal doping nitridation carbon composite
Method.
Background technique
Currently, the catalyst that researcher has been devoted to research high quality is asked with solving energy shortage and environmental disruption etc.
Topic.In design huge effort can have been put into the catalysis material of effective applied solar energy.Wherein, carbonitride is because it has
Preparation method is easy, has the characteristics that unique semiconductor electronic band structure and material resources chemical stability are high, has become one
Kind applies universal catalysis material.But the specific surface area of carbonitride is smaller, band gap width is relatively large and the photoproduction of generation
Carrier is easy serious in place of the deficiencies of compound to affect its further applying in the fields such as photocatalysis and environmental treatment.Cause
This has many researchers in research in recent years to prove by carrying out element doping to carbonitride so as to shorten its forbidden band
Width improves its utilization rate to visible light, to reach the photocatalytic activity for improving carbonitride in visible region.
There are mainly of two types for the doping of carbonitride, nonmetal doping and metal-doped.Unit metal is mainly used at present
Doping, there are photocarriers to be easy compound, the problems such as catalytic efficiency is not high.
Summary of the invention
It is an object of the invention to overcome the problems of the prior art, it is compound to provide a kind of multi-element metal doping carbonitride
The preparation method of material.
It is another object of the present invention to provide a kind of nitridation carbon composites being prepared containing the above method
Photochemical catalyst.
The purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of multi-element metal doping nitridation carbon composite, comprising the following steps:
S1. a variety of transition metal salts and carbonitride are mixed and is scattered in water or ethyl alcohol, it is ultrasonic under conditions of 200 ~ 1000W
10 ~ 60min, wherein the concentration of every metal ion species is 0.0001 ~ 0.02mol/L in a variety of transition metal salts；It is described more
According to the molar ratio, one of metal salt is 1 part to kind transition metal salt, other metal salts are 0.1 ~ 9 part；The concentration of carbonitride is
0.5~2g/L；
S2. obtained suspension after step S1 ultrasound is filtered；
S3. filter residue step S2 being obtained by filtration calcines 1 ~ 3h time under the conditions of 200 ~ 400 DEG C；A variety of transition metal
Salt includes two or more in molysite, mantoquita, nickel salt, cobalt salt or manganese salt.
Above-mentioned carbonitride can be obtained using customary preparation methods, or be obtained from commercially available approach.
The method that the present invention uses transition metal salt ultrasonic disperse, metal cation can be more uniformly and in carbonitride
N element lone electron combine.The metal ion in be distributed the uniform of carbonitride more is conducive to composite material energy band and reduces, thus
Be conducive to electron transition, play better photocatalytic effect.Carbonitride is doped simultaneously using a variety of different metals, by
It is different in conduction of the different metal to photocarrier, it is also different to the influence degree that photocarrier is compound.
Due to the carrier transmission effect difference using different metal dopants to carbonitride, such as carbonitride
Material has a wider fluorescent belt in 460nm or so, produced when being approximately equal to carbonitride band-gap energy this is mainly due to luminous energy
Band-to-band fluorescence phenomenon.When with same amount of iron and copper doping corresponding to carbonitride respectively, the composite material of Fe2O3 doping exists
460nm fluorescence has apparent reduction, and the composite material of Copper-cladding Aluminum Bar is very weak in the reduction of 460nm fluorescent belt.And fluorescence is strong
The height of degree reflects the degree of carrier separation indirectly, and the more low then carrier separation of fluorescence intensity is faster, and photocatalytic activity is got over
It is high.
It is different that the above phenomenon can be seen that different monatomic doping influence the photocatalytic activity of carbonitride.When using polynary
When element is doped carbonitride, since different metal atom can be living to the photocatalysis of carbonitride in carbonitride apparent competitive relationship
The influence of property can be more complicated.The catalytic performance of the atom doped obtained composite material of dissimilar metals is unpredictable.The present invention
It preferably can using two or more the transition metal salt in molysite, mantoquita, nickel salt, cobalt salt or manganese salt by research discovery
To obtain relatively good catalytic activity.
According to the molar ratio, one of metal salt is 1 part to transition metal salt, other metal salts are 0.1 ~ 9 part, for example, carbon
Change and adulterates the molar ratio of metal salt used in binary transition metal carbonitride in nitrogen as (0.1 ~ 9): 1, adulterate ternary transition metal nitrogen
The molar ratio for changing metal salt used in carbon is (0.1 ~ 9): (0.1 ~ 9): 1, adulterate metal salt used in quaternary transitional metal nitride carbon
Molar ratio is (0.1 ~ 9): (0.1 ~ 9): (0.1 ~ 9): 1, adulterating the molar ratio of metal salt used in five element/transition metal carbonitrides is
(0.1 ~ 9): (0.1 ~ 9): (0.1 ~ 9): (0.1 ~ 9): 1.Molar ratio described above is the ratio of the amount of the substance of this metal salt
Example.
It is highly preferred that the molar ratio of various metal salts is identical.
It is highly preferred that being employed nitrogen as in the step S3 to protect gas, heating rate is 3 ~ 6 DEG C/min.Made with nitrogen
For protection gas prevent during heating material be oxidized.It is heated with the heating rate of 3 ~ 6 DEG C/min, when temperature is increased to
Stop heating at 200 ~ 400 DEG C, calcines 1 ~ 3h at this temperature.
Preferably, after a variety of transition metal salts first being dissolved in step S1, then with carbonitride mix.
Preferably, the carbonitride is graphite phase carbon nitride.
A kind of photochemical catalyst, the multi-element metal doping nitridation carbon composite obtained including the preparation method.
Above-mentioned photochemical catalyst is being degraded on big ring resinae antibiotic using with preferable effect.
Compared with prior art, the present invention has following technical effect that
The present invention provides the preparation methods that a kind of multi-element metal adulterates nitridation carbon composite, are made by preferred transition metal salt
The separation that carrier can be better achieved for the composite material that dopant obtains reaches better photocatalysis effect.Into one
Step, the photochemical catalyst of the nitridation carbon composite containing above method preparation have the degradation of big ring resinae antibiotic excellent
Effect.
Detailed description of the invention
Fig. 1 is the shape appearance figure of iron, copper, nickel ternary doping carbonitride；
Fig. 2 is material extinction optical picture (Zuo Shichun carbonitride, the right side are ternary doping carbonitrides)；
Fig. 3 is the degradation property figure of iron, copper, the big ring resinae antibiotic of nickel ternary metal doping carbonitride (TDCN-1)；
Fig. 4 is the degradation property figure of iron, nickel, manganese, the big ring resinae antibiotic of the metal-doped carbonitride of cobalt quaternary (QDCN-1)；With
And；
Fig. 5 is the degradation property figure of iron, copper, nickel, manganese, the big ring resinae antibiotic of five yuan of cobalt metal-doped carbonitrides (FDCN).
Specific embodiment
It to make the object, technical solutions and advantages of the present invention clearer, combined with specific embodiments below will with comparative example
Technical solution of the present invention is described in detail.Obviously, described embodiments are only a part of the embodiments of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative labor
Obtained all other embodiment under the premise of dynamic belongs to the range that the present invention is protected.
Except specified otherwise, equipment used in the present embodiment, comparative example and experimental example is routine experiment equipment, used
Material, reagent be commercially available.
Embodiment 1
0.01mmol iron chloride, 0.01mmol copper acetate, 0.01mmol nickel nitrate is taken to be added sequentially to 100ml ethanol solution
In, ultrasonic disperse 60min after 0.10g nitridation carbon dust is added, so that metallic site is uniformly dispersed in stirring and dissolving 10min
Carbonitride (g-C3N4) surface on.After ultrasonic disperse, product is filtered with Suction filtration device and is separated, uses deionized water respectively
It is respectively cleaned with dehydrated alcohol three times, products therefrom is placed in 60 DEG C of vacuum drying oven and is dried in vacuo 1 day.Sample grinding after drying is standby
With.
By the sample after grinding under the protection of nitrogen, with 5 DEG C/min of heating rate, the condition that calcination time is 400 DEG C
Under, calcine 2h.It is after calcining, products therefrom ball milling is stand-by.As iron, copper, nickel ternary metal doping carbonitride (TDCN-1) produce
Object.
Embodiment 2
0.01mmol ferric nitrate, 0.01mmol nickel nitrate, 0.01mmol manganese acetate is taken to be added sequentially to 100ml ethanol solution
In, ultrasonic disperse 30min after 0.10g nitridation carbon dust is added, so that metallic site is uniformly dispersed in stirring and dissolving 10min
Carbonitride (g-C3N4) surface on.After ultrasonic disperse, product is filtered with Suction filtration device and is separated, uses deionized water respectively
It is respectively cleaned with dehydrated alcohol three times, products therefrom is placed in 60 DEG C of vacuum drying oven and is dried in vacuo 1 day.Sample grinding after drying is standby
With.
By the sample after grinding under the protection of nitrogen, with 4 DEG C/min of heating rate, the condition that calcination time is 300 DEG C
Under, calcine 1h.It is after calcining, products therefrom ball milling is stand-by.As iron, nickel, manganese ternary metal doping carbonitride (TDCN-2) produce
Object.
Embodiment 3
0.01mmol ferric nitrate, 0.01mmol nickel nitrate, 0.01mmol manganese acetate, 0.02mmol cobalt nitrate is taken to be added sequentially to
In 100ml ethanol solution, ultrasonic disperse 30min after 0.10g nitridation carbon dust is added, so that metal in stirring and dissolving 10min
Site is uniformly dispersed in carbonitride (g-C3N4) surface on.After ultrasonic disperse, product is filtered with Suction filtration device and is divided
From, respectively cleaned three times with deionized water and dehydrated alcohol respectively, by products therefrom be placed in 60 DEG C of vacuum drying oven be dried in vacuo 1 day.
Sample grinding after drying is spare.
By the sample after grinding under the protection of nitrogen, with 6 DEG C/min of heating rate, the condition that calcination time is 350 DEG C
Under, calcine 1h.It is after calcining, products therefrom ball milling is stand-by.As iron, nickel, manganese, the metal-doped carbonitride of cobalt quaternary (QDCN-1)
Product.
Embodiment 4
Take 0.01mmol ferric nitrate, 0.01mmol copper acetate, 0.01mmol nickel nitrate, 0.01mmol manganese acetate, 0.01mmol nitre
Sour cobalt is added sequentially in 100ml ethanol solution, stirring and dissolving 10min, and ultrasonic disperse after 0.10g nitridation carbon dust is added
30min, so that metallic site is uniformly dispersed in carbonitride (g-C3N4) surface on.After ultrasonic disperse, Suction filtration device is used
Product is filtered and is separated, is respectively cleaned three times with deionized water and dehydrated alcohol respectively, products therefrom is placed in 60 DEG C of vacuum drying oven
Vacuum drying 1 day.Sample grinding after drying is spare.
By the sample after grinding under the protection of nitrogen, with 5 DEG C/min of heating rate, the condition that calcination time is 400 DEG C
Under, calcine 2h.It is after calcining, products therefrom ball milling is stand-by.As five yuan of iron, copper, nickel, manganese, cobalt metal-doped carbonitrides
(FDCN) product.
Experimental example 1
The metal-doped nitridation carbon composite that embodiment 1 is obtained carries out surface topography characterization.As shown in Figure 1.As shown in Figure 2
For material extinction optical picture.The above-mentioned photochemical catalyst prepared is taken to carry out photocatalysis effect experiment, specific experiment process are as follows: weigh
100mg photochemical catalyst is added in the big ring resinae antibiotic solution that 150mL concentration is 10mg/L, is stirred at dark
30min reaches adsorption equilibrium, then provides radiation of visible light using 300W xenon lamp and carries out light-catalyzed reaction, takes every 5min
About 7ml solution, centrifugal filtration catalyst, using the absorbance of antibiotic solution in measurement of ultraviolet-visible spectrophotometer filtrate,
Using the time as abscissa, the concentration ratio of the concentration and original concentration of antibiotic solution is that ordinate is made in filtrate when measurement
Figure, catalytic effect experimental result are as shown in Figure 3.The result shows that synthesized ternary transition metal adulterates carbonitride TDCN-1
Photocatalysis performance be better than pure carbonitride, photodegradation rate is can achieve in 150min shown in 99%, Fig. 4, synthesized
The photodegradation rate of the transient metal doped carbonitride QDCN-1 of quaternary can achieve 98% in 120min, as shown in figure 5, synthesized
Five element/transition metals doping carbonitride FCND photodegradation rate can achieve 99% in 120min.
Claims (8)
1. a kind of preparation method of multi-element metal doping nitridation carbon composite, which comprises the following steps:
S1. a variety of transition metal salts and carbonitride are mixed and is scattered in water or ethyl alcohol, it is ultrasonic under conditions of 200 ~ 1000W
10 ~ 60min, wherein the concentration of every metal ion species is 0.0001 ~ 0.02mol/L in a variety of transition metal salts；It is described more
According to the molar ratio, one of metal salt is 1 part to kind transition metal salt, other metal salts are 0.1 ~ 9 part；The concentration of carbonitride is
0.5~2g/L；
S2. obtained suspension after step S1 ultrasound is filtered；
S3. filter residue step S2 being obtained by filtration calcines 1 ~ 3h time under the conditions of 200 ~ 400 DEG C；A variety of transition metal
Salt includes two or more in molysite, mantoquita, nickel salt, cobalt salt or manganese salt.
2. the preparation method of multi-element metal doping nitridation carbon composite according to claim 1, which is characterized in that described more
Kind transition metal salt is two or more in iron chloride, copper acetate, nickel nitrate, cobalt nitrate or manganese acetate.
3. the preparation method of multi-element metal doping nitridation carbon composite according to claim 1, which is characterized in that described more
Every kind of molar ratio is identical in kind transition metal salt.
4. the preparation method of multi-element metal doping nitridation carbon composite according to claim 1, which is characterized in that the step
It is employed nitrogen as in rapid S3 to protect gas, heating rate is 3 ~ 6 DEG C/min.
5. the preparation method of multi-element metal doping nitridation carbon composite according to claim 1, which is characterized in that step S1
It is middle a variety of transition metal salts are first dissolved after, then with carbonitride mix.
6. according to claim 1 to the preparation method of the 5 multi-element metal doping nitridation carbon composites, which is characterized in that institute
Stating carbonitride is graphite phase carbon nitride.
7. a kind of photochemical catalyst, which is characterized in that adulterate nitridation including the multi-element metal that preparation method described in claim 1 obtains
Carbon composite.
8. catalyst described in a kind of claim 7 is in the application of big ring resinae antibiotic of degrading.
Priority Applications (1)
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