CN108579785A - Efficient visible light decomposes aquatic products H2Sulfur doping carbonitride preparation method - Google Patents
Efficient visible light decomposes aquatic products H2Sulfur doping carbonitride preparation method Download PDFInfo
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- CN108579785A CN108579785A CN201810359238.1A CN201810359238A CN108579785A CN 108579785 A CN108579785 A CN 108579785A CN 201810359238 A CN201810359238 A CN 201810359238A CN 108579785 A CN108579785 A CN 108579785A
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- aquatic products
- sulfur doping
- doping carbonitride
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- carbonitride
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007146 photocatalysis Methods 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000012719 thermal polymerization Methods 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulphur Hydrazone Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003643 water by type Substances 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
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to nano-photocatalyst material technical fields, specifically disclose a kind of for visible photocatalysis aquatic products H2Sulfur doping carbonitride (S g C3N4) preparation method, include the following steps：1) appropriate ammonium salt is weighed in container plus diluted acid dissolves, and is added certain proportion melamine in wherein mixing, is heated close dry；2) 500~600 DEG C of 3~6h of temperature lower calcination, cooled to room temperature under air atmosphere obtain efficient visible light and decompose aquatic products H2Sulfur doping carbonitride.It is an advantage of the invention that：One step thermal polymerization method, reaction is simple, quick, easily operated, and reaction process green non-pollution and yield height are suitable for practical application.
Description
Technical field
The present invention relates to nano-photocatalyst material technical fields, specifically disclose a kind of for visible photocatalysis aquatic products H2's
Sulfur doping carbonitride (S-g-C3N4) preparation method.
Background technology
H2It is considered as the fuel of future ideality as a kind of reproducible clean energy resource of green.Current 90% or more H2
It is to be obtained by methane vapor reforming and Water gas shift/WGS, preparation process needs a large amount of fossil energies therefore to utilize solar energy
Conversion production H2It is significant, be extremely challenging research work.Water is decomposed under visible light generates H2It is current important new
Using energy source research hotspot, compare thermocatalytic, photocatalysis in energy conservation and environmental protection, reduce cost in terms of have a clear superiority, but at present
Photocatalysis efficiency is also very low.How while cost is reduced, photocatalysis Decomposition aquatic products H is improved2Activity, the stability of system
And selectivity, become photocatalysis Decomposition aquatic products H2The key of research, therefore find the efficiency light for having that yield is high, simple, economic
Catalyst is then the task of top priority.Semi-conducting material has extensive in fields such as solar cell, optical electro-chemistry catalysis, photocatalysis
Using being considered as the indispensable catalysis material of the following potential green clean energy resource.Graphite phase carbon nitride (g-C3N4) from
It is found to produce H under visible light2Performance since, the research hotspot of production capacity is just rapidly become as a kind of non-metallic catalyst,
There is prodigious development potentiality in solar energy conversion.But its lower specific surface area (10m2g-1), higher light induced electron it is empty
Cave combined efficiency seriously constrains its catalytic activity, causes its photocatalysis performance relatively low.In order to solve this problem, can pass through
It introduces defect, the means such as adulterate or be chemically modified to g-C3N4It is modified, regulates and controls its composition, electronic structure and specific surface
The properties such as product, can effectively improve disadvantages mentioned above, improve its catalytic activity.Such as by g-C3N4When carrying out sulphur atom doping, lead to
It crosses generated reactive gas and can reach and mix the economic benefits and social benefits of sulphur and stripping and answer, pass through and regulate and control g-C3N4Composition, electronic structure and thickness, obtain
To the ultra-thin g-C for mixing sulphur3N4, specific surface area significantly increases, while surface generates abundant carbon omission, exposes more activity
Site is conducive to absorption of the water in catalyst surface, enhances g-C3N4Photocatalysis Decomposition aquatic products H2Reactivity, while surface
Abundant nitrogen is also exposed, is conducive to adsorb heavy metal, can be applied to the detection of heavy metal in environment.Lead is a kind of accumulation
Property poisonous substance, easily absorbed by stomach, passing through blood influences enzyme and cell metabolism.Therefore, content of the lead in environmental water sample be
One important indicator of environment measuring control.Water quality Pb is provided in existing National Environmental standard detecting method2+Measurement have double sulphur
Hydrazone spectrophotometry and atomic absorption method, detection are limited to 10ug/L, but Pb in environmental water sample2+Content it is relatively low, these methods are not
The measurement requirement of trace lead can be met, therefore, be highly desirable a kind of quick, sensitive Pb of structure at present2+Detection method.
But preparing at present, there is visible light catalytic to decompose aquatic products H2g-C3N4Method, general yield is all very low, and prepare
The shortcomings of required time is grown, and method is complicated, expensive, limits its practical application.Therefore finding has yield height, simple, warp
The modification g-C of Ji3N4Preparation method and it can apply to efficient visible light catalytic decomposition aquatic products H2With heavy metal Pb in environmental water sample2+
Measurement be of great immediate significance.
Invention content
The technical problem to be solved by the present invention is to propose a kind of for visible photocatalysis water for the above-mentioned prior art
Produce H2Sulfur doping carbonitride (S-g-C3N4) preparation method, graphite phase carbon nitride (g-C can be solved3N4) specific surface area
(10m2g-1) low, surface-active site is few and defect is less and H is produced in visible light catalytic water decomposition2The relatively low problem of activity.
The technical solution adopted by the present invention to solve the technical problems is：For visible photocatalysis aquatic products H2Sulfur doping nitrogen
The preparation method for changing carbon, includes the following steps：
1) appropriate ammonium salt is weighed in container plus diluted acid dissolves, and is added certain proportion melamine in wherein mixing, is added
It is hot close dry；
2) 500~600 DEG C of 3~6h of temperature lower calcination, cooled to room temperature obtain efficient visible light under air atmosphere
Decompose aquatic products H2Sulfur doping carbonitride.
By said program, ammonium salt is ammonium sulfate, ammonium persulfate or ammonium chloride in step 1).
By said program, diluted acid is dilute sulfuric acid or dilute hydrochloric acid, a concentration of 0.1molL in step 1)-1
By said program, ammonium salt and melamine molar ratio are 0.5~1.5 in step 1).
By said program, the heating rate of the step 2) calcining is 5~15 DEG C/min.Rate is slower, and the hot polymerization time gets over
Long, yield is lower；Rate is faster, and the hot polymerization time is shorter, but the lamella of product is thicker.
What above-mentioned preparation method obtained is used for visible photocatalysis aquatic products H2Sulfur doping carbonitride.
By said program, the sulfur doping carbonitride is the vacant ultra-thin S-g-C of carbon3N4, thickness is 2~8nm, compares table
Area is 90~189m2/g。
Application of the sulfur doping carbonitride of gained of the invention as elctro-catalyst in environmental water sample in the measurement of lead.
The present invention generates a large amount of NH using melamine and one step thermal polymerization method of ammonium sulfate, by ammonium sulfate heat resolve3、
SO2And N2Gas is inserted in melamine hot polymerization and controls its extent of polymerization, while being generated by ammonium sulfate thermal decomposition
SO2Gas, which realizes, to be mixed the economic benefits and social benefits of sulphur and stripping and answers, and is prepared for having the vacant ultra-thin S-g-C of abundant carbon3N4, thickness is
2.5nm, and specific surface area is up to 189m2/ g, photocatalysis Decomposition aquatic products H2Rate can reach 4923 μm of olh-1·g-1, respectively
It is unmodified g-C3N411.8 times and 12.9 times.The present invention can also Pb in constructing environment water sample2+Electrochemical determination method,
Detection is limited to 3nmoL/L, and the recovery of standard addition of actual water sample is 88-103%, and this method has sensitivity low, selective good, accurate
The high feature of exactness.
It is an advantage of the invention that：One step thermal polymerization method, reaction it is simple, quick, easily operated, reaction process green non-pollution and
Yield is high, is suitable for practical application.
Description of the drawings
Fig. 1 is the S-g-C of present invention gained3N4(a) transmission electron microscope (TEM)；(b) atomic force microscopy diagram (AFM)；c)X
X ray diffration pattern x (XRD)；
Fig. 2 is the S-g-C of present invention gained3N4(a) XPS compose entirely；(b)S2pSpectrum；
Fig. 3 is the S-g-C of present invention gained3N4(a) photoelectricity flow graph；(b) impedance diagram；
Fig. 4 is the S-g-C of present invention gained3N4(a) photocatalysis Decomposition aquatic products hydrogen figure；(b) photocatalysis Decomposition aquatic products hydrogen speed
Rate figure.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
By ammonium sulfate 5mL 0.1molL-1H2SO4Dissolving is added 1:After the melamine of 1 molar ratio stirs evenly, add
Heat is to close dry, then after calcining 4h in 550 DEG C of Muffle furnaces with the heating rate of 7.5 DEG C/min, cooled to room temperature to get to
S-g-C3N4(1)It is denoted as A, yield 30%, and bulk g-C3N4Yield is generally also only 40%.Fig. 1 be its TEM, AFM and
XRD diagram.S-g-C can be clearly visible from TEM figures3N4For flake, it is 2.5nm that lamellar spacing is clearly visible in AFM figures, should
Product uses ratio surface area instrument to measure specific surface area as 189m2/g.From XRD diagram it can be seen that S-g-C3N413.1 ° composition planes
3-s- triazine structural units be formed by (100) crystal face characteristic peak and disappear, and 27.5 ° of graphite linings by pi-conjugated plane
Shape is accumulated and (002) crystal face characteristic peak is caused to be substantially reduced, and illustrates that lamella is apparent thinning.From Fig. 2 (a) as can be seen that product
In contain tri- element of C, N and S, Fig. 2 (b) can obviously analyze S combination can be 168.1eV, explanation consistent with bibliography
S is successfully mixed in carbonitride, and its C/N illustrates that S occupies carbon potential, surface occurs than becoming 0.64 from the 0.75 of bulk
Apparent carbon is vacant.
Embodiment 2
The ratio for only changing ammonium sulfate and melamine is 1:1.5,0.5:1, remaining step is the same as embodiment 1.Obtain S-g-
C3N4(1.5)And S-g-C3N4(0.5), it is denoted as B and C respectively.
Embodiment 3
It is 15 DEG C/min only to change heating rate, remaining step is with embodiment 1 to get to 15 DEG C of-S-g-C3N4(1), 420nm
Visible light illumination produces H after three hours2Amount and production H2Rate is respectively：726 μm of ol and 4841 μm of olh-1·g-1。
Embodiment 4
Photoelectricity current test：
By photochemical catalyst (A, B, C) and bulk-g-C3N4The aqueous dispersions of 1.0mg/L are respectively configured as, 5 μ L drop coatings are drawn
To the glassy carbon electrode surface of a diameter of 3mm.In the case where wavelength is the illumination condition of 420nm, in 1mol/L Na2SO4It is measured in solution
The photoelectric current ratio of catalyst is A:B:C:bulk-g-C3N4It is approximately equal to 8:6:3:1, as shown in Fig. 3 (a) figures, the wherein photoelectricity of A
Stream is maximum, illustrates that visible light catalytic performance is best.
Embodiment 5
Electrochemical impedance spectroscopy is tested：
By photochemical catalyst A and bulk-g-C3N4The aqueous dispersions of 1.0mg/L are respectively configured as, draw 5 μ L drop coatings to diameter
For the glassy carbon electrode surface of 3mm, in K containing 0.005mol/L3[Fe(CN)6]/K4[Fe(CN)6] and 0.1mol/L KCl solution
In, it measures photochemical catalyst A impedances and is significantly less than bulk-g-C3N4, impedance value is respectively 53.9 Ω and 240.6 Ω, illustrates that light is urged
The charge transport rate on the surfaces agent A is faster, and electronics and hole separative efficiency are higher, and electrocatalysis characteristic is better, as a result sees Fig. 3
(b)。
Embodiment 6
Visible light catalytic decomposes the test of aquatic products hydrogen：
1) by the photochemical catalyst of 50mg (A, B, C) and bulk-g-C3N4It is added separately in 90mL deionized waters, is added
10mL triethanolamines and 1wt%Pt, in Photoreactor, (Labsolar III (AG), light source are 300W xenon lamps, are inserted into 420nm and filter
Piece) in illumination produce H after three hours2Amount is respectively：A-739 μm of ol, B-530 μm of ol, C-147 μm of ol, bulk-57 μm of ol.Produce H2Speed
Rate is respectively：A–4923μmol·h-1·g-1, B-3530 μm of olh-1·g-1, C-980 μm of olh-1·g-1, bulk-382 μ
mol·h-1·g-1, wherein A is bulk-g-C3N412.9 times, photochemical catalyzing hydrogen generation efficiency highest, than general literature report
The g-C in road3N4It is all high, as a result see Fig. 4.
2) according to 1) method, it is separately added into the photochemical catalyst of 25mg and 100mg, the illumination of 420nm visible lights is produced after three hours
H2Amount is respectively：245 μm of ol and 904 μm of ol produce H2Rate is respectively 3273 μm of ol g-1h-1With 3012 μm of ol g-1h-1。
Embodiment 7
The measurement of lead in environmental water sample：
Weigh S-g-C3N4It for dressing agent, is dispersed in aqueous solution, then drop coating passes through L- on glass-carbon electrode
Modified electrode is made in Cysteine electropolymerizations；Add in pH=4.4NaAc-HAc buffer solutions in 410nm radiation of visible light 2min
Enter 0.4mLSDS and various concentration Pb2+Solution carries out differential pulse method scanning, according to Pb after 1.4v current potentials are enriched with 100s2+Oxygen
Change the linear equation of peak current intensity and its concentration：IPb2+(μ A)==0.078CPb2+(μM)+0.31 (R=0.988)；Linear model
It encloses for 2.5*10-6mol/L-7.5*10-8Mol/L can measure Pb2+Content, detection are limited to 3nmoL/L, are applied to actual water sample
Recovery of standard addition is 88-103% (RSD 1.05%).100 times of Pb2+Concentration：K+、Na+、Zn2+、Ca2+、Mg2+、Fe3+、Hg2+、
Cl-、Ac-、NO3-It is noiseless；50 times of Pb2+Concentration：Cr3+、Co3+It is noiseless；10 times of Pb2+Concentration：Cd2+It is noiseless.Constructed by explanation
Method have higher sensitivity and selectivity.
Claims (8)
1. being used for visible photocatalysis aquatic products H2Sulfur doping carbonitride preparation method, include the following steps：
1) appropriate ammonium salt is weighed in container plus diluted acid dissolves, and adds certain proportion melamine in wherein mixing, heating is close
It is dry；
2) 500~600 DEG C of 3~6h of temperature lower calcination, cooled to room temperature under air atmosphere obtain efficient visible light decomposition
Aquatic products H2Sulfur doping carbonitride.
2. as described in claim 1 be used for visible photocatalysis aquatic products H2Sulfur doping carbonitride preparation method, it is characterised in that
Ammonium salt is ammonium sulfate, ammonium persulfate or ammonium chloride in step 1).
3. as described in claim 1 be used for visible photocatalysis aquatic products H2Sulfur doping carbonitride preparation method, it is characterised in that
Diluted acid is dilute sulfuric acid or dilute hydrochloric acid, a concentration of 0.1molL in step 1)-1。
4. as described in claim 1 be used for visible photocatalysis aquatic products H2Sulfur doping carbonitride preparation method, it is characterised in that
Ammonium salt and melamine molar ratio are 0.5~1.5 in step 1).
5. as described in claim 1 be used for visible photocatalysis aquatic products H2Sulfur doping carbonitride preparation method, it is characterised in that
The heating rate of the step 2) calcining is 5~15 DEG C/min.
6. what any one of claim 1-5 was obtained is used for visible photocatalysis aquatic products H2Sulfur doping carbonitride.
7. as described in claim 6 be used for visible photocatalysis aquatic products H2Sulfur doping carbonitride, it is characterised in that the sulphur is mixed
Miscellaneous carbonitride is the vacant ultra-thin S-g-C of carbon3N4, thickness is 2~8nm, and specific surface area is 90~189m2/g。
8. application of the sulfur doping carbonitride as elctro-catalyst in environmental water sample in the measurement of lead described in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810359238.1A CN108579785B (en) | 2018-04-20 | 2018-04-20 | High-efficiency visible light decomposition aquatic product H2Preparation method of sulfur-doped carbon nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810359238.1A CN108579785B (en) | 2018-04-20 | 2018-04-20 | High-efficiency visible light decomposition aquatic product H2Preparation method of sulfur-doped carbon nitride |
Publications (2)
| Publication Number | Publication Date |
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| CN108579785A true CN108579785A (en) | 2018-09-28 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569689A (en) * | 2018-12-17 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the carbon-based elctro-catalyst of hydrogen manufacturing and products thereof and application |
| CN109735963A (en) * | 2019-01-16 | 2019-05-10 | 江苏理工学院 | A kind of preparation method and applications of azotized carbon nano fiber |
| CN110624588A (en) * | 2019-09-23 | 2019-12-31 | 北京交通大学 | D-g-C3N4Preparation method and application of visible light catalytic material |
| CN112495413A (en) * | 2020-10-30 | 2021-03-16 | 江苏大学 | Ammonium persulfate induced porous carbon nitride nanosheet and preparation method and application thereof |
| CN114100656A (en) * | 2021-11-16 | 2022-03-01 | 武汉工程大学 | Preparation method of S-CN-D homogeneous nano heterojunction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN104292236A (en) * | 2014-09-15 | 2015-01-21 | 浙江大学 | Preparation method of three-dimensional porous g-C3N4 material |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| CN105271141A (en) * | 2015-11-19 | 2016-01-27 | 南京工程学院 | Method for preparing porous graphite-phase carbon nitride material |
| CN105642329A (en) * | 2016-01-01 | 2016-06-08 | 三峡大学 | Loaded graphite phase carbonized nitrogen composite material as well as preparation method and application thereof |
-
2018
- 2018-04-20 CN CN201810359238.1A patent/CN108579785B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN104292236A (en) * | 2014-09-15 | 2015-01-21 | 浙江大学 | Preparation method of three-dimensional porous g-C3N4 material |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| CN105271141A (en) * | 2015-11-19 | 2016-01-27 | 南京工程学院 | Method for preparing porous graphite-phase carbon nitride material |
| CN105642329A (en) * | 2016-01-01 | 2016-06-08 | 三峡大学 | Loaded graphite phase carbonized nitrogen composite material as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 牛萍 等: "具有高光催化活性的类石墨烯g-C3N4纳米片", 《第十三届全国太阳能光化学与光催化学术会议学术论文集》 * |
| 王栋萍: "类石墨相氮化碳电极材料的制备及其在铅离子检测中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569689A (en) * | 2018-12-17 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the carbon-based elctro-catalyst of hydrogen manufacturing and products thereof and application |
| CN109735963A (en) * | 2019-01-16 | 2019-05-10 | 江苏理工学院 | A kind of preparation method and applications of azotized carbon nano fiber |
| CN109735963B (en) * | 2019-01-16 | 2021-12-21 | 江苏理工学院 | Preparation method and application of carbon nitride nanofiber |
| CN110624588A (en) * | 2019-09-23 | 2019-12-31 | 北京交通大学 | D-g-C3N4Preparation method and application of visible light catalytic material |
| CN110624588B (en) * | 2019-09-23 | 2021-05-04 | 北京交通大学 | D-g-C3N4Preparation method and application of visible light catalytic material |
| CN112495413A (en) * | 2020-10-30 | 2021-03-16 | 江苏大学 | Ammonium persulfate induced porous carbon nitride nanosheet and preparation method and application thereof |
| CN114100656A (en) * | 2021-11-16 | 2022-03-01 | 武汉工程大学 | Preparation method of S-CN-D homogeneous nano heterojunction |
| CN114100656B (en) * | 2021-11-16 | 2023-03-07 | 武汉工程大学 | Preparation method of S-CN-D homogeneous nano heterojunction |
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