CN105772055A - Preparation method for carbon nitride visible-light-induced photocatalyst - Google Patents
Preparation method for carbon nitride visible-light-induced photocatalyst Download PDFInfo
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- CN105772055A CN105772055A CN201610208528.7A CN201610208528A CN105772055A CN 105772055 A CN105772055 A CN 105772055A CN 201610208528 A CN201610208528 A CN 201610208528A CN 105772055 A CN105772055 A CN 105772055A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 48
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 47
- 239000001103 potassium chloride Substances 0.000 claims description 24
- 235000011164 potassium chloride Nutrition 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 5
- 235000013877 carbamide Nutrition 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000012719 thermal polymerization Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 CARBON NITRIDES Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- 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
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- 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 invention belongs to the field of nanometer catalyst material synthesis and specifically relates to a microwave ion heat ultra-fast preparation method for a carbon nitride visible-light-induced photocatalyst. According to the method, an organic precursor is taken as a raw material, a fused salt is taken as a reaction medium, the thermal polymerization reaction is carried out under microwave irradiation, and a solid matter acquired from the thermal polymerization reaction is treated and then a carbon nitride catalyst is acquired. According to the method provided by the invention, a microwave ion heating method is adopted for increasing the moving speed of the fused salt, the collision probability of the reactants is increased, the reaction speed is increased and the reaction time is greatly shortened.
Description
Technical field
The invention belongs to nano-catalyst material synthesis field, be specifically related to the microwave plasma ultrafast preparation method of heat of a kind of carbonitride visible light catalyst.
Background technology
The sun carries 3 × 10 to the earth every year24The energy of J, how efficiently utilizing solar energy is the key subject that human society solves energy problem.Solar energy can directly utilize or be converted into other convenient form of energy utilized, including biomass photosynthesis, solar energy power generating, solar energy photodissociation Aquatic product hydrogen etc..High efficiency photocatalyst plays a decisive role in solar energy photodissociation Aquatic product hydrogen.Effective catalyst design and the preparation of solar energy photocatalytic hydrogen production by water decomposition, is focus and the forward position of regenerative resource research and development, has important science and using value.
At present, studying more solid-phase photocatalyst has transition metal oxide nano brilliant (such as titanium oxide, zinc oxide etc.), metal sulfide nanocrystalline (zinc sulfide, cadmium sulfide etc.), carbonitride nanocrystalline, and their composite construction etc. [Appl.Catal.B-Environ.2015,170-171,74;Langmuir2015,31,4314;Appl.Catal.B-Environ.2015,164,1].These catalysis material majorities exist that electronic band structure does not mate with solar spectral, catalytic efficiency is not high, catalyst itself is unstable, be difficult to the technical bottlenecks such as volume production, limit the industry development of solar energy catalyzing manufacturing of hydrogen.The new catalyst of solar visible light can be efficiently utilized to be developed into the research focus of material and chemical science man.Wherein, graphite phase carbon nitride visible light catalyst, band gap, at about 2.7eV, has good visible light catalytic performance, and chemical stability is high, competent acid or alkali environment, be most application prospect one of new catalyst [Nat.Mater.2009,8,76]。
Graphite phase carbon nitride catalyst is cheap, green, preparation in macroscopic quantity technology breakthrough is the precondition obtaining commercial applications.At present; graphite phase carbon nitride visible light catalyst preparation method; mainly with containing presomas such as C, the carbamide of N element, tripolycyanamide, dicyandiamides for raw material, in air or protective atmosphere, at 500 ~ 600 DEG C of temperature of resistance furnace, be incubated 3 ~ 4 hours, by presoma thermal polymerization [Angew.Chem.2014,126,9394].The method heat treatment time is long, and presoma easily and air reaction, causes that productivity is extremely low.Additionally, carbonitride preparation process is sensitive to the seal of reaction vessel, the poor stability of product property, repeatability is difficult to ensure that.The technical bottlenecks such as productivity low, response time length, the product poor repeatability that existing preparation method exists, strongly limit the scale preparation of carbon nitride catalyst and popularization and application, need the controlled synthesis new method that development carbon nitride catalyst is quick, efficient, energy-conservation badly.
It is fast and have the feature of non-thermal effect that microwave has body heat characteristic, programming rate, have in the preparation process of catalyst material important application [Chem.Rev.2014,114,6462].The absorption of microwave is had selectivity by material, and the most cases therefore prepared at material needs to add microwave absorption auxiliary agent in the feed to assist intensification, for instance patent (graphite-like structure carbon nitride material quickly prepared by 201310404491.1 microwave heatings).But, directly utilizing in the process of microwave synthesis, influence factor is more, course of reaction is not easily controlled and course of reaction is fierce, the direct preparation process of microwave method requires that reaction vessel has good seal, the temperature that reaction needed is higher, and is held requirement accurately the time.
Summary of the invention
It is an object of the invention to provide a kind of method adopting microwave plasma full-boiled process quickly to prepare carbonitride visible light catalyst.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of a kind of carbonitride visible light catalyst, the method is raw material with organic precursor, is reaction medium with fused salt, carries out heat polymerization in microwave exposure, and heat polymerization gained solids is post-treated obtains carbon nitride catalyst.
Organic precursor is one or more in tripolycyanamide, carbamide, dicyandiamide.
Fused salt is the mixture of potassium chloride and lithium chloride, and the fusing point of fused salt is not less than 353 DEG C and not higher than heat polymerization temperature.
The mass ratio of organic precursor and fused salt is 0.2-1.
Microwave exposure carries out in microwave workstation, and microwave power is 2-4KW, and heat treatment temperature is 400-600 DEG C, and temperature retention time is 1-60min.Preferred 480-580 DEG C of heat treatment temperature, the preferred 10-30min of temperature retention time.
Microwave workstation is microwave Muffle furnace, microwave tube type oven.
Specifically comprise the following steps that 1) determine the mass ratio of lithium chloride and potassium chloride in fused salt according to phasor fusing point；
2) by the organic precursor of set amount with and the fused salt mixed grinding of step 1) uniform；
3) step 2) mixed powder that obtains is placed in microwave workstation and carries out heat polymerization；
4) gained solids scrubbed (using 50-80 DEG C of hot water) after step 3) heat polymerization, dry, obtains carbon nitride catalyst.
When determining the fusing point of fused salt, make the fusing point of fused salt be not less than 353 DEG C and not higher than heat polymerization temperature, so can ensure that during reaction, fused salt dissolves, and provides a liquid phase environment for reaction；Determine the fusing point of fused salt, determine the mass ratio of lithium chloride and potassium chloride according to phasor fusing point.
The invention is intended to seek a kind of preparation method easy, gentle, easy-operating, in microwave preparation process, liquid phase is introduced so exploring, however, it was found that general microwave liquid phase synthesis temperature is relatively low, the ambient temperature that carbon nitride photocatalyst preparation is required cannot be met, the last present invention utilizes fused salt to serve as the liquid phase medium in hot environment, forming ionic liquid when heating, the polycondensation for organic precursor provides stable liquid phase environment, is more beneficial for its reaction；The ionic liquid that fused salt is formed simultaneously prevents organic precursor to contact with the undue of air, reduce the dependence to reaction vessel seal, the productivity of carbonitride is greatly improved, by regulating and controlling, carbon nitride product can be made to may be up to 71% relative to the productivity of organic precursor.Additionally, carbon nitride product is had certain template action by the fused salt added, by fused salt composition and the regulation and control of fusing point, in conjunction with the optimization of microwave treatment, can quickly prepare carbonitride visible light catalyst；The NANO CRYSTALLINE CARBON NITRIDES generated is main in the form of sheets, and this two-dimensional structure is conducive to improving reaction photocatalytic activity.
In the present invention, microwave and fused salt interact, and the migration of microwave assisted fused salt ion increases the collision probability of reactant, improves reaction rate, response time is greatly shortened, compares being greatly shortened for 3-4 hour required for current resistance furnace thermal polymerization method prepares carbonitride；Form ionic liquid under fused salt high temperature, provide a more stable response system for reactant, reduce the interference of unstable factor in microwave process, this method can be called " microwave plasma heat " method.The microwave plasma full-boiled process of the present invention is a kind of stable, green, new method that high yield prepares NANO CRYSTALLINE CARBON NITRIDES, and the carbonitride visible light catalyst of the method synthesis improves a lot than traditional resistor thermal polymerization product on catalysis H2-producing capacity, hydrogen-producing speed reaches 0.6-1.8mmol/ (g h), has the visible light catalytic H2-producing capacity of excellence.
This patent adopts the reaction heater that a kind of microwave workstation with microwave-assisted absorption function reaction cavity synthesizes as catalyst, and arbitrary substance can quickly be heated by this microwave workstation (Muffle furnace or tube furnace), it does not have significantly selectivity；Sodium chloride/lithium chloride the fused salt mixt introduced carries out the reaction medium of thermal polymerization as organic precursors, but not microwave absorption medium.This preparation method has essential distinction with the method (graphite-like structure carbon nitride material quickly prepared by 201310404491.1 microwave heatings) reported for work.
Accompanying drawing explanation
Fig. 1 is the digital photograph of embodiment 1 carbonitride visible light catalyst；
Fig. 2 is the X ray diffracting spectrum of embodiment 1 carbonitride visible light catalyst；
Fig. 3 is the stereoscan photograph of embodiment 1 carbonitride visible light catalyst；
Fig. 4 is the H2-producing capacity curve of embodiment 1 carbonitride visible light catalyst；
Fig. 5 is the X ray diffracting spectrum of embodiment 2 carbonitride visible light catalyst；
Fig. 6 is the stereoscan photograph of embodiment 2 carbonitride visible light catalyst；
Fig. 7 is the H2-producing capacity curve of embodiment 2 carbonitride visible light catalyst；
Fig. 8 is the X ray diffracting spectrum of embodiment 3 carbonitride visible light catalyst；
Fig. 9 is the stereoscan photograph of embodiment 3 carbonitride visible light catalyst；
Figure 10 is the transmission electron microscope photo of embodiment 3 carbonitride visible light catalyst;；
Figure 11 is the H2-producing capacity curve of embodiment 3 carbonitride visible light catalyst；
Figure 12 is the H2-producing capacity curve of embodiment 4 carbonitride visible light catalyst；
Figure 13 is the H2-producing capacity curve of embodiment 4 carbonitride visible light catalyst；
Figure 14 is the scanning electron microscopic picture of embodiment 6 carbonitride visible light catalyst；
Figure 15 is the H2-producing capacity curve of embodiment 6 carbonitride visible light catalyst；
Figure 16 is the X ray diffracting spectrum of embodiment 7 carbonitride visible light catalyst；
Figure 17 is the H2-producing capacity curve of embodiment 7 carbonitride visible light catalyst；Figure 18 is the H2-producing capacity curve of embodiment 8 carbonitride visible light catalyst.
Detailed description of the invention
Embodiment 1
Using 1.356 grams lithium chlorides and 1.644 grams of potassium chloride mix homogeneously as fused salt (fused salt fusing point: 353 DEG C), add 1.26 grams of tripolycyanamide；After grinding 20min, above-mentioned solid mixture is put in alumina ceramic crucible (capacity 20ml).This crucible is positioned over microwave Muffle furnace centre position, under air ambient, carries out microwave combustion method: risen to 550 DEG C with the programming rate of 10 DEG C/min by room temperature, be incubated 30min；After cooling by 50 DEG C of hot washes of solids of obtaining repeatedly, dissolving potassium chloride and lithium chloride, at 80 DEG C dry 12 hours, obtain carbonitride visible light catalyst, productivity is 56%.
In this embodiment, the mass ratio of tripolycyanamide and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 59.2%:40.8%.
The digital photograph of gained sample is as it is shown in figure 1, be Powdered, for light yellow.Fig. 2 is the XRD figure spectrum of gained sample, it can be seen that this sample has certain degree of crystallinity.
Fig. 3 is the stereoscan photograph of gained sample, and the carbonitride of gained is reunion shape, has part club shaped structure, and there is microspike on surface, and there is sheet deposit in some areas.
As shown in Figure 4, the hydrogen-producing speed under its visible ray reaches 1.1mmol/ (g h) to the visible light catalytic H2-producing capacity of gained carbonitride visible light catalyst.
Embodiment 2
Using 1.356g lithium chloride and 1.644g potassium chloride mix homogeneously as fused salt (fused salt fusing point: 353 DEG C), add 1.26g tripolycyanamide, after grinding 20min, put in the ceramic crucible of 20ml；This crucible is positioned over microwave Muffle furnace centre position, by following temperature schedule heat treatment: programming rate is 10 DEG C/min, operating temperature 580 DEG C, temperature retention time 45min.The 80 DEG C of hot washes of sample that will obtain, at 80 DEG C, dry 12h, obtains carbonitride visible light catalyst, productivity 54%.
In this embodiment, the mass ratio of tripolycyanamide and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 59.2%:40.8%.
The stereoscan photograph of gained carbonitride visible light catalyst as shown in Figure 6, is substantially slightly reunited by laminated structure and is formed, and there is an accumulation of small pieces on large stretch of surface, and local is it is observed that club shaped structure.
Gained carbonitride visible light catalyst visible light catalytic photocatalytic water H2-producing capacity is as it is shown in fig. 7, the hydrogen-producing speed under its visible ray reaches 1.13mmol/ (g h).
Embodiment 3
Using 1.1043g lithium chloride and 1.8957g potassium chloride mix homogeneously as fused salt (fused salt fusing point: 450 DEG C), add 1.26g tripolycyanamide, after grinding 20min, put in the ceramic crucible of 20ml.This crucible is positioned over microwave Muffle furnace centre position, according to following temperature schedule heat treatment: programming rate is 10 DEG C/min, operating temperature 550 DEG C, temperature retention time 30min；By after the sample hot wash that obtains, at 80 DEG C, dry 12h, obtains carbonitride visible light catalyst, and productivity is 55%.
In this embodiment, the mass ratio of tripolycyanamide and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 50.6%:49.4%.
The stereoscan photograph of gained sample as it is shown in figure 9, its transmission electron microscope photo as shown in Figure 10.In the form of sheets, structure is comparatively loose for gained sample, and its lamellar structure is very thin, has lattice fringe clearly, good crystallinity.
As shown in figure 11, the hydrogen-producing speed under its visible ray reaches 1.5mmol/ (g h) to the visible light catalytic photocatalytic water H2-producing capacity of gained sample.
Embodiment 4
Using 1.1043g lithium chloride and 1.8957g potassium chloride mix homogeneously as fused salt (fused salt fusing point: about 450 DEG C), add 1.26g dicyanodiamine, after grinding 20min, put in the ceramic crucible of 20ml.This crucible is positioned over microwave Muffle furnace centre position, according to following temperature schedule heat treatment: programming rate is 10 DEG C/min, operating temperature 550 DEG C, temperature retention time 30min；By after the sample hot wash that obtains, at 80 DEG C, dry 12h, obtains carbonitride visible light catalyst, productivity 71%.
In this embodiment, the mass ratio of dicyanodiamine and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 50.6%:49.4%.
As shown in figure 12, the hydrogen-producing speed under its visible ray reaches 1.3mmol/ (g h) to gained carbonitride visible light catalyst visible light catalytic photocatalytic water H2-producing capacity.
Embodiment 5
Using 1.356g lithium chloride and 1.644g potassium chloride mix homogeneously as fused salt (fused salt fusing point: 353 DEG C), add 1.5g carbamide, ground, put in the ceramic crucible of 20ml；This crucible is positioned over microwave Muffle furnace centre position, by following temperature schedule heat treatment: programming rate is 10 DEG C/min, operating temperature 550 DEG C, temperature retention time 30min.The sample hot wash that will obtain, at 80 DEG C, dry 12h, obtains carbonitride visible light catalyst, productivity 3%.
In this embodiment, the mass ratio of carbamide and fused salt is the mol ratio of 50:100, lithium chloride and potassium chloride is 59.2%:40.8%.
As shown in figure 13, the hydrogen-producing speed under its visible ray reaches 1.5mmol/ (g h) to gained carbonitride visible light catalyst visible light catalytic photocatalytic water H2-producing capacity.
Embodiment 6
Using 1.356 grams lithium chlorides and 1.644 grams of potassium chloride mix homogeneously as fused salt (fused salt fusing point: 353 DEG C), add 1.26 grams of tripolycyanamide；After grinding 20min, above-mentioned solid mixture is put in alumina ceramic crucible (capacity 20ml).This crucible is positioned over microwave Muffle furnace centre position, under air ambient, carries out microwave combustion method: risen to 480 DEG C with the programming rate of 10 DEG C/min by room temperature, be incubated 30min；After cooling by 50 DEG C of hot washes of solids of obtaining repeatedly, dissolving potassium chloride and lithium chloride, at 80 DEG C dry 12 hours, obtain carbonitride visible light catalyst, productivity is 71%.
In this embodiment, the mass ratio of tripolycyanamide and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 59.2%:40.8%.
Gained scanning electron microscopic picture is that in Figure 13, figure, it is abundant lamellar as seen, and its hydrogen-producing speed is 0.68mmol/ (g h).
Embodiment 7
Using 2.26 grams lithium chlorides and 2.74 grams of potassium chloride mix homogeneously as fused salt (fused salt fusing point: 353 DEG C), add 1 gram of tripolycyanamide；After grinding 20min, above-mentioned solid mixture is put in alumina ceramic crucible (capacity 20ml).This crucible is positioned over microwave Muffle furnace centre position, under air ambient, carries out microwave combustion method: risen to 550 DEG C with the programming rate of 10 DEG C/min by room temperature, be incubated 30min；After cooling by the solids hot wash that obtains repeatedly, dissolving potassium chloride and lithium chloride, at 80 DEG C dry 12 hours, obtain carbonitride visible light catalyst, productivity is 66%.
In this embodiment, the mass ratio of tripolycyanamide and fused salt is the mol ratio of 20:100, lithium chloride and potassium chloride is 59.2%:40.8%.
As shown in figure 16, its hydrogen output is 0.82mmol/ (g h) to its hydrogen output picture.
Embodiment 8
Using 1.1043g lithium chloride and 1.8957g potassium chloride mix homogeneously as fused salt (fused salt fusing point: about 450 DEG C), add 0.63g dicyanodiamine and 0.63g tripolycyanamide, after grinding 20min, put in the ceramic crucible of 20ml.This crucible is positioned over microwave Muffle furnace centre position, according to following temperature schedule heat treatment: programming rate is 10 DEG C/min, operating temperature 550 DEG C, temperature retention time 30min；By after the sample hot wash that obtains, at 80 DEG C, dry 12h, obtains carbonitride visible light catalyst, productivity 71%.
In this embodiment, the mass ratio of presoma and fused salt is the mol ratio of 42:100, lithium chloride and potassium chloride is 50.6%:49.4%.
As shown in figure 18, the hydrogen-producing speed under its visible ray reaches 1.8mmol/ (g h) to gained carbonitride visible light catalyst visible light catalytic photocatalytic water H2-producing capacity.
The H2-producing capacity of embodiment 1-8 products therefrom all than with tripolycyanamide be raw material, the H2-producing capacity (0.1mmol/ (g h)) of carbonitride prepared of resistance furnace ordinary hot polymerization had large increase, when surveying H2-producing capacity, catalyst amount is unified for 50mg.
Claims (7)
1. the preparation method of a carbonitride visible light catalyst, it is characterized in that: the method is raw material with organic precursor, is reaction medium with fused salt, carries out heat polymerization in microwave exposure, heat polymerization gained solids is post-treated obtains carbon nitride catalyst.
2. the preparation method of carbonitride visible light catalyst as claimed in claim 1, it is characterised in that organic precursor is one or more in tripolycyanamide, carbamide, dicyandiamide.
3. the preparation method of carbonitride visible light catalyst as claimed in claim 1 or 2, it is characterised in that fused salt is the mixture of potassium chloride and lithium chloride, and the fusing point of fused salt is not less than 353 DEG C and not higher than heat polymerization temperature.
4. the preparation method of carbonitride visible light catalyst as claimed in claim 1, it is characterised in that the mass ratio of organic precursor and fused salt is 0.2-1.
5. the preparation method of carbonitride visible light catalyst as claimed in claim 1, it is characterised in that microwave exposure carries out in microwave workstation, and microwave power is 2-4KW, and heat treatment temperature is 400-600 DEG C, and temperature retention time is 1-60min.
6. the preparation method of carbonitride visible light catalyst as claimed in claim 5, it is characterised in that microwave workstation is microwave Muffle furnace, microwave tube type oven.
7. the preparation method of carbonitride visible light catalyst as claimed in claim 1, it is characterised in that specifically comprise the following steps that 1) determine the mass ratio of lithium chloride and potassium chloride in fused salt according to phasor fusing point；
2) by the organic precursor of set amount with and the fused salt mixed grinding of step 1) uniform；
3) step 2) mixed powder that obtains is placed in microwave workstation and carries out heat polymerization；
4) after step 3) heat polymerization, gained solids is scrubbed, dry, obtains carbonitride visible light catalyst.
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