CN104857978A - Water decomposition photocatalyst, preparation method and applications thereof - Google Patents

Water decomposition photocatalyst, preparation method and applications thereof Download PDF

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CN104857978A
CN104857978A CN201510092785.4A CN201510092785A CN104857978A CN 104857978 A CN104857978 A CN 104857978A CN 201510092785 A CN201510092785 A CN 201510092785A CN 104857978 A CN104857978 A CN 104857978A
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quantum dot
carbon quantum
solution
catalyst
preparation
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康振辉
李述汤
刘阳
耶沙亚胡·里弗西兹
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Suzhou Fangsheng Optoelectronics Equipment & Technology Co Ltd
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Suzhou Fangsheng Optoelectronics Equipment & Technology Co Ltd
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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 present invention provides a water decomposition photocatalyst and a preparation method thereof, wherein the catalyst is a carbon quantum dot-carbon nitride composite catalyst, the carbon quantum dot concentration in the catalyst is 4.8*10<-3>, and carbon quantum dots are respectively performed, the carbon quantum dot solution is further treated through ammonia water, and the obtained material and carbon nitride are subjected to compounding preparation. According to the present invention, the catalyst can have good stability after being subjected to dry reuse 200 times, and the quantum efficiency of the catalyst does not produce significant degeneration after 50 cycles.

Description

Water decomposition photoactivation agent and preparation method thereof and application
Technical field
The present invention relates to a kind of oxidizing process by two step two electronics, effectively utilized that visible ray realizes efficiently, stably catalytic decomposition water, realize a kind of photochemical catalyst of hydrogen making and oxygen simultaneously and preparation method thereof.
Background technology
In today of fossil energy crisis, manufacturing clean energy resource is at low cost one of effective way realizing human kind sustainable development.But the decomposition of water needs to realize under stricter experiment condition usually, such as brine electrolysis, light-Electricity Federation conjunction decomposition water etc. all need in reaction system, inject certain electric energy.Decomposing water with solar energy is utilized to produce H 2and O 2it is a kind of mode of promising storage rechargeable energy.In in the past 40 years, many inorganic, organic systems are all used as photochemical catalyst decomposition water (typical bibliographical information: J. Am. Chem. Soc. 133,11054-11057 (2011) under visible light; Energy Environ. Sci., 6,1983-2002 (2013); J. Phys. Chem. C, 117,17879-17893 (2013); Chem. Soc. Rev., 38,253-278 (2009)).But, the lower and less stable of the quantum efficiency of these photochemical catalysts.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of water decomposition photoactivation agent and preparation method thereof and application thereof.
The present invention is achieved through the following technical solutions.
A kind of water decomposition photoactivation agent, described catalyst is carbon quantum dot-carbonitride composite catalyst, and in described catalyst, carbon quantum dot concentration is 4.8x10 -3.
Preferably, comprise the steps,
S1, preparation carbon quantum dot, described carbon quantum dot is prepared by the method for electrochemical etching;
S11, graphite rod is inserted in ultra-pure water, respectively as negative electrode and anode, between two electrodes, add DC voltage, do not stop to stir successive reaction 120 hours;
S12, drying are weighed, and after reaction, colourless ultra-pure water becomes buff, and by dry for the solution obtained, obtained powder, weighs;
S13, preparation carbon quantum dot solution, be configured to carbon quantum dot solution by the powder dispersion of acquisition to ultra-pure water, solution concentration is 4 mg/L;
S2, prepare carbonitride, urea is put in the alumina crucible of adding a cover, in Muffle furnace, be heated to 550 DEG C with the programming rate of 0.5 DEG C/min, react 3 hours; After being cooled to room temperature, light yellow C can be obtained 3n 4powder;
The compound of S3, carbon quantum dot and carbonitride;
S31, in urea, add CDots solution, to put in the alumina crucible of adding a cover with the heating rate of 0.5 DEG C/min to 550 DEG C after mixing, be incubated 3 hours, the light brown powder of generation is cooled to room temperature;
S32, filtration drying, clean powder with ultra-pure water, collecting by filtration, more at room temperature drying obtains carbon quantum dot-carbonitride composite catalyst.
Preferably, also need through following steps after carbon quantum dot solution preparation in the preparation of described carbon quantum dot,
S14, WITH AMMONIA TREATMENT step, be mixed into mixed liquor by the solution of gained in ammoniacal liquor and S13 according to volume ratio 1:1, then transfer in polytetrafluoroethylene (PTFE) stainless steel autoclave by above-mentioned mixed solution, keep 7 h at 150 DEG C;
S15, centrifugation, collected yellow solution by centrifugation, places and remove unnecessary ammonia in atmosphere, until the pH value of solution is 7;
S16, oven dry are weighed, and are dried by the carbon quantum dot solution obtained, weigh, and be mixed with the carbon quantum dot solution that concentration is 2 mg/L after centrifugation in 60 DEG C of air.
Preferably, described method comprises the steps:
S1, preparation carbon quantum dot, described carbon quantum dot is prepared by the method for electrochemical etching;
S11, graphite rod is inserted in ultra-pure water, respectively as negative electrode and anode, between two electrodes, add DC voltage, do not stop to stir successive reaction 120 hours;
S12, drying are weighed, and after reaction, colourless ultra-pure water becomes buff, and by dry for the solution obtained, obtained powder, weighs;
S13, preparation carbon quantum dot solution, the powder dispersion obtained weighing is configured to the carbon quantum dot solution of 4 mg/L in ultra-pure water;
S14, WITH AMMONIA TREATMENT step, uniformly mix into mixed liquor with the solution of gained in S13 with volume ratio 1:1 by ammoniacal liquor, then transfers in polytetrafluoroethylene (PTFE) stainless steel autoclave by above-mentioned mixed solution, is incubated at 150 DEG C;
S15, centrifugation, afterwards by centrifugation by the carbon quantum dot solution collection after WITH AMMONIA TREATMENT, place remove unnecessary ammonia in atmosphere, until the pH value of solution is 7;
S16, oven dry are weighed, and are dried by the carbon quantum dot solution obtained, weigh, and be mixed with 2 mg/L carbon quantum dot solution in 60 DEG C of air;
S2, prepare carbonitride, 10 g urea are put in the alumina crucible of adding a cover, in Muffle furnace, is heated to 550 DEG C with the programming rate of 0.5 DEG C/min, react 3 hours; After being cooled to room temperature, light yellow C can be obtained 3n 4powder;
The compound of S3, carbon quantum dot and carbonitride,
S31, in urea, add the CDots solution that concentration is 2 mg/L, to put into after mixing in the alumina crucible of adding a cover with the heating rate of 0.5 DEG C/min to 550 DEG C, insulation, is cooled to room temperature by the light brown powder of generation, containing 0.6 g C in described powder 3n 4;
S32, filtration drying, clean powder with ultra-pure water, collecting by filtration, more at room temperature drying obtains carbon quantum dot-carbonitride composite catalyst.
Preferably, described carbon quantum dot-carbonitride composite catalyst is used for photocatalytic water splitting, and the amount adding described carbon quantum dot-carbonitride composite catalyst when catalytic decomposition water is 0.067-0.7 g/L, and makes solar energy can reach 2% to the transformation efficiency of hydrogen.
Preferably, the consumption of described catalyst is 0.53 g/L.
CDots-C 3n 4composite catalyst (4.8x10 -3g cDots/ g catalyst) solar energy can reach 2% to the transformation efficiency of hydrogen.
CDots-C 3n 4composite catalyst (1.6x10 -5g cDots/ g catalyst) after catalyst drying reuses 200 times, still there is good stability, at higher CDots concentration (4.8x10 -3g cDots/ g catalyst) catalyst quantum efficiency 50 circulation after significantly do not fail.
Compared with prior art, beneficial effect of the present invention is embodied in: catalyst drying can be reused after 200 times and still have good stability, and the quantum efficiency of catalyst does not significantly fail after 50 circulations.
Accompanying drawing explanation
Fig. 1 is the CDots-C prepared in embodiment 3n 4transmission electron microscope (TEM) photo of nano-composite catalyst.
Fig. 2 is for being supported on C 3n 4on carbon nano-particles high-amplification-factor under transmission electron microscope (TEM) photo.
Fig. 3 is carbon nano-particles high-resolution-ration transmission electric-lens (HRTEM) photo.
Fig. 4 is the compound CDots-C prepared in embodiment 3n 4grain size distribution.
Fig. 5 is the CDots-C prepared in embodiment 3n 4(CDots concentration, 1.6 ' 10 -5g cDots/ g catalyst) photodissociation aquatic products hydrogen (oxygen) amount under visible light and the relation curve of time, catalyst circulation uses 200 days.
Fig. 6 is under different wavelengths of light irradiates, CDots-C 3n 4(CDots concentration, 1.6 ' 10 -5g cDots/ g catalyst) photocatalytic water experiment in quantum efficiency and lambda1-wavelength between graph of a relation.Bandpass filter specification used in experiment is respectively 420 ± 20 nm, 460 ± 20 nm, 500 ± 20 nm, 540 ± 20 nm, 580 ± 15 nm, 600 ± 10 nm, 630 ± 20 nm, and uses the edge filter of long wavelength acquisition wavelength to be greater than the incident light of 700 nm.
Fig. 7 is the catalysis quantum efficiency contrast that the concentration regulating and controlling different carbon nano-particles prepares composite catalyst.
Fig. 8 is the graph of relation between the consumption of catalyst in photocatalysis experiment and quantum efficiency.
Specific embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
The present invention is pyrolysis urea synthesizing C 3n 4method, by composite carbon nano dot, preparation CDots-C 3n 4composite nano-catalyst, realizes visible light catalytic decomposition water.In this description, CDots all represents carbon quantum dot.
preparation CDots;
CDots is synthesized by the method for electrochemical etching.Two graphite rods are inserted ultra-pure water as anode and negative electrode, add 30 V DC voltages between two electrodes, successive reaction 120 h under ceaselessly stirring.After reaction, colourless ultra-pure water becomes buff.
By dry for the solution obtained, the powder obtained is weighed.
Then the carbon quantum dot solution being configured to 4 mg/L is distributed in ultra-pure water.
prepare the CDots through WITH AMMONIA TREATMENT;
CDots through WITH AMMONIA TREATMENT can catalytic decomposition hydrogen peroxide effectively, is therefore processed further by the carbon quantum dot solution of above-mentioned acquisition.Concrete grammar: the solution being the CDots of 4 mg/L by 30 mL ammoniacal liquor and 30 mL concentration mixes, and stirs into uniform solution.Then above-mentioned mixed solution is transferred in 100 mL polytetrafluoroethylene (PTFE) stainless steel autoclaves, at 150 DEG C, keep 7 h.
By centrifugation, yellow solution is collected, place and remove unnecessary ammonia in atmosphere, until the pH value of solution is 7.Next the CDots solution obtained is dried in 60 DEG C of air, weigh, and be mixed with the carbon quantum dot solution of 2 mg/L.
This carbon quantum dot solution decomposable asymmetric choice net hydrogen peroxide 1 per hour mmol.
preparation C 3 n 4 and CDots-C 3 n 4 catalyst;
Preparation C 3n 4, 10 g urea are put in the alumina crucible of adding a cover, in Muffle furnace, are heated to 550 DEG C with the programming rate of 0.5 DEG C/min, react 3 hours.After being cooled to room temperature, light yellow C can be obtained 3n 4powder.
Preparation CDots-C 3n 4, in 10 g urea, add the CDots solution that 5 mL concentration are 2 mg/L, to put in the alumina crucible of adding a cover with the heating rate of 0.5 DEG C/min to 550 DEG C after mixing, be incubated 3 h.The light brown powder of generation is cooled to room temperature, cleans with ultra-pure water, collecting by filtration, more at room temperature dry.The catalyst scales/electronic balance weighing obtained, gross mass is about 0.6 g ± 0.05 g.
When adding 2 mg/L CDots solution, in the catalyst of acquisition, CDots concentration is 1.6x10 -5g cDots/ g catalyst.The catalyst containing different CDots concentration can be obtained by change CDots solution addition.G in description cDots/ g catalystrepresent the concentration gravity units of carbon quantum dot in catalyst.
photocatalysis performance is tested, and obtained catalyst is carried out to the test of optical property.
The light-catalyzed reaction of composite photo-catalyst connects a closed gas-circulating system at external irradiation quartz reactor.By stirring, 80 mg photochemical catalysts being dispersed in the ultra-pure water of 150 mL, vacuumizing and removing air.And 300 W Xenon light shinings of visible ray (wavelength is greater than 420 nm) are obtained with band optical filter.
The speed that photocatalysis water produces hydrogen is analyzed by online SP-6890 gas-chromatography.
Photocatalytic water experiment in by magnetic agitation (400 rpm) to prevent its sedimentation.The test of catalyst has different modes: (1) continuously photocatalytic water reacts 45 days, and (2) catalyst illumination is dry in 60 ° of C baking ovens after 1 day, repetitive cycling photocatalytic water again of weighing tests 200 times.
Catalytic efficiency
CDots-C 3n 4(CDots concentration is 1.6x10 to catalyst -5g cDots/ g catalyst, catalyst loadings is 0.53 g/L) and be that quantum yield under 580 nm is lower at wavelength, be about 0.3%.By promoting C 3n 4the loading of upper CDots, under 420 nm ± 20 nm illumination, quantum yield can reach 16%.
In an experiment (80 mg catalyst, 150 mL water, 300 W xenon lamp band >420 nm edge filter illumination), under high CDots concentration, hydrogen generation rate improves 5.4 times.Most suitable CDots loading (4.8x10 -3g cDots/ g catalyst) time, the quantum efficiency of catalyst and carbon point concentration are at 1.6x10 -5g cDots/ g catalysttime quantum efficiency compare and significantly increase.It reaches 6.29%(when l=580 ± 15 nm is 1.6x10 -5g cDots/ g catalystthe twice of catalyst quantum efficiency), be 4.42% during the nm of l=600 ± 10.And under l>650 nm wavelength illumination, the quantum efficiency of two antigravity systems is all 0.
Catalyst stability
CDots-C 3n 4composite catalyst (1.6x10 -5g cDots/ g catalyst) after catalyst drying reuses 200 times, still there is good stability, at higher CDots concentration (4.8x10 -3g cDots/ g catalyst) catalyst quantum efficiency 50 circulation after significantly do not fail.
Gained CDots-C 3n 4catalyst carries out photocatalysis test, and its quantum efficiency is with CDots concentration and excitation wavelength change.
CDots concentration (g cDots/ g catalyst) be respectively 1.6x10 -5, 4.8x10 -3..., 8x10 -3deng.
Excitation wavelength is respectively l=280-400,400-440,440-480,480-520,520-560,565-595,590-610,610-650,620-680, and 700-4000 nm.
Most suitable CDots loading is 4.8x10 -3g cDots/ g catalyst.Optimum catalyst concentration is 0.53 g/L.
Urea of the present invention, described ammoniacal liquor is purity is that analysis is pure.
Photocatalysis performance is tested
The light-catalyzed reaction of composite photo-catalyst connects a closed gas-circulating system at external irradiation quartz reactor.By stirring, 80 mg photochemical catalysts being dispersed in the ultra-pure water of 150 mL, vacuumizing and removing air.And 300 W Xenon light shinings of visible ray (wavelength is greater than 420 nm) are obtained with band optical filter.The speed that photocatalysis water produces hydrogen is analyzed by online SP-6890 gas-chromatography.In photocatalytic water experiment, we use magnetic agitation (400 rpms) to prevent its sedimentation always.The test of catalyst has different modes: (1) continuously photocatalytic water reacts 45 days, and (2) catalyst illumination is dry in 60 ° of C baking ovens after 1 day, repetitive cycling photocatalytic water again of weighing tests 200 times.
Catalytic efficiency
CDots-C 3n 4(CDots concentration is 1.6x10 to catalyst -5g cDots/ g catalyst, catalyst loadings is 0.53 g/L) and be that quantum yield under 580 nm is lower at wavelength, be about 0.3%.By promoting C 3n 4the loading of upper CDots, under 420 nm ± 20 nm illumination, quantum yield can reach 16%.In an experiment (80 mg catalyst, 150 mL water, 300 W xenon lamp band >420 nm edge filter illumination), under high CDots concentration, hydrogen generation rate improves 5.4 times.Most suitable CDots loading (4.8x10 -3g cDots/ g catalyst) time, the quantum efficiency of catalyst and carbon point concentration are at 1.6x10 -5g cDots/ g catalysttime quantum efficiency compare and significantly increase.It reaches 6.29%(when l=580 ± 15 nm is 1.6x10 -5g cDots/ g catalystthe twice of catalyst quantum efficiency), be 4.42% during the nm of l=600 ± 10.And under l>650 nm wavelength illumination, the quantum efficiency of two antigravity systems is all 0.
Catalyst stability
CDots-C 3n 4composite catalyst (1.6x10 -5g cDots/ g catalyst) after catalyst drying reuses 200 times, still there is good stability, at higher CDots concentration (4.8x10 -3g cDots/ g catalyst) catalyst quantum efficiency 50 circulation after significantly do not fail.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (6)

1. a water decomposition photoactivation agent, is characterized in that: described catalyst is carbon quantum dot-carbonitride composite catalyst, and in described catalyst, carbon quantum dot concentration is 4.8x10 -3.
2. the preparation method of water decomposition photoactivation agent as claimed in claim 1, is characterized in that: comprise the steps,
S1, preparation carbon quantum dot, described carbon quantum dot is prepared by the method for electrochemical etching;
S11, graphite rod is inserted in ultra-pure water, respectively as negative electrode and anode, between two electrodes, add DC voltage, do not stop to stir successive reaction 120 hours;
S12, drying are weighed, and after reaction, colourless ultra-pure water becomes buff, and by dry for the solution obtained, obtained powder, weighs;
S13, preparation carbon quantum dot solution, be configured to carbon quantum dot solution by the powder dispersion of acquisition to ultra-pure water, solution concentration is 4 mg/L;
S2, prepare carbonitride, urea is put in the alumina crucible of adding a cover, in Muffle furnace, be heated to 550 DEG C with the programming rate of 0.5 DEG C/min, react 3 hours; After being cooled to room temperature, light yellow C can be obtained 3n 4powder;
The compound of S3, carbon quantum dot and carbonitride;
S31, in urea, add CDots solution, to put in the alumina crucible of adding a cover with the heating rate of 0.5 DEG C/min to 550 DEG C after mixing, be incubated 3 hours, the light brown powder of generation is cooled to room temperature;
S32, filtration drying, clean powder with ultra-pure water, collecting by filtration, more at room temperature drying obtains carbon quantum dot-carbonitride composite catalyst.
3. the preparation method of water decomposition photoactivation agent as claimed in claim 2, is characterized in that: also need through following steps after carbon quantum dot solution preparation in the preparation of described carbon quantum dot,
S14, WITH AMMONIA TREATMENT step, be mixed into mixed liquor by the solution of gained in ammoniacal liquor and S13 according to volume ratio 1:1, then transfer in polytetrafluoroethylene (PTFE) stainless steel autoclave by above-mentioned mixed solution, keep 7 h at 150 DEG C;
S15, centrifugation, collected yellow solution by centrifugation, places and remove unnecessary ammonia in atmosphere, until the pH value of solution is 7;
S16, oven dry are weighed, and are dried by the carbon quantum dot solution obtained, weigh, and be mixed with the carbon quantum dot solution that concentration is 2 mg/L after centrifugation in 60 DEG C of air.
4. the preparation method of water decomposition photoactivation agent as claimed in claim 3, is characterized in that: described method comprises the steps:
S1, preparation carbon quantum dot, described carbon quantum dot is prepared by the method for electrochemical etching;
S11, graphite rod is inserted in ultra-pure water, respectively as negative electrode and anode, between two electrodes, add DC voltage, do not stop to stir successive reaction 120 hours;
S12, drying are weighed, and after reaction, colourless ultra-pure water becomes buff, and by dry for the solution obtained, obtained powder, weighs;
S13, preparation carbon quantum dot solution, the powder dispersion obtained weighing is configured to the carbon quantum dot solution of 4 mg/L in ultra-pure water;
S14, WITH AMMONIA TREATMENT step, be that 1:1 uniformly mixes into mixed liquor by the solution of ammoniacal liquor and gained in S13 with volume ratio, then transfer in polytetrafluoroethylene (PTFE) stainless steel autoclave by above-mentioned mixed solution, be incubated at 150 DEG C;
S15, centrifugation, afterwards by centrifugation by the carbon quantum dot solution collection after WITH AMMONIA TREATMENT, place remove unnecessary ammonia in atmosphere, until the pH value of solution is 7;
S16, oven dry are weighed, and are dried by the carbon quantum dot solution obtained, weigh, and be mixed with 2 mg/L carbon quantum dot solution in 60 DEG C of air;
S2, prepare carbonitride, 10 g urea are put in the alumina crucible of adding a cover, in Muffle furnace, is heated to 550 DEG C with the programming rate of 0.5 DEG C/min, react 3 hours; After being cooled to room temperature, light yellow C can be obtained 3n 4powder;
The compound of S3, carbon quantum dot and carbonitride,
S31, in urea, add the CDots solution that concentration is 2 mg/L, to put into after mixing in the alumina crucible of adding a cover with the heating rate of 0.5 DEG C/min to 550 DEG C, insulation, is cooled to room temperature by the light brown powder of generation, containing 0.6 g C in described powder 3n 4;
S32, filtration drying, clean powder with ultra-pure water, collecting by filtration, more at room temperature drying obtains carbon quantum dot-carbonitride composite catalyst.
5. the application of water decomposition photoactivation agent as claimed in claim 1, it is characterized in that: described carbon quantum dot-carbonitride composite catalyst is used for photocatalytic water splitting, the amount adding described carbon quantum dot-carbonitride composite catalyst when catalytic decomposition water is 0.067-0.7 g/L, and makes solar energy can reach 2% to the transformation efficiency of hydrogen.
6. the application of water decomposition photoactivation agent as claimed in claim 5, is characterized in that: the consumption of described catalyst is 0.53 g/L.
CN201510092785.4A 2015-03-02 2015-03-02 Water decomposition photocatalyst, preparation method and applications thereof Pending CN104857978A (en)

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CN107519907A (en) * 2017-07-19 2017-12-29 广东工业大学 A kind of carbon point and graphite phase carbon nitride composite photo-catalyst and its preparation method and application
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CN107597166B (en) * 2017-09-29 2019-11-12 南昌航空大学 A kind of carbon dots/cadmiumsulfide quantum dot/carbon nitride catalyst and preparation method thereof
CN107597166A (en) * 2017-09-29 2018-01-19 南昌航空大学 A kind of carbon point/cadmiumsulfide quantum dot/carbon nitride catalyst and preparation method thereof
CN108380196A (en) * 2018-03-07 2018-08-10 苏州宝澜环保科技有限公司 A kind of zno-based optic catalytic composite material and preparation method thereof
CN109395763B (en) * 2018-12-14 2021-11-09 山东大学 Sulfur-doped g-C3N4C-dot porous composite photocatalyst and preparation method and application thereof
CN109395763A (en) * 2018-12-14 2019-03-01 山东大学 A kind of sulfur doping g-C3N4Porous composite photo-catalyst of/C-dot and the preparation method and application thereof
CN109554176A (en) * 2018-12-19 2019-04-02 合肥机数科技有限公司 A kind of g-C of embedded carbon quantum dot3N composite material and preparation method and application
CN109603882A (en) * 2018-12-26 2019-04-12 湖南大学 Utilize the method for modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing organic pollutant and photo-catalyst
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CN109999882A (en) * 2019-04-25 2019-07-12 湖南大学 A kind of carbon quantum dot-graphite phase carbon nitride composite material, preparation method and application
CN112742465A (en) * 2019-10-29 2021-05-04 中国石油化工股份有限公司 Modified oxidation catalytic material and preparation method thereof
CN112742465B (en) * 2019-10-29 2023-03-24 中国石油化工股份有限公司 Modified oxidation catalytic material and preparation method thereof
CN112221525A (en) * 2020-09-29 2021-01-15 河海大学 Novel artificial duckweed with sustainable high-efficiency water purification function
CN112221525B (en) * 2020-09-29 2021-12-28 河海大学 Artificial duckweed with sustainable high-efficiency water purification function
CN114289063A (en) * 2022-01-18 2022-04-08 东北大学 Carbon quantum dot and high-crystallinity polyheptazine imide compound and preparation method thereof

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