CN108855195A - A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method - Google Patents

A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method Download PDF

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CN108855195A
CN108855195A CN201810889288.0A CN201810889288A CN108855195A CN 108855195 A CN108855195 A CN 108855195A CN 201810889288 A CN201810889288 A CN 201810889288A CN 108855195 A CN108855195 A CN 108855195A
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carbon
photochemical catalyst
preparation
amorphous carbon
carbon nitride
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曾昱嘉
张璐虹
金正元
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Shenzhen University
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Shenzhen University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/39

Abstract

The invention discloses a kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation methods, wherein photochemical catalyst is formed by biomass fiber and melamine by calcining.The present invention uses pure natural carbon source material(Biomass fiber)As template carbon source, presoma of the melamine as synthesis carbonitride can be prepared by efficient photochemical catalyst by calcining.Equipment requirement needed for this preparation method is low, and raw material biomass fiber, melamine are cheap to be easy to get, and without reaction units such as valuable processing synthesis device and high temperature and pressure, process is simple, meets the theory of environmentally protective new energy, is suitable for high-volume and synthesizes.

Description

A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method
Technical field
The present invention relates to photocatalytic cleavage water technical fields more particularly to a kind of carbon to adulterate amorphous carbon nitride photochemical catalyst And preparation method.
Background technique
Clean energy resource hydrogen is generated using sunlight catalytic splitting water, is the effective way for developing sustainable green energy resource. Realize that highly effective hydrogen yield, photochemical catalyst need to meet following three main aspects:(1)Semiconductor light-catalyst has reasonable bandwidth to inhale Receive maximum solar radiation;(2)Realize photo-generated carrier efficiently separate and photo-generated carrier is low in conjunction with rate;(3)There is height Conductivity realize light induced electron effective transmission.In addition, catalysis material should meet and nontoxic, at low cost be easily obtained and be easy to Preparation etc. requires.
Graphite phase carbon nitride (g-C3N4) it is a kind of organic semiconductor photochemical catalyst by extensive concern and research in recent years. g-C3N4It is stratiform two-dimensional material, it has reasonable bandwidth(~ 2.7 eV), constitution element is simple(C and N), it is easily obtained, The advantages that chemical and thermal stability is high, nontoxic.But original g-C3N4Photocatalyzed Hydrogen Production efficiency it is still very low, its catalytic efficiency It is low to visible light utilization efficiency to be limited to it, specific surface area is small and conductive characteristic is poor.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of carbon doping amorphous carbon nitride light to urge Agent and preparation method, it is intended to solve the problems, such as that existing photochemical catalyst catalytic efficiency is low.
Technical scheme is as follows:
A kind of preparation method of carbon doping amorphous carbon nitride photochemical catalyst, using biomass fiber and melamine by calcining The carbon doping amorphous carbon nitride photochemical catalyst is prepared.
The preparation method of the carbon doping amorphous carbon nitride photochemical catalyst, wherein the biomass fiber is kapok Fiber or bamboo pulp fiber.
The preparation method of the described carbon doping amorphous carbon nitride photochemical catalyst, wherein the biomass fiber and described The mass ratio of melamine is 0.005-0.1:1.
The preparation method of the carbon doping amorphous carbon nitride photochemical catalyst, wherein by the biomass fiber and institute It states melamine to be scattered in organic solvent, then evaporates the organic solvent, then calcined, the carbon doping is prepared Amorphous carbon nitride photochemical catalyst.
The preparation method of the carbon doping amorphous carbon nitride photochemical catalyst, wherein the temperature of calcining is 500-700 ℃。
The preparation method of the carbon doping amorphous carbon nitride photochemical catalyst, wherein the time of calcining is 2.5-4h.
A kind of carbon doping amorphous carbon nitride photochemical catalyst, including:Biomass fiber after carbonization and it is grown on the carbon The amorphous carbon nitride of the carbon dope on biomass fiber after change;The carbon doping amorphous carbon nitride photochemical catalyst is by institute as above The preparation method stated is prepared.
Beneficial effect:The present invention provides a kind of preparation method of photochemical catalyst as described above, the present invention uses pure day Right carbon source material(Biomass fiber)As template carbon source, presoma of the melamine as synthesis carbonitride is obtained by calcining A kind of carbon doping amorphous carbon nitride photochemical catalyst is arrived.The carbon doping amorphous carbon nitride of gained epitaxial growth can be effectively sharp With visible light, light induced electron and hole effectively improve photodestruciton water to can be realized quick separating and be transferred to interface The performance of renewable energy hydrogen is prepared, realizes that Photocatalyzed Hydrogen Production amount reaches more than ten times of increase.Equipment needed for this preparation method It is required that low, raw material melamine is cheap to be easy to get, without the reactions such as valuable processing synthesis device and high temperature and pressure dress It sets, process is simple, meets the theory of environmentally protective new energy, is suitable for high-volume and synthesizes.
Detailed description of the invention
Fig. 1 is the SEM image of 2.5CCN600 prepared by the present invention.
Fig. 2 is the SEM image of carbonitride CN600.
Fig. 3 is the SEM image of bombax cotton.
Fig. 4 is the TEM image of 2.5CCN600 prepared by the present invention.
Fig. 5 is the TEM image of carbonitride CN600.
Fig. 6 is the EDS energy spectrum diagram of 2.5CCN600 prepared by the present invention.
Fig. 7 is the EDS energy spectrum diagram of carbonitride CN600.
Fig. 8 is different bombax cottons of the invention(KF)The carbon doping amorphous carbon nitride of additive amount and the XRD diagram of KF.
Fig. 9 is that the carbon of different bombax cotton additive amounts of the invention adulterates amorphous carbon nitride UV-Vis DRS light Spectrogram(UV-vis DRS).
Figure 10 is that the carbon of different bombax cotton additive amounts of the invention adulterates the bandwidth figure of amorphous carbon nitride.
Figure 11 is different bombax cotton additive amounts of the invention in the resulting carbon doping amorphous carbon nitride of 550 DEG C of sintering Photolysis water hydrogen catalytic performance figure.
Figure 12 is different bombax cotton additive amounts of the invention in the resulting carbon doping amorphous carbon nitride of 600 DEG C of sintering Photolysis water hydrogen catalytic performance figure.
Specific embodiment
The present invention provides a kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation methods, to make mesh of the invention , technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that described herein Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
The present invention provides a kind of preferred embodiments of the preparation method of carbon doping amorphous carbon nitride, by biomass fibre Peacekeeping melamine is formed by calcining.
By using pure natural carbon source material(Biomass fiber)As template carbon source, melamine is as synthesis carbonitride Presoma obtained a kind of carbon doping amorphous carbon nitride photochemical catalyst by calcining.Carbon of the invention adulterates amorphous nitrogen Visible light, light induced electron and hole can be efficiently used to can be realized quick separating and be transferred to interface by changing carbon, and then effectively Improve the performance of photodestruciton water preparation renewable energy hydrogen, high catalytic efficiency in ground.And equipment requirement needed for preparation method is low, The prices of raw materials are cheap to be easy to get, and preparation flow is simple, meets the theory of environmentally protective new energy.
Specifically, first dispersing the biomass fiber and the melamine in organic solvent, wherein biomass Fiber can be bombax cotton or bamboo pulp fiber or other synthesising biological matter fibers, preferably bombax cotton(KF), bombax cotton The characteristic for having surface hydrophobicity characteristic and gently floating is the biomass carbon source of lightweight high-ratio surface, can effectively improve amorphous nitridation The epitaxial growth density of carbon improves catalytic efficiency.Preferably, the mass ratio of the biomass fiber and the melamine is 0.005-0.1:1.Biomass fiber too high levels are readily incorporated excessive carbon fiber, generate shadow effect, and visible light is stopped to shine It is mapped in carbon nitride catalyst, reduces photon utilization efficiency, hamper utilization of the carbonitride to light.
Then for 24 hours by drying at above-mentioned mixed liquor progress solvent evaporation, such as 60 DEG C.Solid matter is put into sintering furnace again In, finally calcined.Preferred calcination temperature is 500-700 DEG C, and temperature is too low, and melamine can not aggregate into carbonitride, And more than 700, carbonitride is unstable, it may occur that disintegrates.Preferred sintering time is 2.5-4h.
The present invention also provides a kind of carbon to adulterate amorphous carbon nitride photochemical catalyst, using the preparation of above-mentioned preparation method At.The carbon adulterates amorphous carbon nitride photochemical catalyst:Biomass fiber after carbonization and after being grown on the carbonization The amorphous carbon nitride of carbon dope on biomass fiber.Bombax cotton shows 10 μm of diameter or so of tubulose, trimerization after sintering Cyanamide, which is put forth effort on, carries out the amorphous carbon nitride that epitaxial growth goes out thin layer carbon dope on the kapok after carbonization.The material is conducive to sufficiently Visible light, light induced electron and hole is absorbed and utilized to can be realized quick separating and be transferred to interface, and then effectively improves light The performance of splitting water preparation renewable energy hydrogen.
Below by embodiment, the present invention is described in detail, for the convenience of description, the carbon doping by synthesis is amorphous The product of carbonitride is named as nCCNx, wherein n is bombax cotton and melamine mass ratio, and ratio is percentage(n%), x For calcination temperature;Such as bombax cotton and melamine mass ratio are 0.005:1, i.e. n=0.5,550 DEG C of sintering products obtained therefroms, life Entitled 0.5CCN550.
Embodiment 1(The preparation of 5CCN550)
The melamine for weighing 0.1g bombax cotton and 2g is placed in crucible, and 2ml ethyl alcohol is then added and stirs, is uniformly dispersed Afterwards, crucible is placed in 60 DEG C of baking ovens of baking oven and is dried for 24 hours;It is again that crucible is with cover, it is placed in Muffle furnace, heats up(2℃/min)Extremely 550 DEG C of calcining 3h, obtain 5CCN550.
Embodiment 2(The preparation of 2.5CCN600)
The melamine for weighing 0.05g bombax cotton and 2g is placed in crucible, and 2ml ethyl alcohol is then added and stirs, is uniformly dispersed Afterwards, crucible is placed in 60 DEG C of baking ovens of baking oven and is dried for 24 hours;It is again that crucible is with cover, it is placed in Muffle furnace, heats up(2℃/min)Extremely 600 DEG C of calcining 3h, obtain 2.5CCN600.
Embodiment 3(The preparation of 0.5CCN650)
The melamine for weighing 0.01g bombax cotton and 2g is placed in crucible, and 2ml ethyl alcohol is then added and stirs, is uniformly dispersed Afterwards, crucible is placed in 60 DEG C of baking ovens of baking oven and is dried for 24 hours;It is again that crucible is with cover, it is placed in Muffle furnace, heats up(2℃/min)Extremely 650 DEG C of calcining 3h, obtain 0.5CCN650.
The reference examples of other ratios and sintering temperature can refer to above method preparation in Figure of description, and the present invention is no longer It repeats.
Characterization and test
Structural characterization:Use X-ray diffraction(XRD)Analysis crystallization situation, uses scanning electron microscope(SEM)With projection Electronic Speculum(TEM)Observation Material morphology and energy disperse spectroscopy(EDS)Carry out detection elements component, with UV-vis DRS spectrum(UV-vis DRS)Characterize material Material strip is wide and to light absorption.
Photocatalysis performance test:By in visible light(λ≥420 nm)Optical intensity density is 100mW/cm2Hydrogen production by water decomposition into Row assessment.Experimentation is as follows:10mg photochemical catalyst is dispersed in equipped with 90ml H2O, 10 ml triethanolamines, 3wt% H2PtCl6In solution, golden source hydrogen manufacturing system is taught to be tested in.In entire illumination, every 30min gas-chromatography GC Automatic sampling detects hydrogen content.
Compare 2.5CCN600 prepared by the present invention(Fig. 1), carbonitride CN600(Fig. 2)And bombax cotton(Fig. 3)SEM Image, it can be seen that purity nitrogen coke build-up it is very close, show the structure of block, bombax cotton shows 10 μm of left sides of diameter Right tubulose, 2.5CCN600 then can see apparent layering, the whole random agaric of topographic image, and thin layer clearly may be used See.
Compare 2.5CCN600 of the invention(Fig. 4)And carbonitride CN600(Fig. 5)TEM image, it can be seen that carbon dope Unformed carbonitride(Fig. 4), pattern is soft very much, layer good dispersion, the side of black, is unformed after bombax cotton is carbonized Carbon, in sintering process, bombax cotton is first carbonized, outer on the bombax cotton of the melamine being mixed then in the carbonized Prolong and grow carbonitride, is introduced into bombax cotton and enables to reach good layered effect in melamine heat polymerization process.And Pure carbonitride(Fig. 5)Show high-crystallinity effect and stacked in layers.
From EDS energy spectrum diagram(Fig. 6, Fig. 7)As can be seen that the essential element of 2.5CCN600 and carbonitride CN600 composition are C and N is added after bombax cotton, and carbon content increases, and illustrates that catalyst realizes carbon dope.And do not have besides oxygen Other miscellaneous elements exist.
Fig. 8 is different bombax cottons prepared by the present invention(KF)The carbon of additive amount adulterates unformed carbonitride and KF's XRD diagram;With the addition of bombax cotton, carbonitride crystallization effect is deteriorated, and amorphization is presented in feature peak broadening, carbonitride.
Fig. 9, Figure 10 be the carbon of different bombax cotton additive amounts prepared by the present invention adulterate that unformed carbonitride is ultraviolet can See the spectrogram UV-vis DRS that diffuses(Fig. 9)And bandwidth figure(Figure 10).After introducing kapok fibre, product is to visible absorption Increase;Catalyst semiconductor bandwidth becomes more and more narrow also with doping increase simultaneously, increases to the utilization rate of visible light.
Figure 11, Figure 12 are different bombax cotton additive amounts prepared by the present invention at 550 DEG C(Figure 11)With 600 DEG C(Figure 12)Resulting carbon adulterates unformed carbonitride photolysis water hydrogen catalytic performance figure.It can be seen that the addition of bombax cotton, i.e. carbon dope Unformed carbon nitride material system is conducive to improve the Photocatalyzed Hydrogen Production activity of carbon nitride material, and catalyst is mentioned with calcination temperature It rises, catalytic activity can have a distinct increment.
After tested, in carbon of the invention doping amorphous carbon nitride, hydrogen output is under six hours light conditions of 5CCN550 19.5umol is 12 times of the pure carbonitride CN550 hydrogen output obtained under the conditions of.Six hours hydrogen outputs of 2.5CCN600 are reachable Nearly 40umol is nearly 7 times of the synthermal lower pure carbonitride CN600 burnt.Six hours hydrogen outputs of 0.5CCN650 are highest, can It is 3 times of the synthermal lower pure carbonitride CN650 burnt to reach 70 umol, 650 DEG C are calcined, and bombax cotton additive amount is When 0.5%, i.e. 0.5CCN650 catalytic efficiency is best.
In conclusion the present invention provides a kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method, the present invention The photochemical catalyst of the carbon doping amorphous carbon nitride of preparation, can efficiently use visible light, light induced electron and hole to can be real Existing quick separating is simultaneously transferred to interface, and then improves the performance of photodestruciton water preparation renewable energy hydrogen, realizes photocatalysis Hydrogen output reaches more than ten times of increase.Equipment requirement needed for this preparation method is low, and raw material melamine is cheap to be easy It arrives, without reaction units such as valuable processing synthesis device and high temperature and pressure, process is simple, meets the reason of environmentally protective new energy It reads, is suitable for high-volume and synthesizes.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims (7)

1. a kind of preparation method of carbon doping amorphous carbon nitride photochemical catalyst, which is characterized in that use biomass fiber and three The carbon doping amorphous carbon nitride photochemical catalyst is prepared by calcining in poly cyanamid.
2. the preparation method of carbon doping amorphous carbon nitride photochemical catalyst according to claim 1, which is characterized in that described Biomass fiber is bombax cotton or bamboo pulp fiber.
3. the preparation method of carbon doping amorphous carbon nitride photochemical catalyst according to claim 1, which is characterized in that described The mass ratio of biomass fiber and the melamine is 0.005-0.1:1.
4. the preparation method of carbon doping amorphous carbon nitride photochemical catalyst according to claim 1, which is characterized in that by institute It states biomass fiber and the melamine is scattered in organic solvent, then evaporate the organic solvent, then calcined, make It is standby to obtain the carbon doping amorphous carbon nitride photochemical catalyst.
5. the preparation method of carbon doping amorphous carbon nitride photochemical catalyst according to claim 1 to 4, feature exist In the temperature of calcining is 500-700 DEG C.
6. the preparation method of carbon doping amorphous carbon nitride photochemical catalyst according to claim 1 to 4, feature exist In the time of calcining is 2.5-4h.
7. a kind of carbon adulterates amorphous carbon nitride photochemical catalyst, which is characterized in that the carbon adulterates amorphous carbon nitride photocatalysis Agent includes:The amorphous nitridation of biomass fiber after carbonization and the carbon dope on the biomass fiber being grown on after the carbonization Carbon;
The carbon doping amorphous carbon nitride photochemical catalyst is prepared by any preparation method of claim 1-6.
CN201810889288.0A 2018-08-07 2018-08-07 A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method Pending CN108855195A (en)

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Cited By (9)

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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
CN110280289A (en) * 2019-07-05 2019-09-27 上海理工大学 A kind of carbonitride catalysis material and preparation method thereof
CN110813353A (en) * 2019-11-07 2020-02-21 中国石油大学(北京) Carbon-doped mesoporous graphitized carbon nitride nanosphere and preparation method and application thereof
CN110860274A (en) * 2019-11-19 2020-03-06 南京工程学院 Method for preparing adsorption coke by using waste lile pillow
CN111389448A (en) * 2020-05-06 2020-07-10 西南科技大学 Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material
CN111517306A (en) * 2020-04-29 2020-08-11 内蒙古民族大学 Graphene-like/biomass carbon fiber aerogel and preparation method and application thereof
CN112138694A (en) * 2019-06-28 2020-12-29 河北工业大学 Graphite phase carbon nitride/silver/biomass charcoal and preparation method and application thereof
CN114410177A (en) * 2022-02-25 2022-04-29 浙江鱼童新材料股份有限公司 Low-surface-energy marine antifouling paint and preparation method thereof
US11351532B2 (en) * 2018-07-30 2022-06-07 Suzhou University of Science and Technology Photocatalytic composite material and preparation method and application thereof

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US11351532B2 (en) * 2018-07-30 2022-06-07 Suzhou University of Science and Technology Photocatalytic composite material and preparation method and application thereof
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
CN112138694A (en) * 2019-06-28 2020-12-29 河北工业大学 Graphite phase carbon nitride/silver/biomass charcoal and preparation method and application thereof
CN112138694B (en) * 2019-06-28 2023-04-14 河北工业大学 Graphite-phase carbon nitride/silver/biomass charcoal and preparation method and application thereof
CN110280289A (en) * 2019-07-05 2019-09-27 上海理工大学 A kind of carbonitride catalysis material and preparation method thereof
CN110280289B (en) * 2019-07-05 2022-07-29 上海理工大学 Carbon nitride photocatalytic material and preparation method thereof
CN110813353A (en) * 2019-11-07 2020-02-21 中国石油大学(北京) Carbon-doped mesoporous graphitized carbon nitride nanosphere and preparation method and application thereof
CN110860274A (en) * 2019-11-19 2020-03-06 南京工程学院 Method for preparing adsorption coke by using waste lile pillow
CN110860274B (en) * 2019-11-19 2022-06-17 南京工程学院 Method for preparing adsorption coke by using waste lile pillow
CN111517306A (en) * 2020-04-29 2020-08-11 内蒙古民族大学 Graphene-like/biomass carbon fiber aerogel and preparation method and application thereof
CN111389448A (en) * 2020-05-06 2020-07-10 西南科技大学 Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material
CN114410177A (en) * 2022-02-25 2022-04-29 浙江鱼童新材料股份有限公司 Low-surface-energy marine antifouling paint and preparation method thereof

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Application publication date: 20181123