CN108311172B - Nonmetal 1D/2D composite material and preparation method and application thereof - Google Patents
Nonmetal 1D/2D composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 15
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 19
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HPTLEXMXHIALNF-UHFFFAOYSA-L platinum(2+) dichlorate Chemical compound Cl(=O)(=O)[O-].[Pt+2].Cl(=O)(=O)[O-] HPTLEXMXHIALNF-UHFFFAOYSA-L 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- 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 relates to a nonmetal 1D/2D composite material and a preparation method and application thereof, belonging to the fields of preparation of nanometer composite materials and clean energy; the invention firstly prepares g-C3N4Standby; then g-C is prepared by adjusting the reaction conditions and the ratio of reactants3N4The invention relates to a PEDOT photocatalyst, which is synthesized into PEDOT/g-C with a nonmetal 1D/2D composite structure by a hydrothermal method3N4The photocatalyst can be used for photocatalytic decomposition of water under visible light to prepare hydrogen; g-C obtained3N4The PEDOT sample has a 1D/2D composite structure, and the hydrogen yield can reach 3636.6 mu mol g‑1Is pure g-C3N45.5 times of that of the above-mentioned compound, which indicates that g-C has a 1D/2D composite structure3N4The PEDOT composite photocatalyst has great potential in the field of hydrogen production through photocatalytic water decomposition.
Description
Technical Field
The invention relates to a nonmetal 1D/2D composite material and a preparation method and application thereof, belonging to the fields of preparation of nanometer composite materials and clean energy.
Background
With the continuous development of human society, the energy demand is expanding, which results in a large amount of fossil fuels being burned and causes serious harm to the ecological environment. However, conventional fossil fuels will be depleted in the near future, which may cause more serious energy shortage problems. And hydrogen is used as a clean energy, and compared with the traditional energy, the hydrogen has the advantages of rich and cheap raw materials, no toxicity, no harm, high productivity and the like, but the hydrogen naturally existing on the earth is very little. Therefore, the semiconductor-catalyzed photolysis of water to produce hydrogen is widely concerned by researchers.
In 1972, a research on water decomposition by using titanium dioxide as a material was first reported by Japanese scientist Fujishima, and a road is indicated for solving the energy crisis. Therefore, titanium dioxide has become a photocatalytic material that has been studied in large quantities. But the larger forbidden band width makes TiO2(3.2 ev) cannot be the most ideal and efficient catalyst for water photolysis. Thus, over the past decades, more photolytic water catalysts with visible light activity have been discovered and studied, e.g., WO3, BiVO4SiC, CdS, etc. Compared with the metal semiconductor photocatalysts, the non-metal photocatalyst has low manufacturing cost, small harm to the environment and wider application prospect. 2008 Wangchen et al propose g-C in Nature Material journal3N4The photocatalyst can be used as a nonmetal photocatalyst to photolyze water under the condition of visible light to produce hydrogen, and the discovery initiates researchers to carry out G-C3N4The study of (2) is hot. g-C3N4As an organic semiconductor polymer, the corresponding band gap width (~ 2.7.7 ev) and the proper conduction band valence band position endow the organic semiconductor polymer with higher oxidation and reduction capability, so that the organic semiconductor polymer has wide application prospect in the field of photocatalysis.
For monomers g-C3N4The photocatalyst, although it has many advantages such as visible light photocatalytic activity, good acid and alkali corrosion resistance, and excellent chemical and thermal stability. But g-C3N4The photocatalyst has high photo-generated electron-hole recombination degree, and the application of the photocatalyst in the field of photocatalysis is limited. Therefore, more and more researchers are working on g-C3N4And (4) modifying. Common modification methods can be broadly divided into three major categories: morphology control, chemical doping and semiconductor compounding. Wherein the semiconductor is compounded by using twoOne or more semiconductors with different energy band widths or special frameworks are synthesized into the composite photocatalytic material, so that the composite photocatalytic material becomes a composite system with multi-aspect performance. At present, the selected composite semiconductor materials mainly comprise transition metal oxides, transition metal sulfides, noble metal materials and the like, but the metal materials are expensive in manufacturing cost and extremely easy to cause metal pollution, so that secondary damage is caused to the ecological environment. The conductive polymer not only can not cause secondary pollution, but also has the performance of semiconductor materials, so that the proper conductive polymer and g-C are selected3N4Compounding is a feasible means with wide prospect. A series of useful conductive polymers have been developed to date: polyaniline, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene-ethylene, and the like. However, the sum of g-C has been reported so far3N4Only simpler conductive polymers such as polyaniline and polypyrrole are compounded, and the influence of the morphology and the structure of the conductive polymer on the photocatalytic performance is not mentioned in reported documents.
Disclosure of Invention
In order to improve the hydrogen production performance of the photocatalyst by decomposing water, the invention aims to provide the g-C with the visible light activity and the nonmetal 1D/2D composite structure3N4The composite material has simple preparation process, good visible light activity and high hydrogen production performance by photolysis of water.
To increase g-C3N4For the utilization rate of sunlight, the invention adopts a conductive polymer with photocatalytic activity, namely PEDOT (poly 3, 4-ethylenedioxythiophene) and g-C3N4A1D/2D composite structure is constructed, and the utilization rate of sunlight and the performance of a photocatalyst are improved.
The invention firstly provides a g-C3N4PEDOT composite material in the form of a rod
g-C compounded into flakes3N4The non-metal 1D/2D composite structure is formed on the surface.
The invention also provides a preparation method of the g-C3N4/PEDOT composite materialThe invention adopts a hydrothermal method to construct g-C with a 1D/2D structure3N4The PEDOT composite material is prepared according to the following steps:
(1) preparation of g-C3N4Photocatalyst:
weighing urea, drying in an oven at 80 deg.C for 24 h, grinding and loading into a crucible, adding a lid, and heating in a muffle furnace at 2.5 deg.C for 2.5 min-1The temperature rising rate is that the mixture is heated from room temperature to 550 ℃ and calcined for 4 hours; taken out and then used for 1 mol L-1The solution was washed with nitric acid overnight, filtered with suction, washed with distilled water 5 ~ 8 times to neutrality and dried in a vacuum oven overnight.
(2) Preparation of g-C3N4PEDOT composite material:
a certain amount of g-C3N4And FeCl3·6H2Dispersing O in deionized water, performing ultrasonic treatment for 10 ~ 30min, adding EDOT (3, 4-ethylenedioxythiophene) in a certain proportion, placing the mixed solution in a reaction kettle, placing the sealed reaction kettle in a drying oven at a certain temperature for reaction, cooling to room temperature after the reaction is finished, performing suction filtration, washing and vacuum drying on the product to obtain g-C3N4Samples of PEDOT.
The g to C3N4、FeCl3·6H2The dosage ratio of O to deionized water is 0.1 ~ 1.0.0 g, 0.2 ~ 1.2.2 g and 20 ~ 70 mL.
The EDOT and g-C3N4The dosage of the medicine is 5 ~ 50 muL to 0.1 ~ 1.0.0 g.
The vacuum drying temperature is 60 ~ 100 ℃.
The reaction temperature is 80 ~ 150 ℃, and the reaction time is 6 ~ 12 h.
The g to C3N4In a PEDOT composite photocatalyst sample, the mass of EDOT accounts for g-C3N40.5% ~ 10% by mass.
In the invention, g-C is subjected to means such as X-ray diffraction (XRD), Transmission Electron Microscope (TEM), Fourier infrared spectrometer, ultraviolet-visible absorption spectrometer and the like3N4Characterization was performed on a/PEDOT photocatalyst. Compared with the prior art, the invention has the beneficial effects ofThe method comprises the following aspects:
(1) the invention has the advantages of rich raw material sources, low price, cleanness and no pollution.
(2) Nonmetal g-C prepared by the invention3N4The PEDOT composite photocatalyst has a 1D/2D composite structure and is mixed with pure g-C3N4Compared with the prior art, the catalyst has higher performance of producing hydrogen by photocatalytic water decomposition.
(3) The preparation method is simple and easy to implement, short in flow, easy to control in operation and mild in reaction conditions.
In summary, in the present invention, the EDOT monomer is reacted at g-C under high temperature and high pressure by hydrothermal method3N4The surface is polymerized to form PEDOT with a 1D structure, and g-C with a nonmetal 1D/2D composite structure is successfully constructed3N4PEDOT photocatalyst, characterization showed pure g-C3N4After PEDOT complexation, g-C was not altered3N4The inherent sheet structure characteristic expands the visible light response range and improves the photocatalytic activity and stability. The hydrothermal method adopted by the invention has the advantages that the shape of the PEDOT can be regulated and controlled to be 1D, the synthesized material has good stability and firm compounding, and the synthesized nonmetal g-C with visible light activity3N4The composite photocatalyst of the PEDOT has a 1D/2D composite structure, is low in cost, does not cause metal pollution, and has excellent hydrogen production performance by photolysis of water. The influence of the morphology control on the performance of the composite material is not negligible, but the factor is not mentioned in the same series of composite materials at present, so that the easily prepared 1D rod-shaped PEDOT is selected to be compounded with the typical 2D sheet-shaped g-C3N4 to construct a 1D/2D composite structure.
Drawings
FIG. 1 shows g-C3N4(a) And g-C3N4XRD spectrum of/PEDOT (b).
FIG. 2 shows g-C3N4(a) And g-C3N4TEM image of/PEDOT (b).
FIG. 3 is g-C3N4(a) And g-C3N4Fourier Infrared of/PEDOT (b)The spectrogram and the right image are partial enlarged images of the left image.
FIG. 4 shows g-C3N4(a) And g-C3N4UV-Vis Spectrum of/PEDOT (b).
FIG. 5 shows PEDOT/g-C with different compounding ratios under visible light3N4Histogram of hydrogen production.
FIG. 6 is 3wt% g-C3N4The cycle use effect of the/PEDOT is shown in the figure, and 4 lines respectively represent the results of continuous 4-cycle hydrogen production.
Detailed Description
In order to clarify the technical solution and the technical object of the present invention, the following embodiments are given to further describe the present invention.
A wt% g-C in the invention3N4the/PEDOT composite material refers to the composite material, wherein the mass of EDOT accounts for g-C3N4A% by mass.
Example 1: preparation of g-C3N4Photocatalyst and process for producing the same
(1) Weighing urea, drying in an oven at 80 deg.C for 24 h, grinding and loading into a crucible, adding a lid, and heating in a muffle furnace at 2.5 deg.C for 2.5 min-1The temperature of the mixture is increased from room temperature to 550 ℃, and the mixture is calcined for 4 hours.
(2) Taken out and then used for 1 mol L-1The solution was washed with nitric acid overnight, filtered with suction, washed with distilled water 5 ~ 8 times to neutrality and dried in a vacuum oven overnight.
Example 2: preparation of 1 wt% g-C3N4PEDOT composite material
(1) Accurately weigh 0.9 g g-C3N4And 0.2 g FeCl3·6H2O was dissolved in 50 mL deionized water and then sonicated for 20 min.
(2) Then 6.7. mu.L of EDOT was added and the mixture was placed in the reaction vessel.
(3) And finally, placing the sealed reaction kettle in a 100 ℃ oven for reaction for 10 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4Samples of PEDOT.
Example 3: preparation of 3wt% g-C3N4PEDOT composite material
(1) Accurately weigh 0.9 g g-C3N4And 0.2 g FeCl3·6H2O was dissolved in 50 mL deionized water and then sonicated for 20 min.
(2) Then 20.1. mu.L of EDOT was added and the mixture was placed in a reaction vessel.
(3) And finally, placing the sealed reaction kettle in a 100 ℃ oven for reaction for 10 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4Samples of PEDOT.
FIG. 1 shows g-C of the present embodiment3N4And g-C3N4XRD spectrogram of/PEDOT, after compounding,
g-C3N4there was little change in the XRD diffraction peak of PEDOT and other substances, probably because the content of PEDOT relative to g-C3N4 was too low.
FIG. 2 shows pure g-C of this example3N4And g-C3N4TEM photograph of/PEDOT, it can be seen that the rod-like shape is
PEDOT of (D) successfully incorporated into sheet-like g-C3N4And constructing a typical 1D/2D composite structure on the surface.
FIG. 3 shows pure g-C of this example3N4And g-C3N4IR spectrum of/PEDOT, g-C3N4/PEDOT
All g-C can be observed in the composite photocatalyst3N4And relative to g-C3N4All absorption peaks were blue-shifted, indicating that the intensity of the C = N and C-N bonds is greater than g-C3N4Is described in g-C3N4And PEDOT, there is a weaker covalent bond interaction. And g-C3N4PEDOT on 1558-1And 1047-12 new absorption peaks appear, which are Cα=CβThe stretching vibration peak and the C-O-C stretching vibration peak further prove that PEDOT is successfully compounded to g-C3N4A surface.
FIG. 4 shows g-C of this example3N4And g-C3N4UV-Vis Spectrum of/PEDOT, wherein
g-C3N4Blue-shifted absorption edge of/PEDOT, probably EDOT in g-C3N4Polymerization of the surface to give g-C3N4The overall conjugation degree of the/PEDOT composite material is improved. At the same time g-C3N4PEDOT has a higher intensity absorption peak at 500 nm, and g-C is improved3N4The absorption of visible light improves the photocatalytic activity.
Example 4: preparation of 5 wt% g-C3N4PEDOT composite material
(1) Accurately weigh 0.9 g g-C3N4And 0.2 g FeCl3·6H2O was dissolved in 50 mL deionized water and then sonicated for 20 min.
(2) Then 33.6. mu.L of EDOT were added and the mixture was placed in the reaction vessel.
(3) And finally, placing the sealed reaction kettle in a 100 ℃ oven for reaction for 10 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4Samples of PEDOT.
Example 5: preparation of 7 wt% g-C3N4PEDOT composite material
(1) Accurately weigh 0.9 g g-C3N4And 0.2 g FeCl3·6H2O was dissolved in 50 mL deionized water and then sonicated for 20 min.
(2) Then 47.0. mu.L of EDOT was added and the mixture was placed in a reaction vessel.
(3) And finally, placing the sealed reaction kettle in a 100 ℃ oven for reaction for 10 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4PEDOT samples。
Example 5: preparation of 6.7 wt% g-C3N4PEDOT composite material
(1) Accurately weigh 0.1 g g-C3N4And 0.1 g FeCl3·6H2O was dissolved in 20 mL deionized water and then sonicated for 20 min.
(2) Then 5. mu.L of EDOT was added and the mixture was placed in a reaction vessel.
(3) And finally, placing the sealed reaction kettle in an oven at 80 ℃ for reaction for 12 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4Samples of PEDOT.
Example 5: preparation of 6.7 wt% g-C3N4PEDOT composite material
(1) Accurately weigh 1 g g-C3N4And 1.2g FeCl3·6H2O was dissolved in 70 mL deionized water and then sonicated for 20 min.
(2) Then 50. mu.L of EDOT was added and the mixture was placed in a reaction vessel.
(3) And finally, placing the sealed reaction kettle in a 150 ℃ oven for reaction for 6 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the product to obtain g-C3N4Samples of PEDOT.
Example 6: g-C3N4Performance testing of/PEDOT composite materials
20% triethanolamine was used as a hole trapping agent, a 270 w xenon lamp was used as a light source, and a 420 nm filter was used. The specific operation is as follows:
(1) 50 mg of the sample was dispersed in 50 mL of triethanolamine solution (20%), sonicated for 10 min,
after dispersion was homogeneous, 1.5 mL of platinum chlorate solution (1 mg/mL) was added.
(2) And pouring the mixed solution into a reactor, exhausting gas for 20 min by using argon, turning on a lamp to perform an illumination reaction, and calculating the corresponding hydrogen content according to the peak area obtained by gas chromatography.
The results are showng-C showing non-metal 1D/2D composite structure prepared by hydrothermal method3N4The PEDOT composite photocatalyst has higher performance of hydrogen production by photocatalytic water decomposition. Furthermore, 3% by weight of g-C3N4The PEDOT photocatalyst has the best performance of decomposing water to produce hydrogen by photocatalysis, and the hydrogen production can reach 3636.6 mu mol g-1Is pure g-C3N45.5 times of the total weight of the powder.
FIG. 5 is g-C3N4With 1 wt%, 3wt%, 5 wt%, 7 wt% of g-C3N4Hydrogen production of/PEDOT
Energy and FIG. 6 is 3wt% g-C3N4The recycling effect of PEDOT can be seen as 3wt% g-C after hydrothermal treatment3N4The hydrogen production performance of the/PEDOT is pure g-C3N4 5.5 times of the total amount of the active component, has good stability, still has high photocatalytic activity after 5 cycles, and obviously improves g-C by a 1D/2D composite structure3N4Indicating g-C having a 1D/2D composite structure3N4The PEDOT composite photocatalyst has great potential in the field of hydrogen production through photocatalytic water decomposition.
Claims (6)
1. g-C3N4The preparation method of the PEDOT composite material is characterized by comprising the following steps:
a certain amount of g-C3N4And FeCl3·6H2Dispersing O in deionized water and ultrasonically dispersing, then adding a certain proportion of EDOT (3, 4-ethylenedioxythiophene), placing the mixed solution in a reaction kettle, finally placing the sealed reaction kettle in a drying oven at a certain temperature for reaction, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing and vacuum drying on the product to obtain g-C3N4A PEDOT sample;
the g to C3N4、FeCl3·6H2The dosage ratio of O to deionized water is 0.1 ~ 1.0.0 g to 0.2 ~ 1.2.2 g to 20 ~ 70 mL, the EDOT and g-C3N4The dosage of the compound is 5 ~ 50 mu L, 0.1 ~ 1.0.0 g, the reaction temperature in an oven is 80 ~ 150 ℃, and the reaction time is 6 ~ 12 h;
the g to C3N4PEDOT composite material in rod shape compounded into sheet-shaped g-C3N4The non-metal 1D/2D composite structure is formed on the surface.
2. A g-C according to claim 13N4The preparation method of the PEDOT composite material is characterized in that the ultrasonic time is 10-30 min.
3. A g-C according to claim 13N4The preparation method of the PEDOT composite material is characterized in that the vacuum drying temperature is 60 ~ 100 ℃.
4. A g-C according to claim 13N4Method for producing a PEDOT composite material, characterized in that g-C is obtained3N4In a PEDOT composite photocatalyst sample, the mass of EDOT accounts for g-C3N40.5% ~ 10% by mass.
5. g-C prepared by the method of any one of claims 1 to 43N4the/PEDOT composite material is characterized in that the material is prepared by compounding rod-shaped PEDOT to sheet-shaped g-C3N4A nonmetal 1D/2D composite structure is formed on the surface; the g to C3N4In the PEDOT composite material, the mass of EDOT accounts for g-C3N40.5% ~ 10% by mass.
6. g-C as claimed in claim 53N4The PEDOT composite material is used for preparing hydrogen by photocatalytic water decomposition.
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