CN103752334B - Graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of ionic liquid - Google Patents
Graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of ionic liquid Download PDFInfo
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- CN103752334B CN103752334B CN201410038958.XA CN201410038958A CN103752334B CN 103752334 B CN103752334 B CN 103752334B CN 201410038958 A CN201410038958 A CN 201410038958A CN 103752334 B CN103752334 B CN 103752334B
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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
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- 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 discloses a preparation method and application of a graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of ionic liquid and belongs to the technical field of material preparation and photocatalysis. A graphite phase carbon nitride nanosheet material is formed by using room-temperature ionic liquid of urea and dialkyl imidazolium tetrafluoroborate as a precursor through high-temperature co-polymerization. The graphite phase carbon nitride prepared by the preparation method has a low-dimensional nanosheet layer microstructure and a suitable forbidden bandwidth and shows more efficient photocatalytic hydrogen production performance than that of conventional body phase carbon nitride under the visible light. The graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of the ionic liquid is simple in synthetic process, is low in cost, has high photocatalytic efficiency, accords with the actual production requirement and has a wide application prospect in the field of photocatalysis.
Description
Technical field
The invention belongs to material preparation and light-catalysed technical field, be specifically related to the preparation method and application that a kind of ionic liquid promotes synthetic graphite phase carbon nitride nanometer sheet visible light catalyst.
Background technology
Hydrogen is a kind of clean type energy source body, and photocatalysis Decomposition aquatic products hydrogen is a kind of method with the solution energy problem of high evaluation.The core of photocatalysis research finds the photochemical catalyst of function admirable, so the exploitation of high efficiency photocatalyst is the core topic of photocatalysis research.But the photochemical catalyst of research at present also exists the problems such as solar energy utilization ratio is low, easy in inactivation, use cost are high mostly, greatly constrains the application of photocatalysis in industrial production.Therefore the core challenge that exploitation is efficient, stable, nontoxic, cheap visible light catalyst is this field.
In recent years, Wang etc. by the organic polymer semiconductor of the not containing metal composition of chemical constitution exceptional stability, graphite phase carbon nitride (g-C
3n
4), be incorporated into photocatalysis field and carry out photodissociation aquatic products hydrogen, produce oxygen, evoked the great interest of people, made the research of polymer semiconductor's photochemical catalyst enter a fast-developing period (Nat. Mater. 2009,8,76-80).But, g-C
3n
4due to the intrinsic propesties of its organic polymer, also there are some problems as photochemical catalyst, exciton binding energy that is as little in specific area, that produce photo-generated carrier is high, photo-generate electron-hole compound is serious, quantum efficiency is low and energy gap is comparatively large and effectively can not utilize sunshine etc., serious its large-scale promotion application in the energy, environmental photocatlytsis field of restriction.For the sciences problems of these objective realities, researcher both domestic and external is around g-C
3n
4, carry out a large amount of research work.
Graphite phase carbon nitride (g-C
3n
4) kind of the photocatalysis performance of semiconductor and predecessor, synthetic method and preparation process be closely related.Because the difference of the improvement of the kind of predecessor, preparation technology (calcining heat, temperature retention time) and preparation method effectively can optimize g-C
3n
4semiconductor energy band structure, nanostructured and surface topography, thus significantly affect its photocatalysis performance.
Ionic liquid is made up of the anion of large cation and weak coordination, has special physicochemical properties, such as fixedness, incombustibility and heat endurance etc.This functional material is widely used as solvent, not long ago, is also used as soft template to synthesize the material of various nanostructured.Have report, ionic liquid promotes that the nitride porous material with carbon element of Heteroatom doping is prepared in two paracyanogen ammonia thermal polymerizations, and can effective Visible Light Induced Photocatalytic dyestuff.But the industrial chemicals adopting this cheapness of urea is carbon nitride precursor, is incorporated in reaction system by ionic liquid and promotes g-C
3n
4the research work of the synthesis of nanometer sheet, have not been reported.Therefore, we utilize urea for raw material, and ionic liquid is as soft template and doping auxiliary agent, successfully obtained graphite phase carbon nitride base nanometer sheet visible light catalyst.Experiment proves, ionic liquid promotes that the graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst of synthesis is a kind of photochemical catalyst of efficient visible photocatalysis aquatic products hydrogen.
Summary of the invention
A kind of ionic liquid is the object of the present invention is to provide to promote the preparation method and application of synthetic graphite phase carbon nitride nanometer sheet visible light catalyst.The photochemical catalyst of the porous nano chip architecture of Heteroatom doping prepared by the present invention, can not only accelerate the migration of photo-generated carrier and can promote mass transport process, realizes the aquatic products of visible ray photodissociation efficiently hydrogen.Present invention process is simple, and with low cost, catalytic efficiency is high, and realistic Production requirement, has broad application prospects in photocatalysis field.
For achieving the above object, the present invention adopts following technical scheme:
Graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst is the semiconductive organic polymer of the porous nano lamellar structure with Heteroatom doping, and specific area is 60 ~ 100 m
2/ g, absorbs visible ray, and has the performance of good photochemical catalyzing hydrogen making, can be used as a kind of photochemical catalyst efficiently.
The method preparing graphite phase carbon nitride visible light catalyst described above be with urea and ionic liquid for predecessor, by high-temperature hot condensation, namely obtain graphite phase carbon nitride nanometer sheet.Described preparation method comprises the following steps: mass ratio is that the urea of 100:1 ~ 15 and different ionic liquid (ionic liquid at room temperature that dialkylimidazolium cation and tetrafluoro boric acid anion are formed) are dissolved in water by (1), stirring at room temperature 2 ~ 12h, evaporate to dryness, grinding; (2) by pressed powder 500 ~ 600 DEG C of heat treatment 1 ~ 4h in Muffle furnace, obtained graphite phase carbon nitride nanosheet photocatalyst.
Described graphite phase carbon nitride nanometer sheet catalyst application decomposition water hydrogen making under visible ray.
Remarkable advantage of the present invention is:
(1) ionic liquid is incorporated in the modification of nanoscale twins carbonitride as soft template and adulterant by the present invention first, increases specific area, promotes the transport efficiency of mass transport process and photo-generated carrier simultaneously.
(2) synthetic graphite phase carbon nitride nanometer sheet of the present invention, its advantage is that preparation technology is simple, and energy consumption is low, catalyst stabilization, nontoxic, be easy to reclaim, reusable edible, realistic need of production.
(3) synthetic graphite phase carbon nitride nanometer sheet of the present invention, the ionic liquid wherein with modifying function is selective in extensive range, has good Modulatory character and universality.
(4) ionic liquid is promoted that the graphite phase carbon nitride nanometer sheet of synthesis is applied to photocatalysis hydrogen making by the present invention first, finds that it has efficient visible ray photocatalytic water H2-producing capacity.Can carry out separating treatment easily in light-catalyzed reaction system, photochemical catalyst renewable is strong, and recycling rate of waterused is high, has very high practical value and application prospect widely.
Accompanying drawing explanation
Fig. 1 is that the ionic liquid of embodiment 2 gained promotes that the X-ray powder diffraction XRD of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.
Fig. 2 is the Fourier transform infrared FT-IR spectrogram of the graphite phase carbon nitride nanometer sheet a of the ionic liquid promotion synthesis of embodiment 2 gained.
Fig. 3 is that the ionic liquid of embodiment 2 gained promotes that the transmission electron microscope TEM of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.
Fig. 4 is the atomic force microscope figure of the graphite phase carbon nitride nanometer sheet a of the ionic liquid promotion synthesis of embodiment 2 gained.
Fig. 5 is that the ionic liquid of embodiment 5 gained promotes that the x-ray photoelectron power spectrum XPS of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.
Fig. 6 is that the ionic liquid of embodiment 2 gained promotes that the UV-vis DRS DRS of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.
Fig. 7 is that the ionic liquid of embodiment 2 gained promotes that the graphite phase carbon nitride nanometer sheet a of synthesis and traditional body phase carbon nitride b carries out the Performance comparision figure of visible light catalytic decomposition water hydrogen making.
Detailed description of the invention
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1
Be urea and the 1-ethyl-3-methylimidazole tetrafluoroborate (EmimBF of 50:1 by mass ratio
4) be dissolved in water, stirring at room temperature 12h, evaporate to dryness, grinding.By pressed powder 550 DEG C of heat treatment 2h in Muffle furnace, obtained ionic liquid promotes the graphite phase carbon nitride nanometer sheet of synthesis.
embodiment 2
Be urea and the 1-butyl-3-methyl imidazolium tetrafluoroborate (BmimBF of 45:1 by mass ratio
4) be dissolved in water, stirring at room temperature 12h, evaporate to dryness, grinding.By pressed powder 550 DEG C of heat treatment 2h in Muffle furnace, obtained ionic liquid promotes the graphite phase carbon nitride nanometer sheet of synthesis.
embodiment 3
Be urea and the 1-hexyl-3-methyl imidazolium tetrafluoroborate (HmimBF of 40:1 by mass ratio
4) be dissolved in water, stirring at room temperature 12h, evaporate to dryness, grinding.By pressed powder 550 DEG C of heat treatment 2h in Muffle furnace, obtained ionic liquid promotes the graphite phase carbon nitride nanometer sheet of synthesis.
embodiment 4
Be urea and the 1-octyl group-3-methyl imidazolium tetrafluoroborate (OmimBF of 35:1 by mass ratio
4) be dissolved in water, stirring at room temperature 12h, evaporate to dryness, grinding.By pressed powder 550 DEG C of heat treatment 2h in Muffle furnace, obtained ionic liquid promotes the graphite phase carbon nitride nanometer sheet of synthesis.
embodiment 5
Be urea and the 1-butyl-3-methyl imidazolium tetrafluoroborate (BmimBF of 9:1 by mass ratio
4) be dissolved in water, stirring at room temperature 12h, evaporate to dryness, grinding.By pressed powder 550 DEG C of heat treatment 2h in Muffle furnace, obtained ionic liquid promotes the graphite phase carbon nitride nanometer sheet of synthesis.
Performance test
Fig. 1 is that the ionic liquid of embodiment 2 gained promotes that the X-ray powder diffraction XRD of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.Can find 13.0 from figure
owith 27.5
oplace's appearance two significantly belongs to the XRD diffraction maximum of graphite phase carbon nitride (100) and (002) crystal face, confirms that the product of preparation is graphite phase carbon nitride.
Fig. 2 is the Fourier transform infrared FT-IR spectrogram of the graphite phase carbon nitride nanometer sheet a of the ionic liquid promotion synthesis of embodiment 2 gained.As can be seen from the figure gained sample has the characteristic peak of graphite phase carbon nitride material, i.e. 800 cm
-1with 1200 ~ 1600 cm
-1interval, they correspond respectively to the breathing vibration of seven piperazine rings and the stretching vibration of armaticity CN heterocycle.
Fig. 3 is that the ionic liquid of embodiment 2 gained promotes that the transmission electron microscope TEM of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.The product prepared as we can see from the figure is nanoporous flake structure.
Fig. 4 is the atomic force microscope figure of the graphite phase carbon nitride nanometer sheet a of the ionic liquid promotion synthesis of embodiment 2 gained.Can find that from figure the product prepared has nanoscale twins pattern, the general 2 ~ 5nm of lamellar spacing.
Fig. 5 is that the ionic liquid of embodiment 5 gained promotes that the x-ray photoelectron power spectrum XPS of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.As can be seen from the figure gained sample comprises boron, fluorine hetero atom, and can know that boron, fluorine atom are successfully mixed carbonitride matrix from their combination.
Fig. 6 is that the ionic liquid of embodiment 2 gained promotes that the UV-vis DRS DRS of the graphite phase carbon nitride nanometer sheet a of synthesis schemes.Can find that from figure gained sample has obvious and precipitous absorption band edge at about 440 nm, corresponding energy gap is 2.82 eV.
Fig. 7 is that the ionic liquid of embodiment 2 gained promotes the graphite phase carbon nitride nanometer sheet a of synthesis and the Performance comparision figure of body phase carbon nitride b photochemical catalyzing hydrogen making.50mg catalyst, 10 vol. % triethanolamines (hole sacrifice agent), 3 wt. % Pt(co-catalysts), in the water of 100 milliliters, react in upper illuminated reactor.Can find that from figure the hydrogen-producing speed of the product (xenon lamp 300W, filter plate λ > 420 nm) under visible light prepared reaches 130 μm of ol/h, improve 3.7 times compared with body phase carbon nitride (35 μm of ol/h).
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. ionic liquid promotes a method for synthetic graphite phase carbon nitride nanometer sheet visible light catalyst, it is characterized in that: comprise the following steps:
(1) by mass ratio be the urea of 100:1 ~ 15 and ion liquid dissolving in water, stirring at room temperature 2 ~ 12h, evaporate to dryness, grinds to obtain pressed powder;
(2) by the pressed powder of step (1) 500 ~ 600 DEG C of heat treatment 1 ~ 4h in Muffle furnace, obtained graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst, has the porous nano chip architecture of Heteroatom doping;
Described ionic liquid is the ionic liquid at room temperature that dialkylimidazolium cation and tetrafluoro boric acid anion are formed;
Described graphite phase carbon nitride nanometer sheet is applied to visible light catalytic decomposition water hydrogen making.
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| CN109761207B (en) * | 2019-01-30 | 2022-06-21 | 江苏大学 | 3D graphite phase carbon nitride material and preparation method thereof |
| CN110052280A (en) * | 2019-03-26 | 2019-07-26 | 中国科学院生态环境研究中心 | A kind of graphite phase carbon nitride material of polyacid covalent modification and its preparation method and application |
| CN110124737A (en) * | 2019-05-16 | 2019-08-16 | 上海应用技术大学 | The preparation method of composite visible light catalyst ZIF-8@Zn/g- carbonitride |
| CN112167707B (en) * | 2020-09-28 | 2022-08-26 | 江苏中烟工业有限责任公司 | Filter tip capable of selectively reducing ammonia in cigarette smoke and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214878A (en) * | 2013-04-02 | 2013-07-24 | 江苏大学 | Preparation method of graphite type carbon nitride-ionic liquid composite material |
| CN103272639A (en) * | 2013-06-09 | 2013-09-04 | 福州大学 | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst |
-
2014
- 2014-01-27 CN CN201410038958.XA patent/CN103752334B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214878A (en) * | 2013-04-02 | 2013-07-24 | 江苏大学 | Preparation method of graphite type carbon nitride-ionic liquid composite material |
| CN103272639A (en) * | 2013-06-09 | 2013-09-04 | 福州大学 | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| Phosphorus-doped carbon nitride solid: enhanced electrical conductivity and photocurrent generation;Yuanjian Zhang,et al;《Journal of the American Chemical Society》;20100416;第132卷(第18期);第6294页左栏第4段、Figure 2a、Supporting Information S1 * |
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