CN103801354B - A kind of graphite phase carbon nitride hollow ball visible light catalyst of after annealing process - Google Patents

A kind of graphite phase carbon nitride hollow ball visible light catalyst of after annealing process Download PDF

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CN103801354B
CN103801354B CN201410089581.0A CN201410089581A CN103801354B CN 103801354 B CN103801354 B CN 103801354B CN 201410089581 A CN201410089581 A CN 201410089581A CN 103801354 B CN103801354 B CN 103801354B
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hollow ball
carbon nitride
phase carbon
graphite phase
annealing process
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CN103801354A (en
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王心晨
郑丹丹
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Fuzhou University
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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

Graphite phase carbon nitride hollow ball visible light catalyst that the invention discloses a kind of after annealing process and its preparation method and application, belongs to material preparation and light-catalysed technical field.After annealing, as a kind of important post-processing technology, can be eliminated defect that carbonitride hollow ball introduces in preparation process, improves crystalline quality and improve the performance of sample.The graphite phase carbon nitride hollow ball of after annealing modification prepared by the present invention is still keeping the pattern of hollow ball and even particle size distribution after high-temperature process, compared with conventional bulk phase carbon nitride, effective increasing specific surface area thus improve its performance of decomposing aquatic products hydrogen.Synthesis technique of the present invention is simple, and with low cost, catalytic efficiency is high, and realistic Production requirement, has broad application prospects in photocatalysis field.

Description

A kind of graphite phase carbon nitride hollow ball visible light catalyst of after annealing process
Technical field
The invention belongs to material preparation and light-catalysed technical field, graphite phase carbon nitride hollow ball visible light catalyst being specifically related to a kind of after annealing process and its preparation method and application.
Background technology
Hollow ball nanostructured is because the structure of its uniqueness is in Science and Technology field all very attractive.These hollow ball nanostructureds have unique advantage, as: the bearing capacity that density is low, specific area is large, excellent and Thief zone performance etc., can be applicable to the applications such as the encapsulation of medicine and gene delivery, Chu Qing, catalysis and cosmetics and coating as a kind of multi-functional material.In recent years, TiO 2, SnO 2, CdS, CdTe, Cu 2the semiconductor hollow ball nanostructureds such as O by as photochemical catalyst for decomposing aquatic products hydrogen field.But because they contain metallic element, solar energy utilization ratio is low and only has ultraviolet light corresponding, simultaneously the problem such as toxicity large, self is unstable, easy generation photoetch seriously constrains its application in industrial production.
At present, graphite phase carbon nitride semiconductive polymer material is as a kind of not containing metal, the extensive concern that efficient, stable, nontoxic visible light catalyst material is subject to scientist and researchers.Researcher utilizes hard template method successfully to prepare hollow ball-shape carbonitride (NatureCommunications2012,3,1139).It not only has the unique advantage of hollow ball nanostructured, also has the advantage of carbon nitride material concurrently simultaneously.But this material polymerization of being synthesized by high temperature thermopolymerization method not exclusively, there is a large amount of defects in material.These defects may become the right complex centre of photo-generate electron-hole, thus reduce the quantum efficiency of light-catalyzed reaction.
After annealing method is incorporated into the research work of carbonitride hollow ball, have not been reported.Regulated and controled by the structure of after annealing method to carbonitride hollow ball, can eliminate introduce in Material growth process defect, improve crystalline quality and improve the performance (JournalofCatalysis2008,255,59) of sample.Carbonitride hollow ball after the process of high temperature after annealing still keeps the pattern of hollow ball, increase specific area simultaneously, reduce semiconductor band gap width, promote that photo-generated carrier is separated and migration, improve solar energy utilization ratio, have wide practical use in photocatalysis field.Experiment proves, the carbonitride hollow ball visible light catalyst of after annealing process is a kind of photochemical catalyst of efficient visible photocatalysis aquatic products hydrogen.
Summary of the invention
Graphite phase carbon nitride hollow ball visible light catalyst that the object of the present invention is to provide a kind of after annealing process and its preparation method and application.Photochemical catalyst prepared by the present invention still can keep its hollow ball pattern after after annealing process, substantially increase its specific area, thus have more avtive spot, photo-generated carrier separation fast, transfer ability, visible photocatalysis water efficiently can be realized and produce 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:
The graphite phase carbon nitride hollow ball visible light catalyst of after annealing process is a semi-conducting polymer with hollow ball pattern, and chemical formula is C 3n 4, and be class graphite-phase, specific area is 80 ~ 280m 2/ g, absorb visible ray, light absorption band edge at 420 ~ 700nm, and has the performance of good photochemical catalyzing hydrogen making, can be used as a kind of photochemical catalyst efficiently.
The method preparing the graphite phase carbon nitride hollow ball visible light catalyst of after annealing process as above is, use hard template method by removing template after high-temperature hot condensation, then the graphite phase carbon nitride hollow ball after annealing 5h under air atmosphere different temperatures that will obtain.Described preparation method comprises the following steps: (1) synthesis different-grain diameter size and the thick silica spheres (St bersilicasol) of different shell.(2) 3g cyanamide is dissolved in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, and 80 DEG C add thermal agitation, centrifugal, dries, obtains white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.(3) 8mol/LNH is joined 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing, 80 DEG C of vacuum drying, obtain carbonitride hollow ball.(4) by hollow ball carbonitride after annealing 5h at 300-550 DEG C in air atmosphere.
The graphite phase carbon nitride hollow ball visible light catalyst of described combined polymerization modification is applied to decomposition water hydrogen making under visible ray.
Remarkable advantage of the present invention is:
(1) means of after annealing are incorporated into the modification of hollow ball carbonitride by the present invention first, can eliminate defect, raising crystalline quality that carbonitride hollow ball is introduced in preparation process, increase its specific area simultaneously.
(2) the graphite phase carbon nitride hollow ball of after annealing process of the present invention's synthesis, not containing metal, has the advantages such as cheapness, environmental protection, stable, light weight.
(3) the graphite phase carbon nitride hollow ball of the after annealing process of the present invention's synthesis, the method for post processing is comparatively simple, has good Modulatory character and universality.
(4) the graphite phase carbon nitride hollow ball of the post processing annealing of this method synthesis, by the control to the after annealing time in last handling process, can realize the regulation and control of the structure and activity to carbonitride hollow ball.
(5) the graphite phase carbon nitride hollow ball of after annealing process is applied to photochemical catalyzing by the present invention first, finds that after annealing process is conducive to improving the Photocatalyzed Hydrogen Production performance of carbonitride, and has good activity stability.In light-catalyzed reaction system, it can carry out separating treatment easily, and 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 transmission electron microscope (TEM) figure of the graphite phase carbon nitride hollow ball of the after annealing process of embodiment 1-4 gained.
Fig. 2 is the Fourier transform infrared FT-IR spectrogram of the graphite phase carbon nitride hollow ball of the after annealing process of embodiment 4 gained.
Fig. 3 is that the X-ray powder diffraction XRD of the graphite phase carbon nitride hollow ball of the after annealing process of embodiment 4 gained schemes.
Fig. 4 is that the UV-vis DRS DRS of the graphite phase carbon nitride hollow ball of the after annealing process of embodiment 4 gained schemes.
Fig. 5 is the Performance comparision figure that the carbonitride hollow ball of the graphite phase carbon nitride hollow ball of the after annealing process of embodiment 4 gained and the non-modified of comparative example 1 gained carries out 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 dissolved in by 3g cyanamide in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing, 80 DEG C of vacuum drying, obtain carbonitride hollow ball.After annealing 5h at 300 DEG C in air atmosphere.
embodiment 2
Be dissolved in by 3g cyanamide in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing, 80 DEG C of vacuum drying, obtain carbonitride hollow ball.After annealing 5h at 400 DEG C in air atmosphere.
embodiment 3
Be dissolved in by 3g cyanamide in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing, 80 DEG C of vacuum drying, obtain carbonitride hollow ball.After annealing 5h at 500 DEG C in air atmosphere.
embodiment 4
Be dissolved in by 3g cyanamide in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing.80 DEG C of vacuum drying, obtain carbonitride hollow ball.After annealing 5h at 550 DEG C in air atmosphere.
comparative example 1
Be dissolved in by 3g cyanamide in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing.80 DEG C of vacuum drying, obtain carbonitride hollow ball.
performance test
Fig. 1 is transmission electron microscope (TEM) figure of the graphite phase carbon nitride hollow ball through after annealing process of embodiment 1-4 and comparative example 1 gained.Can find that from figure graphite phase carbon nitride hollow ball still has uniform hollow ball pattern after high-temperature process, particle diameter at about 270nm, thick about the 60nm of shell.(a), (b) undressed carbonitride hollow ball; (c) carbonitride hollow ball 300 DEG C of after annealings; (d) carbonitride hollow ball 400 DEG C of after annealings; (e) carbonitride hollow ball 500 DEG C of after annealings; (f) carbonitride hollow ball 550 DEG C of after annealings.
Fig. 2 is the Fourier transform infrared FT-IR spectrogram of the graphite phase carbon nitride hollow ball through 550 DEG C of after annealing process of embodiment 4 gained.As can be seen from the figure hollow ball carbonitride still keeps the structure of graphite phase carbon nitride after high-temperature heat treatment.At 2180cm -1the disappearance locating not to be polymerized itrile group shows to improve through after annealing process the degree of polymerization of sample.
Fig. 3 is that the X-ray powder diffraction XRD of the graphite phase carbon nitride hollow ball through 550 DEG C of after annealing process of embodiment 4 gained 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, does not destroy the structure of graphite phase carbon nitride hollow ball after confirming the process of high temperature after annealing.
Fig. 4 is that the UV-vis DRS DRS of the graphite phase carbon nitride hollow ball through 550 DEG C of after annealing process of embodiment 4 gained schemes.Can find that from figure 550nm is widened in its light absorption of product prepared, confirm that after annealing process makes the pi-conjugated structure of carbonitride hollow ball expand, thus increase its light abstraction width.
Fig. 5 is the Performance comparision figure of the graphite phase carbon nitride hollow ball (HCNS550) through 550 DEG C of after annealing process of embodiment 4 gained and untreated carbonitride hollow ball (HCNS) the photochemical catalyzing hydrogen making of comparative example 1 gained.20mg catalyst and reaction reagent (containing the 100mL triethanolamine aqueous solution of 10vol.%, original position photo-reduction H 2ptCl 6, i.e. 3wt.%Pt) react in upper illuminated reactor.Can find that from figure the hydrogen-producing speed of the product (xenon lamp 300W, filter plate λ >420nm) under visible light prepared reaches 351 μm of ol/h, improve 2 times compared with the carbonitride hollow ball (168 μm of ol/h) without after annealing process.
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. a preparation method for the graphite phase carbon nitride hollow ball visible light catalyst of after annealing process, is characterized in that: carbonitride hollow ball is carried out in air atmosphere the graphite phase carbon nitride hollow ball visible light catalyst that after annealing process obtains described after annealing process; Comprise the following steps:
(1) synthetic silica ball;
(2) 3g cyanamide is dissolved in the aqueous solution of 15.5g silica spheres colloidal sol, ultrasonic, and 80 DEG C add thermal agitation, centrifugal, dries, and in air atmosphere, is that 2.3 DEG C/min is heated to 550 DEG C of insulation 4h with heating rate;
(3) product of step (2) is joined 8mol/LNH 4hF 2stir 48h in solution, filter, washing, then stir 48h, filter, washing, 80 DEG C of vacuum drying, obtain carbonitride hollow ball;
(4) 550 DEG C of after annealing 5h in air atmosphere, obtain the graphite phase carbon nitride hollow ball visible light catalyst of described after annealing process; Chemical formula is C 3n 4, and be class graphite-phase, be a kind of polymer semiconductor;
Described graphite phase carbon nitride is pattern and the micro-nano structure of hollow ball;
The specific area of graphite phase carbon nitride hollow ball is 80 ~ 280m 2/ g, particle size is 270-600nm, the thick 30-100nm of shell, and absorb visible ray, light absorption band edge is at 420 ~ 700nm;
Described graphite phase carbon nitride hollow ball visible light catalyst is applied to photochemical catalyzing hydrogen making under visible ray.
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CN104722325B (en) * 2015-02-27 2017-04-19 清华大学 Three-dimensional macro-scale porous graphite phase carbon nitride photocatalyst and preparation and application of photocatalyst
CN106938198B (en) * 2016-01-04 2019-08-20 中国科学院化学研究所 A kind of graphite phase carbon nitride porous microsphere and preparation method thereof
CN106744742A (en) * 2016-11-11 2017-05-31 天津大学 Many shell graphite phase carbon nitride hollow nano-spheres and its synthetic method and application
CN108584892A (en) * 2018-04-26 2018-09-28 福州大学 A kind of preparation method and applications of crystalline phase azotized carbon nano particle
CN111659451B (en) * 2020-07-14 2023-03-24 中国科学院山西煤炭化学研究所 Preparation method and application of nitrogen vacancy-containing few-layer porous carbon nitride photocatalyst

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