CN103861630A - Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst - Google Patents
Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst Download PDFInfo
- Publication number
- CN103861630A CN103861630A CN201410089569.XA CN201410089569A CN103861630A CN 103861630 A CN103861630 A CN 103861630A CN 201410089569 A CN201410089569 A CN 201410089569A CN 103861630 A CN103861630 A CN 103861630A
- Authority
- CN
- China
- Prior art keywords
- hollow ball
- graphite
- visible light
- carbonitride
- combined polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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 discloses a copolymerization-modified graphite-phase carbon nitride hollow ball visible-light-driven photocatalyst as well as a preparation method and an application thereof and belongs to the technical fields of material preparation and photocatalysis. A carbon nitride hollow ball is synthetized by taking cyanamide and a small organic molecule monomer as precursors, a mesoporous silicon dioxide ball as a template and through the steps of thermal polymerization and template removing. The copolymerization-modified graphite-phase carbon nitride prepared by adopting the method disclosed by the invention is shaped like a hollow ball and is uniform in grain size and proper in band gap; compared with traditional-phase carbon nitride, the graphite-phase carbon nitride is capable of effectively increasing the specific surface area and increasing the utilization rate of sunlight and has the efficient photocatalytic hydrogen generation performance in visible light. The visible-light-driven photocatalyst disclosed by the invention is simple in synthetic process, low in cost and high in catalytic efficiency, meets the actual production requirements and has the broad application prospect in the photocatalysis field.
Description
Technical field
The invention belongs to material preparation and light-catalysed technical field, be specifically related to graphite-phase carbonitride hollow ball visible light catalyst of a kind of combined polymerization modification and its preparation method and application.
Background technology
Utilize solar energy to solve the global energy and environmental problem is an important issue of current scientific research field.Semiconductor light-catalyst can at room temperature make full use of sunshine, has low cost, free of contamination advantage, has great importance for fundamentally solving energy shortage problem.For many years, scientific research personnel is devoted to exploitation always and has stability and high efficiency visible-light photocatalyst, as metal-doped SiTiO
3, TaON, Ta
3n
5polynary sulfide etc.But these photochemical catalysts all exist that solar energy utilization ratio is low, the easy inactivation of photochemical catalyst, quantum efficiency are low and the defect such as photoetch, have suppressed its application in photochemical catalyzing.Therefore efficient, stable, the nontoxic visible light catalytic agent material of preparation is the significant challenge of photocatalysis field.
In recent years, graphite-phase carbonitride semi-conducting polymer material is as the metal-free visible-light photocatalyst of one, be subject to scientist and researchers' extensive concern, be used to the decomposition of visible light catalytic water to realize conversion using (the Nat. Mater. 2009 of solar energy to chemical energy, 8,76).But it still exists very important defect: specific area is little, and active sites is few, cause its quantum efficiency lower.Researcher expects to improve its photocatalytic activity by structure and the pattern of regulation and control carbonitride.Currently reported as the synthetic order mesoporous carbonitride of SBA-15 type (Adv. Funct. Mater. 2013, doi:10.1002/adfm.201203287); Utilize hard template method successfully to prepare hollow ball-shape carbonitride (Nature Communications 2012,3,1139).Hollow ball-shape carbonitride is because its unique pattern receives much concern, its have as: density is low, and specific area is large, and the good advantage such as bearing capacity and high osmosis, has been widely used in the energy, catalysis and environmental area, the decomposition of for example water, oxygen reduction reaction, CO
2the field such as reduction and contaminant degradation in.
Combined polymerization means are incorporated into the research work of hollow ball carbonitride, have not been reported.By copolymerization, the conjugated structure of carbonitride hollow ball is regulated and controled, in strengthening catalyst surface mass transport process, reduce semiconductor band gap width, promote photo-generated carrier to separate and migration, improve solar energy utilization ratio, have wide practical use in photocatalysis field.The hollow ball carbonitride visible light catalyst that experiment showed, combined polymerization modification is the photochemical catalyst that a kind of efficient visible ray decomposes aquatic products hydrogen.
Summary of the invention
The object of the present invention is to provide graphite-phase carbonitride hollow ball visible light catalyst of a kind of combined polymerization modification and its preparation method and application.Photochemical catalyst prepared by the present invention has the hollow ball of high-specific surface area, narrow band gap width, and photo-generated carrier separation fast, transfer ability can be realized efficient visible ray decomposition water and produce hydrogen.Technique of the present invention is simple, with low cost, and 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 carbonitride hollow ball visible light catalyst of combined polymerization modification 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 ~ 280 m
2/ g, absorbs visible ray, and light absorption band edge is at 420 ~ 700 nm, and has the performance of good photochemical catalyzing hydrogen making, can be used as a kind of photochemical catalyst efficiently.
The method of preparing the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification as above is taking cyanamide and organic molecule monomer as predecessor, after using hard template method by high temperature thermal condensation, remove again template, obtain the graphite-phase carbonitride hollow ball of combined polymerization modification.Described preparation method comprises the following steps: (1) synthetic different-grain diameter size and the thick silica spheres (St ber silica sol) of different shells.(2) one of organic molecule monomer 2-aminothiophene-3-formonitrile HCN, diaminomaleonitrile, barbiturates are dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols with 3 g cyanamides, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.(3) join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stirs 48 h, filter, and washing, 80 DEG C of vacuum drying, obtain the hollow ball carbonitride of combined polymerization modification.
The graphite-phase carbonitride 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) the present invention is incorporated into the means of combined polymerization the modification of hollow ball carbonitride first, has increased specific area and has reduced band gap width, and photo-generated carrier separation simultaneously, transport efficiency are improved.
(2) the graphite-phase carbonitride hollow ball of the synthetic combined polymerization modification of the present invention, not containing metal, has the advantages such as cheapness, environmental protection, stable, light weight.
(3) the graphite-phase carbonitride hollow ball of the synthetic combined polymerization modification of the present invention, the organic molecule monomer selectivity wherein with modifying function is in extensive range, has good Modulatory character and universality.
(4) the graphite-phase carbonitride hollow ball of the synthetic combined polymerization modification of this method by the addition to predecessor and the control in reaction time, can be realized particle diameter and the thick regulation and control of shell to carbonitride hollow ball in preparation process.
(5) the present invention is applied to photochemical catalyzing by the graphite-phase carbonitride hollow ball of combined polymerization modification first, finds that combined polymerization modification is conducive to improve 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.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) figure of the graphite-phase carbonitride hollow ball a of the combined polymerization modification of embodiment 1 gained.
Fig. 2 is the UV-vis DRS DRS figure of the graphite-phase carbonitride hollow ball a of the combined polymerization modification of embodiment 1 gained.
Fig. 3 is the Fourier transform infrared FT-IR spectrogram of the graphite-phase carbonitride hollow ball a of the combined polymerization modification of embodiment 1 gained.
Fig. 4 is the X-ray powder diffraction XRD figure of the graphite-phase carbonitride hollow ball a of the combined polymerization modification of embodiment 1 gained.
Fig. 5 is the performance comparison diagram that the graphite-phase carbonitride hollow ball a of combined polymerization modification of embodiment 1 gained and the carbonitride hollow ball b of the non-modified of comparative example 1 gained carry 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.
The cyanamide that is 25:1 by mass ratio and 2-aminothiophene-3-formonitrile HCN are dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stirs 48 h, filter, and washing, 80 DEG C of vacuum drying, obtain the hollow ball carbonitride of combined polymerization modification.
Be that 100:1 cyanamide and 2-aminothiophene-3-formonitrile HCN are dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols by mass ratio, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stirs 48 h, filter, and washing, 80 DEG C of vacuum drying, obtain the hollow ball carbonitride of combined polymerization modification.
Be that 200:1 cyanamide and 2-aminothiophene-3-formonitrile HCN are dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols by mass ratio, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stirs 48 h, filter, and washing, 80 DEG C of vacuum drying, obtain the hollow ball carbonitride of combined polymerization modification.
embodiment 4
The cyanamide that is 1000:1 by mass ratio and 2-aminothiophene-3-formonitrile HCN are dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, obtain white powder, in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stirs 48 h, filter, and washing, 80 DEG C of vacuum drying, obtain the hollow ball carbonitride of combined polymerization modification.
comparative example 1
3g cyanamide is dissolved in the aqueous solution of 15.5 g silica spheres colloidal sols, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, and obtain white powder, and in air or nitrogen atmosphere, in 550 DEG C of insulation 4 h, heating rate is 2.3 DEG C/min, obtains yellow powder.Join 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stir 48 h, 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 carbonitride hollow ball of embodiment 1 gained.From figure, can find that graphite-phase carbonitride has uniform hollow ball pattern, particle diameter is in 270nm left and right, about the thick 60nm of shell.
Fig. 2 is the UV-vis DRS DRS figure of the graphite-phase carbonitride hollow ball of the combined polymerization modification of embodiment 1 gained.From figure, can find preparation its light absorption of product widen 600nm, confirm that it belongs to semi-conducting material.
Fig. 3 is the Fourier transform infrared FT-IR spectrogram of the graphite-phase carbonitride hollow ball of the combined polymerization modification of embodiment 1 gained.As can be seen from the figure at 800 cm
-1with 1200 ~ 1600 cm
-1interval, they correspond respectively to breathing vibration and the stretching vibration of armaticity CN heterocycle of piperazine ring, at 3200 cm
-1interval mainly due to the many not NH of bonding of hollow ball carbonitride surface existence
2, NH is caused, confirms that combined polymerization modification does not change the agent structure of graphite-phase carbonitride.
Fig. 4 is the X-ray powder diffraction XRD figure of the graphite-phase carbonitride hollow ball of the combined polymerization modification of embodiment 1 gained.From figure, can find 13.0
owith 27.5
othere are two XRD diffraction maximums that significantly belong to graphite-phase carbonitride (100) and (002) crystal face in place, confirms that the structure of graphite-phase carbonitride is not subject to the impact of combined polymerization modification.
Fig. 5 is the graphite-phase carbonitride hollow ball a of combined polymerization modification of embodiment 3 gained and the performance comparison diagram of the carbonitride hollow ball b photochemical catalyzing hydrogen making without combined polymerization modification of comparative example 1 gained.20mg catalyst and reaction reagent are (containing the 100mL triethanolamine aqueous solution of 10 vol. %, original position photo-reduction H
2ptCl
6, i.e. 3 wt. % Pt) react in upper photograph in formula reactor.From figure, can find product (xenon lamp 300W under visible ray of preparation, filter plate λ > 455 nm) hydrogen-producing speed reach 286 μ mol/h, improved 1.7 times compared with carbonitride hollow ball (104 μ mol/h) without combined polymerization modification.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing 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 (6)
1. a graphite-phase carbonitride hollow ball visible light catalyst for combined polymerization modification, is characterized in that: chemical formula is C
3n
4, and be class graphite-phase, be a kind of polymer semiconductor.
2. the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification according to claim 1, is characterized in that: described graphite-phase carbonitride has pattern and the micro-nano structure of hollow ball.
3. the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification according to claim 1, is characterized in that: the specific area of carbonitride hollow ball is 80 ~ 280 m
2/ g, particle size is 270-800nm, and the thick 30-100nm of shell absorbs visible ray, and light absorption band edge is at 420 ~ 700 nm.
4. prepare the method for the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification as claimed in claim 1 for one kind, it is characterized in that: taking cyanamide and organic molecule monomer as predecessor, mesoporous silica spheres is that hard template makes graphite-phase carbonitride hollow ball.
5. the preparation method of the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification according to claim 1, is characterized in that: comprise the following steps:
(1) synthetic silica ball;
(2) organic molecule monomer and cyanamide are dissolved in the aqueous solution of silica spheres colloidal sol, ultrasonic, 80 DEG C add thermal agitation, centrifugal, dry, and in air or nitrogen atmosphere, are heated to 550 DEG C of insulation 4 h taking heating rate as 2.3 DEG C/min; Described organic molecule monomer is the one in 2-aminothiophene-3-formonitrile HCN, 2-anthranilo nitrile, diaminomaleonitrile, barbiturates;
(3) product of step (2) is joined to 8 mol/L NH
4hF
2in solution, stir 48 h, filter, washing, then stir 48 h, filter washing, 80 DEG C of vacuum drying, the graphite-phase carbonitride hollow ball visible light catalyst of the combined polymerization modification described in making.
6. an application for the graphite-phase carbonitride hollow ball visible light catalyst of combined polymerization modification as claimed in claim 1, is characterized in that: the graphite-phase carbonitride hollow ball visible light catalyst of described combined polymerization modification is applied to photochemical catalyzing hydrogen making under visible ray.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410089569.XA CN103861630A (en) | 2014-03-12 | 2014-03-12 | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410089569.XA CN103861630A (en) | 2014-03-12 | 2014-03-12 | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103861630A true CN103861630A (en) | 2014-06-18 |
Family
ID=50900993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410089569.XA Pending CN103861630A (en) | 2014-03-12 | 2014-03-12 | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103861630A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492470A (en) * | 2015-01-09 | 2015-04-08 | 江苏大学 | Preparation method of graphite type carbon nitride photocatalytic material |
| CN104525234A (en) * | 2014-12-17 | 2015-04-22 | 上海交通大学 | Preparation method for graphite-phase carbon nitride photocatalytic material |
| CN104607231A (en) * | 2015-02-16 | 2015-05-13 | 江苏理工学院 | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method of carbon nitride photocatalyst |
| CN104815682A (en) * | 2015-03-31 | 2015-08-05 | 大连理工大学 | High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof |
| CN105195192A (en) * | 2015-07-29 | 2015-12-30 | 阜阳师范学院 | Composite photocatalyst CN-CNI as well as preparation method and application thereof |
| CN109499594A (en) * | 2018-11-07 | 2019-03-22 | 江苏大学 | A kind of CdIn2S4 nanometers of octahedra modification Ta3N5The preparation method of nucleocapsid composite photo-catalyst |
| CN110639585A (en) * | 2019-09-19 | 2020-01-03 | 浙江大学 | Copolymerization modified layered graphite phase carbon nitride photocatalyst and preparation method and application thereof |
| CN112371161A (en) * | 2020-12-25 | 2021-02-19 | 郑州大学 | Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof |
| CN112466670A (en) * | 2020-12-11 | 2021-03-09 | 湘潭大学 | Porous CTF nano sheet and preparation method and application thereof |
| CN113942983A (en) * | 2021-10-19 | 2022-01-18 | 陕西科技大学 | Preparation method of novel carbon nitride-based material combining copolymerization and thermal induction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1941946A1 (en) * | 2007-01-04 | 2008-07-09 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Carbonitrides as catalysts |
| JP2011195412A (en) * | 2010-03-23 | 2011-10-06 | National Institute Of Advanced Industrial Science & Technology | Carbon nitride involving metal, and method for production thereof |
| CN103240119A (en) * | 2013-05-13 | 2013-08-14 | 福州大学 | Chirality graphite phase carbon nitride polymer semiconductor photocatalyst |
| CN103272639A (en) * | 2013-06-09 | 2013-09-04 | 福州大学 | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst |
-
2014
- 2014-03-12 CN CN201410089569.XA patent/CN103861630A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1941946A1 (en) * | 2007-01-04 | 2008-07-09 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Carbonitrides as catalysts |
| JP2011195412A (en) * | 2010-03-23 | 2011-10-06 | National Institute Of Advanced Industrial Science & Technology | Carbon nitride involving metal, and method for production thereof |
| CN103240119A (en) * | 2013-05-13 | 2013-08-14 | 福州大学 | Chirality graphite phase carbon nitride polymer semiconductor photocatalyst |
| 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 (5)
| Title |
|---|
| JIANHUA SUN ET AL.: "Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles", 《NATURE COMMUNICATIONS》, vol. 2152, 16 October 2012 (2012-10-16), pages 1 - 7 * |
| JINSHUI ZHANG ET AL.: "Co-Monomer Control of Carbon Nitride Semiconductors to Optimize Hydrogen Evolution with Visible Light", 《ANGEW.CHEM.INT.ED.》, vol. 51, 14 February 2012 (2012-02-14), pages 3183 - 3187 * |
| JINSHUI ZHANG ET AL.: "Molecular doping of carbon nitride photocatalysts with tunable bandgap and enhanced activity", 《JOURNAL OF CATALYSIS》, vol. 310, 12 February 2013 (2013-02-12), pages 24 - 30 * |
| SOHEE HWANG ET AL.: "Template-directed synthesis of highly ordered nanoporous graphitic carbon nitride through polymerization of cyanamide", 《APPLIED SURFACE SCIENCE》, vol. 253, 27 December 2006 (2006-12-27), pages 5656 - 5659, XP022031455, DOI: doi:10.1016/j.apsusc.2006.12.032 * |
| 郑华荣等: "二氨基马来腈共聚合改性氮化碳光催化剂", 《物理化学学报》, vol. 28, no. 10, 10 September 2012 (2012-09-10), pages 2336 - 2342 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525234A (en) * | 2014-12-17 | 2015-04-22 | 上海交通大学 | Preparation method for graphite-phase carbon nitride photocatalytic material |
| CN104492470A (en) * | 2015-01-09 | 2015-04-08 | 江苏大学 | Preparation method of graphite type carbon nitride photocatalytic material |
| CN104607231A (en) * | 2015-02-16 | 2015-05-13 | 江苏理工学院 | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method of carbon nitride photocatalyst |
| CN104815682A (en) * | 2015-03-31 | 2015-08-05 | 大连理工大学 | High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof |
| CN104815682B (en) * | 2015-03-31 | 2017-04-12 | 大连理工大学 | High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof |
| CN105195192A (en) * | 2015-07-29 | 2015-12-30 | 阜阳师范学院 | Composite photocatalyst CN-CNI as well as preparation method and application thereof |
| CN109499594A (en) * | 2018-11-07 | 2019-03-22 | 江苏大学 | A kind of CdIn2S4 nanometers of octahedra modification Ta3N5The preparation method of nucleocapsid composite photo-catalyst |
| CN109499594B (en) * | 2018-11-07 | 2021-11-23 | 江苏大学 | CdIn2S4 nano octahedron modified Ta3N5Preparation method of core-shell composite photocatalyst |
| CN110639585A (en) * | 2019-09-19 | 2020-01-03 | 浙江大学 | Copolymerization modified layered graphite phase carbon nitride photocatalyst and preparation method and application thereof |
| CN112466670A (en) * | 2020-12-11 | 2021-03-09 | 湘潭大学 | Porous CTF nano sheet and preparation method and application thereof |
| CN112371161A (en) * | 2020-12-25 | 2021-02-19 | 郑州大学 | Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof |
| CN113942983A (en) * | 2021-10-19 | 2022-01-18 | 陕西科技大学 | Preparation method of novel carbon nitride-based material combining copolymerization and thermal induction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103861630A (en) | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst | |
| CN103272639B (en) | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst | |
| CN103861632B (en) | A kind of preparation method of nitride porous carbon catalysis material of sulfur doping | |
| CN103752334B (en) | Graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of ionic liquid | |
| CN102671683B (en) | Preparation method of nanosheet self-assembled C-doped (BiO)2CO3 microsphere visible light catalyst | |
| CN107115884B (en) | g-C3N4/TiO2Nano-wire assembled structure photocatalyst | |
| CN103623856B (en) | Spherical mesoporous carbon nitride photocatalyst with multistage nano structure | |
| CN107159313A (en) | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst | |
| CN109046425A (en) | Composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method | |
| CN107081166A (en) | A kind of g C3N4/TiO2Multilevel hierarchy and preparation method thereof | |
| CN108786874A (en) | Load the graphite phase carbon nitride nanometer sheet material and its preparation method and application of manganese dioxide | |
| CN105597803A (en) | Mesoporous carbonitride photocatalyst and preparation method thereof | |
| CN109012731A (en) | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application | |
| CN102633303A (en) | Three-dimensional graded titanium dioxide hollow nanometer box and preparation method of same | |
| CN103638950A (en) | CuS nanosheet photocatalytic material and preparation method thereof | |
| CN103801354B (en) | A kind of graphite phase carbon nitride hollow ball visible light catalyst of after annealing process | |
| CN109126852A (en) | The preparation method of orderly classifying porous graphite phase carbon nitride catalysis material | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN103721745A (en) | Copolymerization modified ordered mesoporous carbon nitride photocatalyst | |
| CN113441145B (en) | Preparation method of barium titanate/iron oxyhydroxide photocatalyst | |
| CN113457745B (en) | Selective reduction of nitrate to N2Preparation method and application of photocatalyst | |
| CN113058601B (en) | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting | |
| CN113231101A (en) | Preparation and application of Cu-NM-101(Fe) photocatalyst | |
| CN113101980A (en) | TiO with visible light catalytic activity2Preparation method and application of/UiO-66 composite material | |
| CN105879855B (en) | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140618 |