CN104310321A - Preparation method of porous g-C3N4 semi-conducting material - Google Patents
Preparation method of porous g-C3N4 semi-conducting material Download PDFInfo
- Publication number
- CN104310321A CN104310321A CN201410469169.1A CN201410469169A CN104310321A CN 104310321 A CN104310321 A CN 104310321A CN 201410469169 A CN201410469169 A CN 201410469169A CN 104310321 A CN104310321 A CN 104310321A
- Authority
- CN
- China
- Prior art keywords
- ball milling
- ball
- carrying
- porous
- preparation
- 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
Abstract
The invention relates to the field of semi-conducting materials and provides a preparation method of a porous g-C3N4 semi-conducting material. The preparation method comprises the following steps of putting melamine powder into a crucible boat, putting the crucible boat with melamine powder into a tubular furnace, carrying out heating treatment, carrying out cooling to obtain yellow blocky g-C3N4 solids, carrying out grinding, putting the g-C3N4 particles into a ball milling tank, carrying out ball milling pretreatment, adding the slurry obtained by ball milling with a same ball milling solvent, carrying out drying to obtain g-C3N4 particles, dispersing the g-C3N4 particles into ethanol, carrying out ultrasonic treatment for dispersion, adding sulfuric acid into the ethanol dispersion solution of g-C3N4 to adjust a pH value of the ethanol dispersion solution, and carrying out a hydro-thermal reaction process to obtain the porous g-C3N4. Through combination of a ball milling technology and protonation effects, the preparation method conveniently prepares the porous g-C3N4 and solves the problem that the traditional method produces g-C3N4 having a small specific surface area and low efficiency.
Description
Technical field
The invention relates to field of semiconductor materials, particularly porous g-C
3n
4the preparation method of semiconductor material.
Background technology
G-C
3n
4be a kind of novel metalloid semiconductor light-catalyst, its special characteristic of semiconductor, high chemical stability, nontoxic easy preparation, the feature such as with low cost, make it have broad application prospects in photocatalysis field.But lower specific surface area and quantum yield but significantly limit its development.At present, porous g-C is prepared
3n
4become a kind of method of conventional increasing specific surface area and quantum yield, many documents all report prepares porous g-C by hard template method and soft template method
3n
4.But hard template method preparation process is loaded down with trivial details, and cost is higher, large to environmental hazard, be unfavorable for that large scale investment is produced; And soft template method easily causes the problems such as carbon remains.Therefore, without Template preparation porous g-C
3n
4become the focus of current research.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of porous g-C
3n
4the preparation method of semiconductor material.
For solving the problems of the technologies described above, solution of the present invention is:
A kind of porous g-C is provided
3n
4the preparation method of semiconductor material, comprises the steps:
Steps A: first get trimeric cyanamide powder and be evenly placed in corundum crucible boat; and put it in tube furnace; pass into argon gas the air in tube furnace is drained; under argon atmosphere; 380 DEG C are warmed up in 10min, and then with the ramp of 5 DEG C/min to thermal treatment temp, after to be heated; be cooled to room temperature, obtain yellow block g-C
3n
4solid; By block g-C
3n
4solid grinds in agate mortar, obtains g-C
3n
4particle;
Wherein, the thermal treatment temp in tube furnace is 500 DEG C ~ 600 DEG C; Heat treatment time is 2h ~ 5h;
Step B: by g-C
3n
4particle loads in agate jar, then adds agate ball, ball milling solvent successively, and loads in planetary ball mill and carry out ball milling pretreatment; Add isopyknic identical ball milling solvent in slip after ball milling, stir 10min; Slip is put into the oven dry of 60 DEG C, baking oven, obtain the g-C of ball milling pretreatment
3n
4particle;
Wherein, the mass ratio of agate ball and ball milling solvent is 10:1 ~ 50:1; g-C
3n
4the mass ratio of particle and ball milling solvent is 1:0.4 ~ 1:1.4;
The Ball-milling Time of described ball milling pretreatment is 1h ~ 8h, rotational speed of ball-mill is 100r/min ~ 500r/min;
Step C: the g-C that ball milling pretreatment is obtained
3n
4granular composite is in ethanol, and supersound process makes it be uniformly dispersed in 1 hour; At g-C
3n
4alcohol dispersion liquid in dropwise to add aqueous sulfuric acid regulation system pH value be 1 ~ 4, then by its pre-treatment under water bath condition, be finally transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction 1 ~ 3 time; Be cooled to after room temperature centrifugal until it, and wash three times respectively with deionized water and ethanol, the product of gained, at 60 DEG C of drying and processings, prepares porous g-C
3n
4;
Wherein, g-C
3n
4particle solid content is in ethanol 10g/L ~ 30g/L; Aqueous sulfuric acid concentration is 10g/L ~ 60g/L;
Under described water bath condition, pretreated water bath processing temperature is 60 DEG C ~ 90 DEG C, the time is 2h ~ 4h; Hydrothermal temperature is 120 DEG C ~ 180 DEG C, and the hydro-thermal reaction time is 12h ~ 24h.
In the present invention, in described step B, ball milling solvent is any one in acetone, Virahol, normal hexane.
Principle of work of the present invention: first the present invention adopts high-energy ball-milling process to g-C
3n
4block carries out pre-treatment, by large size g-C
3n
4block is pulverized as submicron particles.Then with the g-C after ball milling
3n
4particle is raw material, and under utilizing hydrothermal condition, strong acid is to g-C
3n
4protonated effect, make submicron g-C
3n
4particle surface decomposes and is partly dissolved formation vesicular structure, thus effectively improves g-C
3n
4specific surface area.
Compared with prior art, the invention has the beneficial effects as follows:
By the combination of ball-milling technology and protonation, prepare porous g-C comparatively easily
3n
4, avoid the technique of template loaded down with trivial details and unfriendly etc. not enough to environment, solve g-C prepared by traditional method
3n
4the problem that specific surface area is little, quantum yield is low.Meanwhile, the g-C for preparing of the method
3n
4surface has more avtive spot, thus shows more excellent photocatalysis performance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Porous g-C
3n
4the preparation method of semiconductor material, comprises the following steps:
Steps A: first get trimeric cyanamide powder and be evenly placed in corundum crucible boat; and put it in tube furnace; pass into argon gas the air in tube furnace is drained; under argon atmosphere; 380 DEG C are warmed up in 10min, and then with the ramp of 5 DEG C/min to thermal treatment temp, after thermal treatment certain hour; be cooled to room temperature, obtain yellow block g-C
3n
4solid; By block g-C
3n
4solid grinds in agate mortar, obtains g-C
3n
4particle;
Wherein, the thermal treatment temp in tube furnace is 500 DEG C ~ 600 DEG C; Heat treatment time is 2h ~ 5h;
Step B: by g-C
3n
4particle loads in agate jar, then adds agate ball, ball milling solvent successively, and loads in planetary ball mill and carry out ball milling pretreatment; Add isopyknic identical ball milling solvent in slip after ball milling, stir 10min; Slip is put into the oven dry of 60 DEG C, baking oven, obtain the g-C of ball milling pretreatment
3n
4particle;
Wherein, the mass ratio of agate ball and ball milling solvent is 10:1 ~ 50:1; g-C
3n
4the mass ratio of particle and ball milling solvent is 1:0.4 ~ 1:1.4; The Ball-milling Time of described ball milling pretreatment is 1h ~ 8h, rotational speed of ball-mill 100r/min ~ 500r/min.
Step C: the g-C that ball milling pretreatment is obtained
3n
4granular composite is in ethanol, and supersound process makes it be uniformly dispersed in 1 hour; At g-C
3n
4alcohol dispersion liquid in dropwise to add aqueous sulfuric acid regulation system pH value be 1 ~ 4, then by its pre-treatment under water bath condition, be finally transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction 1 ~ 3 time; Be cooled to after room temperature centrifugal until it, and wash three times respectively with deionized water and ethanol, the product of gained, at 60 DEG C of drying and processings, prepares porous g-C
3n
4;
Wherein, g-C
3n
4particle solid content is in ethanol 10g/L ~ 30g/L; Aqueous sulfuric acid concentration is 10g/L ~ 60g/L; Under described water bath condition, pretreated water bath processing temperature is 60 DEG C ~ 90 DEG C, water-curing treatment duration is 2h ~ 4h; Hydrothermal temperature is 120 DEG C ~ 180 DEG C, and the hydro-thermal reaction time is 12h ~ 24h.
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.Successfully porous g-C is obtained respectively by 8 embodiments
3n
4the preparation method of semiconductor material, the testing data in each embodiment sees the following form 1.
Table 1 embodiment data sheet
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (2)
1. porous g-C
3n
4the preparation method of semiconductor material, is characterized in that, comprises the steps:
Steps A: first get trimeric cyanamide powder and be evenly placed in corundum crucible boat; and put it in tube furnace; pass into argon gas the air in tube furnace is drained; under argon atmosphere; 380 DEG C are warmed up in 10min, and then with the ramp of 5 DEG C/min to thermal treatment temp, after to be heated; be cooled to room temperature, obtain yellow block g-C
3n
4solid; By block g-C
3n
4solid grinds in agate mortar, obtains g-C
3n
4particle;
Wherein, the thermal treatment temp in tube furnace is 500 DEG C ~ 600 DEG C, and heat treatment time is 2h ~ 5h;
Step B: by g-C
3n
4particle loads in agate jar, then adds agate ball, ball milling solvent successively, and loads in planetary ball mill and carry out ball milling pretreatment; Add isopyknic identical ball milling solvent in slip after ball milling, stir 10min; Slip is put into the oven dry of 60 DEG C, baking oven, obtain the g-C of ball milling pretreatment
3n
4particle;
Wherein, the mass ratio of agate ball and ball milling solvent is 10:1 ~ 50:1; g-C
3n
4the mass ratio of particle and ball milling solvent is 1:0.4 ~ 1:1.4; The Ball-milling Time of described ball milling pretreatment is 1h ~ 8h, rotational speed of ball-mill is 100r/min ~ 500r/min;
Step C: the g-C that ball milling pretreatment is obtained
3n
4granular composite is in ethanol, and supersound process makes it be uniformly dispersed in 1 hour; At g-C
3n
4alcohol dispersion liquid in dropwise to add aqueous sulfuric acid regulation system pH value be 1 ~ 4, then by its pre-treatment under water bath condition, be finally transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction 1 ~ 3 time; Be cooled to after room temperature centrifugal until it, and wash three times respectively with deionized water and ethanol, the product of gained, at 60 DEG C of drying and processings, prepares porous g-C
3n
4;
Wherein, g-C
3n
4particle solid content is in ethanol 10g/L ~ 30g/L; Aqueous sulfuric acid concentration is 10g/L ~ 60g/L;
Under described water bath condition, pretreated water bath processing temperature is 60 DEG C ~ 90 DEG C, the time is 2h ~ 4h; Hydrothermal temperature is 120 DEG C ~ 180 DEG C, and the hydro-thermal reaction time is 12h ~ 24h.
2. preparation method according to claim 1, is characterized in that, in described step B, ball milling solvent is any one in acetone, Virahol, normal hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410469169.1A CN104310321A (en) | 2014-09-15 | 2014-09-15 | Preparation method of porous g-C3N4 semi-conducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410469169.1A CN104310321A (en) | 2014-09-15 | 2014-09-15 | Preparation method of porous g-C3N4 semi-conducting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104310321A true CN104310321A (en) | 2015-01-28 |
Family
ID=52365676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410469169.1A Pending CN104310321A (en) | 2014-09-15 | 2014-09-15 | Preparation method of porous g-C3N4 semi-conducting material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104310321A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006581A (en) * | 2016-05-20 | 2016-10-12 | 太原理工大学 | Method for solvothermal preparation of fluorescent carbon nitride quantum dots |
| CN106115639A (en) * | 2016-06-29 | 2016-11-16 | 南京理工大学 | A kind of crimping blade shape nano lamellar g C3n4preparation method |
| CN106379874A (en) * | 2016-09-27 | 2017-02-08 | 浙江大学 | Preparation method of g-C3N4 nanosphere |
| CN106430125A (en) * | 2016-09-27 | 2017-02-22 | 浙江大学 | Preparation method of porous g-C3N4 rod |
| CN106938198A (en) * | 2016-01-04 | 2017-07-11 | 中国科学院化学研究所 | A kind of graphite phase carbon nitride porous microsphere and preparation method thereof |
| CN107352517A (en) * | 2017-07-21 | 2017-11-17 | 桂林理工大学 | A kind of preparation method of the graphite phase carbon nitride nanometer bouquet with amorphous surface |
| CN107537541A (en) * | 2016-06-27 | 2018-01-05 | 中国科学院金属研究所 | A kind of fast preparation method of high visible-light activity nitride porous carbon material |
| CN108313992A (en) * | 2018-05-02 | 2018-07-24 | 盐城工学院 | The preparation method of porous class graphite-like nitrogen carbide |
| CN109046420A (en) * | 2018-07-09 | 2018-12-21 | 江苏大学 | A kind of preparation method of nitride porous carbon photochemical catalyst |
| CN109908937A (en) * | 2019-03-25 | 2019-06-21 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of nanoscale visible light catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153055A (en) * | 2010-12-02 | 2011-08-17 | 北京化工大学 | Solvent heat preparation method for batch graphite type carbon nitride |
| CN102874777A (en) * | 2012-09-28 | 2013-01-16 | 常州大学 | High-specific-surface-area mesoporous graphite-phase carbon nitride material and preparation method thereof |
| CN103193785A (en) * | 2013-04-11 | 2013-07-10 | 江苏大学 | Graphene-like C3N4 material, as well as preparation method and use thereof |
-
2014
- 2014-09-15 CN CN201410469169.1A patent/CN104310321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153055A (en) * | 2010-12-02 | 2011-08-17 | 北京化工大学 | Solvent heat preparation method for batch graphite type carbon nitride |
| CN102874777A (en) * | 2012-09-28 | 2013-01-16 | 常州大学 | High-specific-surface-area mesoporous graphite-phase carbon nitride material and preparation method thereof |
| CN103193785A (en) * | 2013-04-11 | 2013-07-10 | 江苏大学 | Graphene-like C3N4 material, as well as preparation method and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| JIANCHAO SHEN ET AL.: "Template-free preparation and properties of mesoporousg-C3N4/TiO2nanocomposite photocatalyst", 《CRYSTENGCOMM》 * |
| SI-ZHAN WU ET AL.: "Processing graphitic carbon nitride for improved photocatalytic activity", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》 * |
| XUE LU WANG ET AL.: "Structure disorder of graphitic carbon nitride induced by liquid-assisted grinding for enhanced photocatalytic conversion", 《RSC ADVANCES》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106938198A (en) * | 2016-01-04 | 2017-07-11 | 中国科学院化学研究所 | A kind of graphite phase carbon nitride porous microsphere and preparation method thereof |
| 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 |
| CN106006581A (en) * | 2016-05-20 | 2016-10-12 | 太原理工大学 | Method for solvothermal preparation of fluorescent carbon nitride quantum dots |
| CN106006581B (en) * | 2016-05-20 | 2018-07-31 | 太原理工大学 | A kind of method of solvent hot preparation fluorescence nitridation carbon quantum dot |
| CN107537541A (en) * | 2016-06-27 | 2018-01-05 | 中国科学院金属研究所 | A kind of fast preparation method of high visible-light activity nitride porous carbon material |
| CN106115639A (en) * | 2016-06-29 | 2016-11-16 | 南京理工大学 | A kind of crimping blade shape nano lamellar g C3n4preparation method |
| CN106379874A (en) * | 2016-09-27 | 2017-02-08 | 浙江大学 | Preparation method of g-C3N4 nanosphere |
| CN106430125A (en) * | 2016-09-27 | 2017-02-22 | 浙江大学 | Preparation method of porous g-C3N4 rod |
| CN107352517A (en) * | 2017-07-21 | 2017-11-17 | 桂林理工大学 | A kind of preparation method of the graphite phase carbon nitride nanometer bouquet with amorphous surface |
| CN108313992A (en) * | 2018-05-02 | 2018-07-24 | 盐城工学院 | The preparation method of porous class graphite-like nitrogen carbide |
| CN109046420A (en) * | 2018-07-09 | 2018-12-21 | 江苏大学 | A kind of preparation method of nitride porous carbon photochemical catalyst |
| CN109908937A (en) * | 2019-03-25 | 2019-06-21 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of nanoscale visible light catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104310321A (en) | Preparation method of porous g-C3N4 semi-conducting material | |
| CN104292236A (en) | Preparation method of three-dimensional porous g-C3N4 material | |
| CN110963516A (en) | Preparation method of spherical α -alumina powder | |
| WO2016119644A1 (en) | Method for preparing lithium phosphate powder | |
| CN104891485A (en) | Method for preparing nano graphite sheet | |
| CN104973615A (en) | Microwave burning preparation method of nano gadolinium oxide powder | |
| CN105789590A (en) | Preparation method of SiOx/C cathode material | |
| CN107876795A (en) | A kind of preparation method of monocrystalline copper powder | |
| CN106159235A (en) | A kind of preparation method of graphite negative material of lithium ion battery | |
| CN108557863A (en) | A kind of preparation method of lanthana | |
| CN108165077A (en) | Solar power generation coating and preparation method and application thereof | |
| CN105668627A (en) | Nanometer NaBi(MoO4)2 and preparation method thereof | |
| CN102815733A (en) | Nanometer boehmite and preparation method thereof | |
| CN106430125A (en) | Preparation method of porous g-C3N4 rod | |
| CN103360804B (en) | A kind of graphite radiating coating and preparation method thereof | |
| CN105800571A (en) | Preparation method for two-dimensional nanosheet carbon nitride material | |
| CN108424752A (en) | A kind of conduction oil and preparation method thereof of graphene-containing and nano-particle | |
| CN104307550A (en) | Preparation method of InVO4/g-C3N4 composite material | |
| CN107935598B (en) | Low-temperature sintering method of high-performance silicon carbide ceramic material | |
| CN107138149B (en) | A kind of spherical nano-ZnO/ZnCr of highly effective hydrogen yield2O4The preparation method of composite photo-catalyst | |
| CN103754929B (en) | Preparation method for TiO2/InVO4 composite porous micro-sphere | |
| CN110002498A (en) | A kind of porous nano V2O5Preparation method | |
| CN110061206A (en) | A kind of SiO based nano composite material, cathode and preparation method thereof | |
| CN106542577B (en) | A kind of nanometer antimony trisulfide particle preparation method under controlled condition | |
| CN105441080A (en) | Method for quickly preparing NaYF:Yb/Er upconversion nano particles having different phases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150128 |