WO2006087411A1 - A method for preparing carbon nitride c3n4 - Google Patents

A method for preparing carbon nitride c3n4 Download PDF

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Publication number
WO2006087411A1
WO2006087411A1 PCT/FI2006/000040 FI2006000040W WO2006087411A1 WO 2006087411 A1 WO2006087411 A1 WO 2006087411A1 FI 2006000040 W FI2006000040 W FI 2006000040W WO 2006087411 A1 WO2006087411 A1 WO 2006087411A1
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Prior art keywords
carbon nitride
rodanide
pyrolysis
carried out
vessels
Prior art date
Application number
PCT/FI2006/000040
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French (fr)
Inventor
Reijo Lappalainen
Lev Nicolaevich Blinov
Mohammed Aref Hasan MAMAKHEL
Sergej Nicolaevich Philippov
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Carbodeon Ltd Oy
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Carbodeon Ltd Oy filed Critical Carbodeon Ltd Oy
Priority to EP06708899.7A priority Critical patent/EP1874684B1/en
Priority to US11/816,448 priority patent/US7708971B2/en
Publication of WO2006087411A1 publication Critical patent/WO2006087411A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon

Definitions

  • This invention relates to a method for preparing carbon nitride C 3 N 4 by pyrolysing alkali metal rodanides in a simple, economical and ecologically feasible manner.
  • Prepared carbon nitride has outstanding properties and can be used in manufacturing of electronics, manufacturing of household machinery and medical equipment, in production of blue luminophore, in spray coating of computer hard disc, manufacturing of heavy duty tools used in metal processing, etc.
  • thermochemical decomposition pyrolysis
  • C 3 N 4 production includes loading of melamine (C 3 N 3 )(NH 2 ) 3 and cyanuric chloride (C 3 N 3 )Cl 3 into a reactor with further heating up and generation of the end product C 3 N 4 .
  • the drawback is the fact that the method does not allow to prevent the formation of H 2 and HCN as by-products. This results in an elevated explosiveness and toxicity of the process; [Montigaud H., Tanguy B., Demazeau G., Alves I., Courjault S. C 3 N 4 : dream or reality? Solvothermal synthesis as macroscopic samples of C 3 N 4 graphitic form // J. of Materials Science. 2000. V.35. P.2547-2552].
  • the invention relates to a method for preparing carbon nitride C 3 N 4 by pyrolysing alkalinetal rodanides to give carbon nitride in a simple and by all means feasible manner.
  • alkali metal rodanides can be employed efficiently and in ecologically-friendly way in preparation of carbon nitride by simply pyrolysing said rodanides.
  • the yields are increased and the production costs are decreased dramatically.
  • the production cost can be lowered by factor of 10-20 via using relatively cheap raw material and rising the yield of the ready-made end product.
  • the pyrolysis is preferably carried out in a reactor chamber which is built of at least two connected and sealed vessels in shape.
  • a reactor chamber which is built of at least two connected and sealed vessels in shape.
  • the present invention is directed to a method for preparing carbon nitride C 3 N 4 wherein the alkali metal rodanide is pyrolysed to give carbon nitride C 3 N 4 .
  • pyrolysis is here meant decomposition or transformation of a compound caused by heat.
  • the alkali metal rodanide is sodium rodanide. In another preferred embodiment of the invention, the alkali metal rodanide is potassium rodanide. In a still another embodiment of the invention the alkalimetal rodanide is lithium rodanides.
  • the alkalimetal rodanide can also be a mixture of two or more alkalimetal rodanides. The alkalimetals are not to be limited to the mentioned ones.
  • the pyrolysis is preferably carried out in the substantial absence of oxygen and/or hydrogen. Most preferably, the pyrolysis is carried out in complete absence of oxygen and/or hydrogen.
  • the presence of oxygen dramatically lowers the yield of the product, and hydrogen increases the risk of explosions.
  • such conditions can be achieved by carrying out the pyrolysis in vacuumized conditions.
  • the pressure can between 10 "1 - 10 "9 mmHg, preferably 10 "3 - 10 '7 mmHg and most preferably between 10 '4 - 10 '6 mmHg, possibly using inert gas flow to remove gaseous impurities.
  • the pyrolysis of alkalimetal rodanide or rodanides is carried out under an inert gas atmosphere.
  • inert atmospheres comprise nitrogen or argon.
  • the pyrolysis is carried out with a gradient of T max ⁇ 500 0 C, T m i n ⁇ ambient temperature. Rising the temperature over 500 0 C is in most cases not justifiable, as it may lead to partial decomposing of C 3 N 4 , therefore lowering the yield of the product.
  • the scope of the invention is not restricted to said temperature gradient.
  • the temperature gradient is created essentially throughout the chamber.
  • chamber is here meant a reactor, in which the pyrolysis is carried out.
  • the reactor which is built of at least two connected vessels in shape. Preferably, at that at least one of the vessels is removable.
  • the formed CS 2 and volatile impurities are essentially condensed in one of the vessels.
  • the vessel containing said CS 2 and volatile impurities is preferably removable.
  • the vessel containing carbon nitride product and alkali metal sulphide compounds is removable. Said alkali metal sulphide compounds are washed off the end product C 3 N 4 with water.
  • all vessels are removable.
  • the reactor comprising the vessels is so constructed that all the equipment can be tightly sealed. Examples

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Luminescent Compositions (AREA)

Abstract

The present invention relates to a method for preparing carbon nitride C3 N4 wherein alkali metal thiocyanate is simply pyrolysed to give carbon nitride C3N4 in an efficient, economical and ecologically friendly manner. The employed starting materials are cheap and formed side products are essentially non-toxic and can be easily removed and/or washed away.

Description

A method for preparing carbon nitride C3N4
Field of the invention
This invention relates to a method for preparing carbon nitride C3N4 by pyrolysing alkali metal rodanides in a simple, economical and ecologically feasible manner. Prepared carbon nitride has outstanding properties and can be used in manufacturing of electronics, manufacturing of household machinery and medical equipment, in production of blue luminophore, in spray coating of computer hard disc, manufacturing of heavy duty tools used in metal processing, etc.
State of the art
At present, there is an actual interest in methods of production of carbon nitride by thermochemical decomposition (pyrolysis) of chemical substances or mixtures.
There is a known method of C3N4 production, which includes loading of melamine (C3N3)(NH2)3 and cyanuric chloride (C3N3)Cl3 into a reactor with further heating up and generation of the end product C3N4.
The drawback (of the abovementioned method) is the fact that the method does not allow to prevent the formation of H2 and HCN as by-products. This results in an elevated explosiveness and toxicity of the process; [Montigaud H., Tanguy B., Demazeau G., Alves I., Courjault S. C3N4: dream or reality? Solvothermal synthesis as macroscopic samples of C3N4 graphitic form // J. of Materials Science. 2000. V.35. P.2547-2552].
There is also a known method of synthesis of carbon nitride C3N4 [pat. No 6428762 US]. Powder of cyanuric chloride (C3N3)Cl3 is mixed with powder of lithium nitride Li3N, after which the mixture is placed in a reactor and sealed. Nitrogen flow is put through the reactor, the content is heated up to 300-400 0C and incubated for a certain period of time. In order to remove any byproducts, the ready made carbon nitride is cooled down and washed. The drawbacks of the indicated method are: the process is multistage, is of high cost and gives a low yield of the end product - C3N4.
There is also a known method of C3N4 production, taken here as a prototype. [Dale R. Miller, Jianjun Wang, Edward G. Rapid facile synthesis of nitrogen-rich carbon nitride powders // J. Mater. Chem. 2002. V. 12. P.2463- 2469]. The method includes loading of thrichlormelamine (C3N3)(NHCl)3 into a reaction chamber, after which inert conditions are ensured by a continuous flow of N2 or Ar, and in the flow of this gas environment the heating up to T=SOO0C is carried out. There takes place a decomposition of (C3N3)(NHCl)3 → C3N4+X + 3HCl + (2-x)/2 N2) with generation of C3N4+X, where 0.5 < x < 0.8. The gaseous by-products HCl and N2 are removed with the flow of the inert gas in the (reaction) chamber. After that, the chamber is cooled down for 10 minutes, the end-product is washed with acetone and then dried at T= 13O0C. The method does not allow obtaining C3N4 of stoichiometric composition; moreover, it is not possible to completely remove traces of hydrogen, chlorine and oxygen from carbon nitride.
Summary of the invention
The major drawbacks of the known methods for preparing are that they are costly, hazardous processes often comprising several reaction sequences with moderate end-product yields. Moreover, the byproducts are difficult to remove and the washing processes are ineffective and time-consuming.
The invention that has now been found resolves the problems mentioned above.
The invention relates to a method for preparing carbon nitride C3N4 by pyrolysing alkalinietal rodanides to give carbon nitride in a simple and by all means feasible manner.
Surprisingly we found that alkali metal rodanides can be employed efficiently and in ecologically-friendly way in preparation of carbon nitride by simply pyrolysing said rodanides. Compared to previously known methods, the yields are increased and the production costs are decreased dramatically. The production cost can be lowered by factor of 10-20 via using relatively cheap raw material and rising the yield of the ready-made end product.
The use of alkali metal rodanide leads according to equation 4MeCNS — >
2Me2S + C3N4 + CS2 to generation of carbon nitride C3N4 of stoichiometric composition and impurities, which do not contain toxic HCN, with the temperature gradient ensuring complete decomposition of the furnace charge and condensation of CS2. Metal sulphides, which are co-produced in the reaction process, are well dissolved in water, which ensures the production of pure C3N4. As it is known, by varying the temperature ramp rates of furnace charge it is possible to obtain various structures of carbon nitride.
The pyrolysis is preferably carried out in a reactor chamber which is built of at least two connected and sealed vessels in shape. Such features allows for making the reaction process in a closed volume, which makes the whole process ecologically-friendly, ensures the high purity and the quick removal of any by-products and reduction of the C3N4 production costs.
Detailed description of the invention
The present invention is directed to a method for preparing carbon nitride C3N4 wherein the alkali metal rodanide is pyrolysed to give carbon nitride C3N4. With pyrolysis is here meant decomposition or transformation of a compound caused by heat.
In one preferred embodiment of the invention the alkali metal rodanide is sodium rodanide. In another preferred embodiment of the invention, the alkali metal rodanide is potassium rodanide. In a still another embodiment of the invention the alkalimetal rodanide is lithium rodanides. The alkalimetal rodanide can also be a mixture of two or more alkalimetal rodanides. The alkalimetals are not to be limited to the mentioned ones.
The pyrolysis is preferably carried out in the substantial absence of oxygen and/or hydrogen. Most preferably, the pyrolysis is carried out in complete absence of oxygen and/or hydrogen. The presence of oxygen dramatically lowers the yield of the product, and hydrogen increases the risk of explosions. In one preferred embodiment of the invention, such conditions can be achieved by carrying out the pyrolysis in vacuumized conditions. When carrying out the pyrolysis in vacuumized conditions, the pressure can between 10"1 - 10"9 mmHg, preferably 10"3 - 10'7 mmHg and most preferably between 10'4 - 10'6 mmHg, possibly using inert gas flow to remove gaseous impurities.
In another preferred embodiment of the invention, the pyrolysis of alkalimetal rodanide or rodanides is carried out under an inert gas atmosphere. Preferably, such inert atmospheres comprise nitrogen or argon.
In one preferred embodiment of the invention the pyrolysis is carried out with a gradient of Tmax < 5000C, Tmin < ambient temperature. Rising the temperature over 5000C is in most cases not justifiable, as it may lead to partial decomposing of C3N4, therefore lowering the yield of the product. However, the scope of the invention is not restricted to said temperature gradient.
The temperature gradient is created essentially throughout the chamber. With chamber is here meant a reactor, in which the pyrolysis is carried out. In a preferred embodiment of the invention the reactor which is built of at least two connected vessels in shape. Preferably, at that at least one of the vessels is removable. In an especially preferred embodiment of the invention, the formed CS2 and volatile impurities are essentially condensed in one of the vessels. The vessel containing said CS2 and volatile impurities is preferably removable. In another embodiment of the invention the vessel containing carbon nitride product and alkali metal sulphide compounds is removable. Said alkali metal sulphide compounds are washed off the end product C3N4 with water.
In a still another embodiment of the invention, all vessels are removable. Naturally, the reactor comprising the vessels is so constructed that all the equipment can be tightly sealed. Examples
The method of the invention for preparing carbon nitride C3N4 is described below, yet without restricting the invention to the examples given here. Synthetic carbon nitride C3N4 was identified using X-ray powder diffraction, infrared absorption, and reduction melting in a carrier gas (helium) flow with subsequent chromatographic separation as described in Glass Physics and Chemistry, 2004, 30(6), 573.
Example 1
For obtaining of carbon nitride C3N4, potassium rodanide in quantity of 10.5271 g was taken, loaded into a reaction chamber, which was made of quartz glass and shaped as two connected vessels. The chamber was vacuumized to pressure of 10"4 - 10"5 mmHg and sealed. The chamber was placed into an oven and heated up to T=500°C, making sure the temperature gradient Tmax = 5000C, Tmin = ambient temperature through vessels. The reaction took place:
4KCNS → 2K2S + C3N4 + CS2
Formed CS2 and volatile impurities condensed in one of the vessels due to the existence of the temperature gradient. This vessel has been removed. Potassium sulphide K2S is well dissolved in water, therefore it was removed by simple washing. As a result, carbon nitride C3N4 was obtained as a powder, yield of which was 16%.
Example 2
For obtaining carbon nitride C3N4, sodium rodanide in quantity of 10.6321 g was taken, loaded into a reaction chamber, which was made of quartz glass and shaped as two connected vessels. The chamber was vacuumized to pressure of 10"4 - 10'5 mmHg and sealed. The chamber was placed into an oven and heated up to T=490°C, making sure the temperature gradient Tmax = 49O0C, Tmin = ambient temperature through vessels. The reaction took place:
4NaCNS → 2Na2S + C3N4 + CS2 The vessel with CS2 and by-product compounds was removed. Sodium sulphide Na2S is well dissolved in water; therefore it was removed by simple washing. As a result, carbon nitride C3N4 was obtained as a powder, with the yield of 15%.
If needed, a mixture of sodium and potassium rodanides can be used for production of C3N4.
The application of a proposed method for production of carbon nitride C3N4 enables for obtaining the product in an ecologically friendly way, lowering the production cost by the factor of 10-20 via using relatively cheap raw material and rising the yield of the ready-made end product.

Claims

Claims
1. A method for preparing carbon nitride C3N4, characterized in that alkali metal rodanide is pyrolysed to give carbon nitride C3N4.
2. A method according to claim 1, characterized in that alkali metal rodanide is sodium rodanide, potassium rodanide, lithium rodanide or a mixture of two or several rodanides.
3. A method according to claim 1 or 2, characterized in that the pyrolysis is carried out in the substantial absence of oxygen and/or hydrogen.
4. A method according to claim 3, characterized in that the pyrolysis is carried out in vacuumized conditions.
5. A method according to claim 4, characterized in that the pressure is between 10"1 - 10"9 mmHg, preferably 10'3 - 10"7 mmHg and most preferably between 10'4 - 10"6 mmHg.
6. A method according to claim 3, characterized in that the pyrolysis is carried out under an inert gas atmosphere.
7. A method according to claim 6, characterized in that inert gas atmosphere comprises nitrogen.
8. A method according to claim 6, characterized in that inert gas atmosphere comprises argon.
9. A method according to any of the preceding claims, characterized in that the pyrolysis is carried out with a gradient of Tmax < 5000C, Tmin < ambient temperature.
10. A method according to claim 9, characterized in that the temperature gradient is created essentially throughout the chamber.
11. A method according to any of the preceding claims, characterized in that the pyrolysis is carried out in a reactor which is built of at least two connected vessels in shape.
12. A method according to claim 11, characterized in that at least one of the vessels is removable.
13. A method according to any of the preceding claims, characterized in that formed CS2 and volatile impurities are essentially condensed in one of the vessels.
14. A method according to claim 13, characterized in that the vessel containing formed CS2 and volatile impurities is removable.
PCT/FI2006/000040 2005-02-16 2006-02-09 A method for preparing carbon nitride c3n4 WO2006087411A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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WO2008006935A3 (en) * 2006-07-13 2008-04-17 Carbodeon Ltd Oy Carbon nitride preparation method
DE102009005095A1 (en) 2009-01-19 2010-07-22 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Process for the preparation of carbonitrides via polycondensation or sol-gel processes using hydrogen-free isocyanates
CN103265547A (en) * 2013-05-15 2013-08-28 陆希峰 Miller amino carbon nitrogen compound nanoparticles and diesel engine oil composition containing same
CN110745793A (en) * 2019-09-11 2020-02-04 中国地质大学（武汉） Steam assisted preparation of g-C3N4Method of nanosheet

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WO2007096484A2 (en) * 2006-02-23 2007-08-30 Picodeon Ltd Oy Coating with carbon nitride and carbon nitride coated product
CN102164845A (en) * 2008-09-30 2011-08-24 Nxp股份有限公司 Robust high aspect ratio semiconductor device
JP5711582B2 (en) * 2011-03-28 2015-05-07 株式会社ダイセル Photocatalyst and organic compound oxidation method using the same
US9409936B2 (en) 2014-08-08 2016-08-09 The United States Of America, As Represented By The Secretary Of The Navy Preparation of graphitic C3N3P material
CN104607240A (en) * 2015-02-12 2015-05-13 重庆工商大学 Bi/g-C3N4 semimetal-organic composite photocatalyst and preparation method
RU2663165C1 (en) * 2017-06-16 2018-08-01 федеральное государственное автономное образовательное учреждение высшего образования "Южно-Уральский государственный университет (национальный исследовательский университет)" Method of obtaining carbon materials with high nitrogen content
CN110304613A (en) * 2018-03-20 2019-10-08 中国科学技术大学 A kind of two-dimensional ultrathin metal nitride nanometer sheet and preparation method thereof
CN109384205A (en) * 2018-09-21 2019-02-26 桂林理工大学 A kind of superhard compound phase carbon nitride porous nano chain raw powder's production technology
RU2690810C1 (en) * 2018-10-05 2019-06-05 Федеральное государственное бюджетное учреждение науки Научно-технологический центр уникального приборостроения Российской академии наук (НТЦ УП РАН) Method of producing carbon nitride having an abnormally high level of fluorescence under the action of visible laser radiation
CN110560129B (en) * 2019-09-10 2022-07-01 上海纳米技术及应用国家工程研究中心有限公司 Preparation of modified carbon nitride for improving tetracycline degradation efficiency, and product and application thereof
RU2725796C1 (en) * 2020-01-30 2020-07-06 Федеральное государственное бюджетное учреждение науки Научно-технологический центр уникального приборостроения Российской академии наук (НТЦ УП РАН) Method of producing composite material having high level of fluorescence under action of electromagnetic radiation of visible range
RU2758946C1 (en) * 2021-03-23 2021-11-03 Федеральное государственное бюджетное учреждение науки Научно-технологический центр уникального приборостроения Российской академии наук (НТЦ УП РАН Method for producing a composite photocatalyst based on carbon nitride and titanium dioxide, active under the action of electromagnetic radiation in the visible and ultraviolet range
CN113117721B (en) * 2021-04-19 2022-12-23 中国科学技术大学 Cyano-functionalized g-C 3 N 4 Colloidal catalyst, preparation method and application thereof
CN113976157A (en) * 2021-10-19 2022-01-28 新乡医学院 Three-dimensional porous in-situ carbon-doped g-C3N4Process for preparing catalyst

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WO2008006935A3 (en) * 2006-07-13 2008-04-17 Carbodeon Ltd Oy Carbon nitride preparation method
US7807124B2 (en) 2006-07-13 2010-10-05 Carbodeon Ltd. Oy Carbon nitride preparation method
DE102009005095A1 (en) 2009-01-19 2010-07-22 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Process for the preparation of carbonitrides via polycondensation or sol-gel processes using hydrogen-free isocyanates
CN103265547A (en) * 2013-05-15 2013-08-28 陆希峰 Miller amino carbon nitrogen compound nanoparticles and diesel engine oil composition containing same
CN103265547B (en) * 2013-05-15 2015-06-24 陆希峰 Miller amino carbon nitrogen compound nanoparticles and diesel engine oil composition containing same
CN110745793A (en) * 2019-09-11 2020-02-04 中国地质大学（武汉） Steam assisted preparation of g-C3N4Method of nanosheet

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EP1874684A1 (en) 2008-01-09
EP1874684B1 (en) 2014-09-17
US20090202419A1 (en) 2009-08-13
RU2005104194A (en) 2006-07-27
RU2288170C2 (en) 2006-11-27
US7708971B2 (en) 2010-05-04
EP1874684A4 (en) 2010-02-10

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