EP1874683A1 - Procede de production de nitrure de carbone - Google Patents

Procede de production de nitrure de carbone

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Publication number
EP1874683A1
EP1874683A1 EP06707616A EP06707616A EP1874683A1 EP 1874683 A1 EP1874683 A1 EP 1874683A1 EP 06707616 A EP06707616 A EP 06707616A EP 06707616 A EP06707616 A EP 06707616A EP 1874683 A1 EP1874683 A1 EP 1874683A1
Authority
EP
European Patent Office
Prior art keywords
carbon nitride
heat treatment
products
reaction mixture
ppm
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.)
Withdrawn
Application number
EP06707616A
Other languages
German (de)
English (en)
Inventor
Jürgen Meyer
Jochen Glaser
Katharina Gibson
Sonja Tragl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eberhard Karls Universitaet Tuebingen
Original Assignee
Eberhard Karls Universitaet Tuebingen
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.)
Filing date
Publication date
Application filed by Eberhard Karls Universitaet Tuebingen filed Critical Eberhard Karls Universitaet Tuebingen
Publication of EP1874683A1 publication Critical patent/EP1874683A1/fr
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to a process for the preparation of carbon nitrides, in particular of carbon nitrides, which have a stoichiometric ratio of C to N between 3: 4 and 3: 4.4.
  • the compound C 3 N 4 was first introduced by Franklin in 1922 by presenting a condensed, layered carbon-nitrogen ring system as a structural model (EC Franklin, J. Am. Chem. Soc. 1922, 44, 507). , Subsequent theoretical work, for example, by Cohen (ML Cohen, Phys.Rev. 1985, B32, 7988), Liu (AY Liu, ML Cohen, Science 1989, 245, 841, Phys. Rev.
  • C 3 N 4 Due to the predicted interesting properties of C 3 N 4 , considerable preparative efforts have been made in recent years to produce C 3 N 4 .
  • many of the processes known from the prior art for the production of carbon nitrides of the ideal composition C 3 N 4 are associated with high expenditure on equipment and are not suitable for the production of relatively large amounts.
  • products were always obtained with properties which indicated that the preparations obtained were not pure or not were uniform.
  • the infrared spectra of many products from hitherto known production methods show strong N-V bands in the range from 3000 to 4000 cm -1 .
  • a possible precursor compound for the production of C3N 4 is C 3 N 3 (NH 2 ) 3 (melamine), which is known in the art Autoclave at 500 ° C.
  • the C- and N-containing films are produced by thermal decomposition of the starting materials in a CVD apparatus (Chemical Vapor Deposition). Carbon nitrides produced by the process contain several percent oxygen.
  • Zhang et. al. report the preparation of another carbon nitride compound that has structural similarity to proposed structures of C 3 N 4 graphitic phases (Zhang, Z. Leinenweber, K., Bauer, M. Garvie, L .; McMillan, P. Wolf , G., J. Am. Chem, Soc., 2001, 123, 7788-7796).
  • the prepared compound has the formal composition C 6 N 9 H 3 * HCl and is described as being crystalline. It is obtained by a decomposition of 2-amino-4,6-dichloro-1,3,5-triazine at temperatures between 500 ° C. and 600 ° C. and at pressures in the range between 1.0 and 1.5 GPa.
  • the object of the present invention is to provide the simplest possible access to carbon nitrides with the ideal composition C 3 N 4 .
  • the method should enable the preparation of such carbon nitrides in larger quantities and in particular lead to a very uniform product with the lowest possible levels of impurities.
  • the invention proposes a method with the features of claim 1.
  • Preferred embodiments of the method according to claim 1 are described in the dependent claims 2 to 18.
  • carbonitrides having the features of claims 19 and 20, the preferred embodiments of which are described in claims 21 to 28.
  • the use of the carbon nitrides according to the invention according to the independent claim 29 is also the subject of this invention.
  • the wording of all claims is hereby incorporated by reference into the content of this specification.
  • the process according to the invention comprises a heat treatment of a substituted triazine compound of the formula C 3 N 3 XXXNH 2 ).
  • the variables X and X 'in the formula each denote a halogen atom (fluoro) - A -
  • a reaction mixture forms, i.a. contains the volatile by-products HX and HX '.
  • the process further comprises substantially complete separation of by-products HX and HX 'from the reaction mixture.
  • the process produces, in particular, carbonitrides which have a stoichiometric ratio of C to N of between 3: 4 and 3: 4.4, in particular between 3: 4 and 3: 4.2.
  • the substituted triazine compound is preferably present as a monomeric starting compound.
  • 2-amino-4,6-dichloro-1,3,5-triazine is preferred as the starting compound.
  • the heat treatment comprises a pretreatment preceding a main treatment of the substituted triazine compound.
  • the pretreatment comprises heating the starting compound to a pretreatment temperature, lingering at this pretreatment temperature, and then cooling to room temperature.
  • the pretreatment temperature is preferably in the range between 200 ° C. and 450 ° C., in particular between 300 ° C. and 400 ° C.
  • the duration of the residence is basically an uncritical parameter, but is preferably not less than 1 h.
  • a residence time at the pretreatment temperature is usually between 12 h and 48 h.
  • the pretreatment forms a reaction mixture which, in contrast to the starting compound, preferably the monomerically present substituted triazine compound, is much more difficult to sublime at high temperatures. It is assumed that the monomeric starting compound is partially dimerized or oligomerized as part of the pretreatment, with the formation of relatively high molecular weight, hardly sublimable condensates.
  • the main treatment preferably comprises heating the starting compound or, where appropriate, the reaction mixture resulting from the pretreatment to a main treatment temperature, lingering at this main treatment temperature and cooling to room temperature.
  • the main treatment temperature is preferably in the range between 400 0 C and 600 ° C, in particular between 450 0 C and 550 0 C.
  • the duration of the dwell in the main treatment temperature is also generally not critical and is preferably not less than 1 h. Retention periods of up to several days are possible.
  • the heat treatment of the substituted triazine compound is preferably carried out in a gas-tight container, in particular in an autoclave or in a glass ampoule.
  • a gas-tight container in particular in an autoclave or in a glass ampoule.
  • this is evacuated after filling with the substituted triazine compound and then sealed.
  • the preferred glass ampoules are designed for a maximum internal pressure of 20 bar to 30 bar. Above this pressure, they burst.
  • the heat treatment comprises at least one repetition of the main treatment.
  • a reaction mixture obtained from a pretreatment or from a main treatment is homogenized before each further main treatment. This is done in particular by triturating the mixture to a powder. The trituration is preferably carried out under exclusion of air.
  • the reaction mixture is preferably triturated under solvent, preferably under an organic solvent or solvent mixture, in particular under diethyl ether, ethanol and / or acetone.
  • by-products HX and HX ' are separated from the reaction mixture after each pretreatment and main treatment. If necessary, further by-products are removed as well.
  • the separation of the by-products HX and HX ' preferably comprises a washing of the reaction mixture with a solvent.
  • the reaction mixture is preferably triturated, analogously to the above-described homogenization, under a solvent or under a solvent mixture (preferably organic solvents or solvent mixtures, in particular diethyl ether, ethanol and / or acetone). If another main treatment is followed by the separation, the washing process described here and the process of homogenization described above are identical to one another.
  • the removal of the by-products HX and HX ' should preferably also be understood to mean the release of these by-products, provided they are free.
  • the volatile or gaseous by-products formed during the heat treatment can be allowed to escape, for example, when the gas-tight container is opened.
  • the volatile by-products HX and HX ' are continuously separated from the reaction mixture during the heat treatment.
  • the continuous separation of the volatile by-products is preferably realized by means of negative pressure.
  • the heat treatment is carried out in an evacuated quartz tube or other suitable receptacle connected to a vacuum source (as is the case, for example, in a chemical vapor deposition (CVD) apparatus). Resulting volatile by-products can be separated continuously from such a container. Repeated main treatments followed by separation of the by-products formed (see above) are generally unnecessary in this procedure to achieve the fullest possible conversion.
  • the heat treatment be carried out with the utmost exclusion of oxygen and water. Although this is not absolutely necessary, it has positive effects on the yield and on the purity of the carbon nitrides produced.
  • the heat treatment of the triazine compound is under Addition of a catalyst made.
  • a catalyst metal halides are preferably used.
  • the Lewis acid AICI 3 has proven to be a suitable catalyst.
  • a suitable catalyst such as AICI 3 makes it possible to carry out the heat treatment at much lower temperatures than is the case without a catalyst.
  • the heat treatment with addition of a catalyst at temperatures between 25 ° C and 600 0 C, preferably between 25 0 C and 400 0 C, in particular between 25 0 C and 250 0 C, made.
  • the reaction of substituted triazine compounds to carbon nitrides by the process according to the invention generally proceeds approximately quantitatively. Usually, yields of more than 90% are achieved. Carbonitrides having a substantially uniform elemental composition are reproducibly obtained.
  • the invention likewise relates to carbonitrides which are prepared or can be prepared by the process according to the invention. These preferably have a stoichiometric ratio of C to N between 3: 4 and 3: 4.4, in particular between 3: 4 and 3: 4.2.
  • carbon nitrides according to the invention have a proportion of hydrogen of not more than 0.8% by weight determined by elemental analysis (the term elemental analysis is to be understood here as C, H, N combustion analysis).
  • carbonitrides according to the invention are free of hydrogen.
  • the infrared spectrum of carbon nitrides according to the invention has no NH oscillation bands in the range between 3000 cm -1 and 4000 cm -1 .
  • a carbon nitride according to the invention preferably has a chlorine content of not more than 4% by weight determined by elemental analysis.
  • the proportion of chlorine is not more than 2 wt .-%, in particular, a carbon nitride according to the invention is substantially free of chlorine.
  • a carbon nitride according to the invention preferably has a content of oxygen, determined by elemental analysis, of not more than 2% by weight.
  • the proportion of oxygen is not more than 1 wt .-%, in particular, a carbon nitride according to the invention is substantially free of oxygen.
  • a carbon nitride according to the invention preferably shows no further signals except for a signal in the range between 153 ppm and 159 ppm and in the range between 161 ppm and 167 ppm.
  • the chemical shifts of the signals are related to tetramethylsilane (TMS).
  • a carbon nitride according to the invention in the 13 C solid-state NMR spectrum particularly preferably in each case shows a signal at 156 ppm and one at 164 ppm.
  • a carbon nitride according to the invention is present as a powder.
  • a carbon nitride according to the invention is equally preferred when it is present as a coating.
  • the carbon nitrides according to the invention can be used as precursor or
  • the compounds produced by the process according to the invention have further properties which make their use particularly advantageous in a wide variety of fields, e.g. in the manufacture of lightweight or composite materials, as hydrogen or energy storage, as electrode materials, solid-state electrolytes, (Li-ion) batteries, micro- or nanoelectronic components, optical components (photonic crystals), sensors, fuel cells, membranes and filters with pores in the nm or pm range or as (metal-coated) catalysts.
  • P- or n-type dopants allow the use as semiconductors or semiconducting layers, metallic conductors or superconductors in the construction of electronic components. In this case, the properties can change by reversible incorporation of atoms or electrochemical incorporation of ions, whereby applications such. as electronic switches or optical displays can result.
  • Fig. 1 shows the differential thermal analysis of the course of the reaction in the inventive treatment of C 3 N 3 Cl 2 (NHa) in a closed ampule.
  • the endothermic effect at about 235 0 C corresponds to the melting of C 3 N 3 Cl 2 (NH 2 ).
  • two further thermal effects can be recognized, one between 160 ° C. and 180 ° C., the other at approximately 245 ° C.
  • Fig. 2 shows about 150 mg of carbon nitride powder, which was obtained by the method according to the invention.
  • Fig. 3 shows an infrared spectrum of carbon nitride according to the invention, which was obtained according to Embodiment 1.
  • Fig. 4 shows an infrared spectrum of carbon nitride according to the invention, which was obtained according to Embodiment 2.
  • FIG. 5 shows a 13 C solid-state NMR spectrum of carbon nitride according to the invention. Only 2 signals can be seen, one at 155.81 ppm, the other at 164.1 ppm. The chemical shifts are related to TMS.
  • FIG. 6 shows the result of a thermogravimetric investigation of carbon nitride according to the invention in the N 2 stream.
  • the residue was filled into a silica glass ampule. This was evacuated, sealed and slowly heated to 500 0 C. The ampoule was left at 500 ° C. for about 12 h, and after cooling to room temperature, the product was rehydrated under ether, which was then decanted.
  • the carbon nitride according to the invention was obtained in the form of a brittle, yellow-brown powder.
  • the composition of the obtained powder was determined by a combustion analysis (CHN).
  • CHN combustion analysis
  • the starting material used was X-ray-pure 2-amino-4,6-dichloro-1,3,5-triazine (ADT), which was prepared by reacting cyanuric chloride (Aldrich, 99%) dissolved in diethyl ether (Merck, 99%) with ammonia gas (BASF ) was produced.
  • the reaction aid used was AICI 3 (alpha, 99.99%, ultra-dry). 575 mg ADT and 9.3 mg AICI 3 were placed under an inert gas in an autoclave. This was heated after closing to about 210 0 C and left for 48 h at this temperature. After cooling, any residual pressure that may occur is released. After opening the autoclave, the brittle, yellow to brown reaction product was triturated under diethyl ether. The ether was then decanted.
  • the product was repeatedly triturated with solvent until no more substance went into solution.
  • the product thus obtained was pushed in a boat into a quartz tube, which was subsequently evacuated. Once the final vacuum (in the range from about 10 "2 to 10 '3 mbar) was reached, the mixture was heated to about 500 ° C. This temperature and the vacuum were kept for about 16 hours subjected further workup of an elemental analysis.
  • the formal composition of the material thus obtained was determined to be C 3 N 4 , i 4 ⁇ o, o 6 Cl o, o 4 .
  • the starting material used was X-ray-pure 2-amino-4,6-dichloro-1,3,5-triazine (ADT), which was prepared by reacting cyanuric chloride (Aldrich, 99%) dissolved in diethyl ether (Merck, 99%) with ammonia gas (BASF ) was produced.
  • ADT X-ray-pure 2-amino-4,6-dichloro-1,3,5-triazine
  • a silica glass ampoule about 10 mg ADT and a glass slide are given.
  • the vial is evacuated, sealed and slowly heated to 500 0 C. The temperature is held for 48 h, then cooled to room temperature and the vial opened. On the glass plate has deposited a few microns thick layer of carbon nitride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé comprenant un traitement thermique d'une triazine substituée de formule C3N3XX'(NH2). Les variables X et X' dans la formule représentent respectivement un atome d'halogène (fluor, chlore, brome ou iode) ou un groupe azide. Un mélange réactionnel contenant entres autres les sous-produits volatils HX et HX' est formé lors du traitement thermique. Le procédé selon l'invention comprend par ailleurs une étape consistant à séparer sensiblement totalement du mélange réactionnel les sous-produits HX et HX' formés. Ce procédé permet de produire en particulier des nitrures de carbone présentant un rapport stoechiométrique entre C et N compris entre 3:4 et 3:4,4.
EP06707616A 2005-03-24 2006-03-21 Procede de production de nitrure de carbone Withdrawn EP1874683A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510014590 DE102005014590A1 (de) 2005-03-24 2005-03-24 Verfahren zur Herstellung von Kohlenstoffnitrid
PCT/EP2006/002551 WO2006100022A1 (fr) 2005-03-24 2006-03-21 Procede de production de nitrure de carbone

Publications (1)

Publication Number Publication Date
EP1874683A1 true EP1874683A1 (fr) 2008-01-09

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EP06707616A Withdrawn EP1874683A1 (fr) 2005-03-24 2006-03-21 Procede de production de nitrure de carbone

Country Status (3)

Country Link
EP (1) EP1874683A1 (fr)
DE (1) DE102005014590A1 (fr)
WO (1) WO2006100022A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009005095A1 (de) 2009-01-19 2010-07-22 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Verfahren zur Herstellung von Carbonitriden über Polykondensations- bzw. Sol-Gel-Verfahren unter Verwendung Wasserstoff-freier Isocyanate

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
US5606056A (en) * 1994-05-24 1997-02-25 Arizona Board Of Regents Carbon nitride and its synthesis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006100022A1 *

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WO2006100022A1 (fr) 2006-09-28
DE102005014590A1 (de) 2006-09-28

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