JP2005089264A - Carbon nitride substance containing metal and its manufacturing method, and hydrogen occlusion material - Google Patents
Carbon nitride substance containing metal and its manufacturing method, and hydrogen occlusion material Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000463 material Substances 0.000 title abstract description 3
- 239000000126 substance Substances 0.000 title abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000000470 constituent Substances 0.000 claims abstract description 17
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims abstract description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000011232 storage material Substances 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 35
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910017961 MgNi Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
Description
本発明は水素吸蔵性能を有する含金属窒化炭素物及びその製造方法、該含金属窒化炭素物からなる水素吸蔵材に関する。 The present invention relates to a metal-containing carbon nitride having hydrogen storage performance, a method for producing the same, and a hydrogen storage material comprising the metal-containing carbon nitride.
近年、主としてエネルギー源としての水素を貯蔵する方法の開発が広く行われている。 In recent years, development of a method for storing hydrogen mainly as an energy source has been widely performed.
従来から行われている水素の貯蔵方法としては、例えば１０〜８０ＭＰａの圧力を水素に加えて高圧水素ボンベに水素を貯蔵する方法、２０Ｋの温度にまで冷却され液化された水素を液体水素ボンベに貯蔵する方法がある。 Conventional hydrogen storage methods include, for example, a method in which a pressure of 10 to 80 MPa is applied to hydrogen to store hydrogen in a high-pressure hydrogen cylinder, and hydrogen that has been cooled and liquefied to a temperature of 20 K is converted into a liquid hydrogen cylinder. There are ways to store.
しかしながら、高圧水素ボンベに水素を貯蔵する方法は、水素ボンベとして用いる容器を高圧力に耐えることができるように肉厚にする必要がある。そのため容器の大きさ、質量が大きくなるという課題がある。また、液体水素ボンベに液化した水素を貯蔵する方法は、温度を２０Ｋ以下にまで冷却して水素を液化しなければならず、また液体水素ボンベに用いる容器は２０Ｋ以下に耐えることができる極低温用の容器にしなければならないという課題がある。さらに、容器を厳重にシールしても液体水素が気化して水素が消失してしまうという課題がある。 However, in the method of storing hydrogen in a high-pressure hydrogen cylinder, the container used as the hydrogen cylinder needs to be thick so that it can withstand high pressure. Therefore, there exists a subject that the magnitude | size and mass of a container become large. The method of storing liquefied hydrogen in a liquid hydrogen cylinder must cool the temperature to 20K or lower to liquefy the hydrogen, and the container used for the liquid hydrogen cylinder can withstand 20K or lower. There is a problem that it must be made into a container for use. Furthermore, even if the container is tightly sealed, there is a problem that liquid hydrogen is vaporized and hydrogen disappears.
近年、別の水素吸蔵方法としてＬａ、Ｍｇ、Ｎｉ等を主成分とする水素吸蔵合金の開発も広く行われている。しかしながらこの方法では、合金への水素の吸蔵量が少ないために単位あたりの水素吸蔵量が大きく取れず、運搬や取扱に課題があった。 In recent years, hydrogen storage alloys mainly composed of La, Mg, Ni and the like have been widely developed as another hydrogen storage method. However, in this method, since the amount of hydrogen stored in the alloy is small, the amount of hydrogen stored per unit cannot be increased, and there is a problem in transportation and handling.
さらに近年、カーボンナノチューブ、カーボンナノファイバー等の炭素系材料が見出された。これらの材料は軽量且つ水素を貯蔵するとされていることから、新規な水素吸蔵方法として注目されている。例えば、特許文献１にはナノサイズとミクロンオーダーの中間的な径を有する新規な炭素化合物が開示されている。しかしながら、この方法ではポリテトラフルオロエチレンを電解還元等の方法によって一旦カルビン系炭素を得、さらに減圧下加熱するという方法であり、合成に手順がかかると同時に生産性が低いという課題があった。 In recent years, carbon-based materials such as carbon nanotubes and carbon nanofibers have been found. Since these materials are light and store hydrogen, they are attracting attention as a novel hydrogen storage method. For example, Patent Document 1 discloses a novel carbon compound having an intermediate diameter between nano size and micron order. However, in this method, polytetrafluoroethylene is obtained by once obtaining carbine carbon by a method such as electrolytic reduction, and further heated under reduced pressure, and there is a problem that the synthesis takes a procedure and productivity is low.
炭素系材料に異種の原子を導入して水素吸蔵性能を高める方法として、特許文献２にカーボンナノチューブにＰｔまたはＰｄを担持させる方法、特許文献３にカーボンナノファイバーにＬｉまたはＫを担持させる方法が開示されている。しかしながら、これらの方法では一旦得られたカーボンナノチューブ、カーボンナノファイバーを担持させるために、合成に手順がかかると同時に生産性が低く、さらに加工が難しいという課題がある。また、室温では用途によっては水素吸蔵性能も必ずしも十分とはいえなかった。 As methods for improving the hydrogen storage performance by introducing different kinds of atoms into the carbon-based material, Patent Document 2 has a method of supporting Pt or Pd on carbon nanotubes, and Patent Document 3 has a method of supporting Li or K on carbon nanofibers. It is disclosed. However, in these methods, since the carbon nanotubes and carbon nanofibers obtained once are supported, a procedure is required for synthesis, and at the same time, productivity is low and further processing is difficult. Further, at room temperature, the hydrogen storage performance is not always sufficient depending on the application.
さらに、炭素系水素吸蔵材が水素を吸蔵するのは例えば４０Ｋの低温であることが多く、冷却等の設備を必要とするために、これらを含めた水素吸蔵設備全体の体積及び質量が大きくなり、実用化のためにはさらに水素吸蔵材の改良が必要であった。 Furthermore, carbon-based hydrogen storage materials often store hydrogen at a low temperature of 40K, for example, and require equipment such as cooling, which increases the volume and mass of the entire hydrogen storage equipment including these. In order to put it to practical use, it was necessary to further improve the hydrogen storage material.
本発明の課題は、上記問題を解決し、常温で優れた水素吸蔵性能を有する水素吸蔵材を提供することにある。 The subject of this invention is providing the hydrogen storage material which solves the said problem and has the outstanding hydrogen storage performance at normal temperature.
本発明の第一は、少なくとも金属と窒素と炭素を構成元素とする含金属窒化炭素物であって、
ラマン散乱スペクトルにおいて、
（Ａ）１５７０〜１５８０ｃｍ-1のバンドのピーク強度（ＩG）と、１３４１〜１３６０ｃｍ-1のバンドのピーク強度（ＩD）の比（ＩG／ＩD）が１未満、
（Ｂ）１５７０〜１５８０ｃｍ-1のバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上であることを特徴とする。
The first of the present invention is a metal-containing carbon nitride containing at least a metal, nitrogen and carbon as constituent elements,
In the Raman scattering spectrum,
(A) and the peak intensity of the bands of 1570~1580cm -1 (I G), the ratio of the peak intensity of the bands of 1341~1360cm -1 (I D) (I G / I D) is less than 1,
(B) The peak of the band of 1570 to 1580 cm −1 is not observed,
Either
The relative abundance ratio (N 1s / C 1s ) of N 1s and C 1s in the X-ray photoelectron spectrum is 0.1 / 100 or more.
本発明の第二は、少なくとも金属と窒素と炭素を構成元素とする含金属窒化炭素物であって、
Ｘ線光電子スペクトルにおいて、
（ａ）３９８〜４００ｅＶのバンドのピーク強度（Ｘt）と４０１〜４０３ｅＶのバンドのピーク強度（Ｘp）の比（Ｘp／Ｘt）が１未満、
（ｂ）３９８〜４００ｅＶのバンドのピークが観察され、４０１〜４０３ｅＶのバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上であることを特徴とする。
The second of the present invention is a metal-containing carbon nitride containing at least metal, nitrogen and carbon as constituent elements,
In the X-ray photoelectron spectrum,
(A) the ratio of the band peak intensity (X t) and the peak intensity of the bands of 401~403eV of 398~400eV (X p) (X p / X t) is less than 1,
(B) A peak of a band of 398 to 400 eV is observed, and a peak of a band of 401 to 403 eV is not observed,
Either
The relative abundance ratio (N 1s / C 1s ) of N 1s and C 1s in the X-ray photoelectron spectrum is 0.1 / 100 or more.
上記本発明の含金属窒化炭素物においては、下記の構成を好ましい態様として含む。
金属と窒素と炭素以外に、構成元素として水素と酸素とを含む化合物である。
構成元素である金属が、金属塩、金属錯体、金属酸化物、半導体、金属単体、及び２種類以上の金属からなる合金の中から選ばれた少なくとも一種の形で存在している。
金属種が、リチウム、ナトリウム、アルミニウム、カリウム、マンガン、鉄、コバルト、ニッケル、銅、ルビジウム、ストロンチウム、パラジウム、銀、セシウム、白金の中から選ばれた少なくとも一種である。
The metal-containing carbon nitride of the present invention includes the following configuration as a preferred embodiment.
It is a compound containing hydrogen and oxygen as constituent elements in addition to metal, nitrogen and carbon.
The constituent metal is present in at least one form selected from metal salts, metal complexes, metal oxides, semiconductors, simple metals, and alloys composed of two or more metals.
The metal species is at least one selected from lithium, sodium, aluminum, potassium, manganese, iron, cobalt, nickel, copper, rubidium, strontium, palladium, silver, cesium, and platinum.
本発明の第三は、上記本発明第一及び／または第二の含金属窒化炭素物からなることを特徴とする水素吸蔵材である。 A third aspect of the present invention is a hydrogen storage material comprising the first and / or second metal-containing carbon nitride of the present invention.
本発明の第四は、本発明第一及び第二の含金属窒化炭素物の製造方法であって、窒化炭素物に金属イオンを含有する水溶液を反応させることを特徴とする。 A fourth aspect of the present invention is the first and second method for producing a metal-containing carbon nitride according to the present invention, wherein the carbon nitride is reacted with an aqueous solution containing metal ions.
本発明の第四の製造方法においては、金属水酸化物を用いて水溶液中に金属イオンを含有させること、及び／または、窒化炭素物に金属イオンを含有する水溶液を反応させた後、加熱処理することが好ましい。 In the fourth production method of the present invention, the metal hydroxide is used to contain metal ions in the aqueous solution, and / or the carbon nitride is reacted with the aqueous solution containing metal ions, followed by heat treatment. It is preferable to do.
本発明によれば、常温での水素吸蔵が可能で単位質量あたりの水素吸蔵量が多く、良好な水素吸蔵材が簡易な製造方法により提供される。 ADVANTAGE OF THE INVENTION According to this invention, hydrogen storage at normal temperature is possible, there are many hydrogen storage amounts per unit mass, and a favorable hydrogen storage material is provided with a simple manufacturing method.
本発明の含金属窒化炭素物は、少なくとも金属と窒素と炭素を構成元素とする化合物であって、下記の〔Ｉ〕、〔ＩＩ〕の少なくとも一方の特性を有することを特徴とする。 The metal-containing carbon nitride of the present invention is a compound having at least metal, nitrogen, and carbon as constituent elements, and has at least one of the following properties [I] and [II].
〔Ｉ〕ラマン散乱スペクトルにおいて、
（Ａ）１５７０〜１５８０ｃｍ-1のバンドのピーク強度（ＩG）と、１３４１〜１３６０ｃｍ-1のバンドのピーク強度（ＩD）の比（ＩG／ＩD）が１未満、
（Ｂ）１５７０〜１５８０ｃｍ-1のバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上である。
[I] In the Raman scattering spectrum,
(A) and the peak intensity of the bands of 1570~1580cm -1 (I G), the ratio of the peak intensity of the bands of 1341~1360cm -1 (I D) (I G / I D) is less than 1,
(B) The peak of the band of 1570 to 1580 cm −1 is not observed,
Either
The relative abundance ratio (N 1s / C 1s ) of N 1s and C 1s in the X-ray photoelectron spectrum is 0.1 / 100 or more.
〔ＩＩ〕Ｘ線光電子スペクトルにおいて、
（ａ）３９８〜４００ｅＶのバンドのピーク強度（Ｘt）と４０１〜４０３ｅＶのバンドのピーク強度（Ｘp）の比（Ｘp／Ｘt）が１未満、
（ｂ）３９８〜４００ｅＶのバンドのピークが観察され、４０１〜４０３ｅＶのバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上である。
[II] In the X-ray photoelectron spectrum,
(A) the ratio of the band peak intensity (X t) and the peak intensity of the bands of 401~403eV of 398~400eV (X p) (X p / X t) is less than 1,
(B) A peak of a band of 398 to 400 eV is observed, and a peak of a band of 401 to 403 eV is not observed,
Either
The relative abundance ratio (N 1s / C 1s ) of N 1s and C 1s in the X-ray photoelectron spectrum is 0.1 / 100 or more.
本発明の含金属窒化炭素物中における窒素と炭素の含有量は特に制約はないが、好ましくは含金属窒化炭素物を構成する元素から金属と水素と酸素を除いた元素の総質量中の窒素と炭素の含有量が５０質量％以上、さらに好ましくは７０質量％以上である。最も好ましくは１００質量％である。該含有量が５０質量％未満の場合は、含金属窒化炭素物が十分な水素吸蔵性能を示さない場合があり好ましくない。 The nitrogen and carbon contents in the metal-containing carbon nitride of the present invention are not particularly limited, but preferably nitrogen in the total mass of elements excluding metal, hydrogen and oxygen from the elements constituting the metal-containing carbon nitride. The carbon content is 50% by mass or more, more preferably 70% by mass or more. Most preferably, it is 100 mass%. When the content is less than 50% by mass, the metal-containing carbon nitride may not exhibit sufficient hydrogen storage performance, which is not preferable.
本発明の含金属窒化炭素物は、構成元素として少なくとも金属と窒素と炭素を有していれば良いが、これら以外の元素を含んでいても差し支えない。例えば、窒化炭素物に直接結合している水素、窒化炭素物に水酸基として結合している水素及び酸素等が挙げられる。また、構成元素として、ホウ素及びケイ素以外の元素を含んでいるものも好ましい。中でも、水素と酸素のみを他の構成元素として含んでいる含金属窒化炭素物が特に好ましい。金属、水素と酸素以外の構成元素を含んでいる含金属窒化炭素物の場合、構成元素によっては十分な水素吸蔵性能を示さないことがあり好ましくないものもある。 The metal-containing carbon nitride of the present invention only needs to contain at least metal, nitrogen, and carbon as constituent elements, but may contain other elements. For example, hydrogen directly bonded to the carbon nitride, hydrogen and oxygen bonded to the carbon nitride as a hydroxyl group, and the like can be given. Moreover, what contains elements other than boron and silicon as a constituent element is also preferable. Among these, a metal-containing carbon nitride containing only hydrogen and oxygen as other constituent elements is particularly preferable. In the case of a metal-containing carbon nitride containing a constituent element other than metal and hydrogen and oxygen, depending on the constituent element, a sufficient hydrogen occlusion performance may not be exhibited, which is not preferable.
本発明の含金属窒化炭素物においては、適当量の窒素を有していない場合は十分な水素吸蔵性を示さない。本発明の含金属窒化炭素物中における窒素と炭素の存在比はＸ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）で示される。本発明においては該比が０．１／１００以上が好ましく、さらに好ましくは３／１００以上である。一方、Ｎ1s／Ｃ1s比は１００／１００以下であることが好ましい。Ｎ1s／Ｃ1s比が１００／１００を超えると、場合によっては十分な水素吸蔵性能を示さないことがあり好ましくない。 The metal-containing carbon nitride of the present invention does not exhibit sufficient hydrogen storage properties when it does not have an appropriate amount of nitrogen. The abundance ratio of nitrogen and carbon in the metal-containing carbon nitride of the present invention is represented by the relative abundance ratio of N 1s and C 1s (N 1s / C 1s ) in the X-ray photoelectron spectrum. In the present invention, the ratio is preferably 0.1 / 100 or more, more preferably 3/100 or more. On the other hand, the N 1s / C 1s ratio is preferably 100/100 or less. When the N 1s / C 1s ratio exceeds 100/100, it is not preferable because sufficient hydrogen storage performance may not be exhibited in some cases.
本発明の含金属窒化炭素物中の金属量は特に制約はないが、好ましくは含金属窒化炭素物中の金属質量比で０．０１質量％以上５０質量％以下である。含金属窒化炭素物中の金属質量比が０．０１質量％未満の場合は、窒化炭素物中に金属を含有する効果に乏しく、含金属窒化炭素物中の金属質量比が５０質量％を超える場合は、窒化炭素物による水素吸蔵性能の効果に乏しく好ましくない。 The amount of metal in the metal-containing carbon nitride of the present invention is not particularly limited, but is preferably 0.01% by mass or more and 50% by mass or less in terms of the metal mass ratio in the metal-containing carbon nitride. When the metal mass ratio in the metal-containing carbon nitride is less than 0.01% by mass, the effect of containing a metal in the carbon nitride is poor, and the metal mass ratio in the metal-containing carbon nitride exceeds 50% by mass. In this case, the effect of the hydrogen storage performance by the carbon nitride is poor, which is not preferable.
本発明の含金属窒化炭素物中の金属は、窒化炭素物中にどのような形で存在していても差し支えないが、金属塩、金属錯体、金属酸化物、半導体、金属単体、２種類以上の金属からなる合金の少なくとも一種の形で存在していることが好ましい。 The metal in the metal-containing carbon nitride of the present invention may be present in any form in the carbon nitride, but metal salts, metal complexes, metal oxides, semiconductors, simple metals, two or more types It is preferable that it exists in the form of at least 1 type of the alloy which consists of these metals.
また、金属種としては、好ましくは、リチウム、ナトリウム、アルミニウム、カリウム、マンガン、鉄、コバルト、ニッケル、銅、ルビジウム、ストロンチウム、パラジウム、銀、セシウム、白金が挙げられる。これら金属種は１種類であってもよいし、２種類以上の金属種からなる金属及び／または金属化合物の混合物、及び／または合金であっても差し支えない。２種類以上の金属種からなる合金の具体例としては、ＴｉＭｎ1.5、ＺｒＶ2、ＺｒＭｎ2、Ｍｇ2Ｎｉ、Ｃａ1-xＭｇxＮｉ2（０≦ｘ≦０．６５）、ＲＭｇ2Ｎｉ9（ＲはＹ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄの少なくとも１種）、Ｌａ2ＭｇＮｉ9、Ｌａ5Ｍｇ2Ｎｉ23、Ｌａ3ＭｇＮｉ14、Ｌａ0.7Ｍｇ3Ｎｉ2.8Ｃｏ0.5等が挙げられる。もちろんこれ以外の合金であっても何ら差し支えない。 Moreover, as a metal seed | species, Preferably, lithium, sodium, aluminum, potassium, manganese, iron, cobalt, nickel, copper, rubidium, strontium, palladium, silver, cesium, platinum is mentioned. These metal species may be one type, or may be a metal and / or a mixture of metal compounds and / or alloys composed of two or more types of metal. Specific examples of the alloy composed of two or more kinds of metal include TiMn 1.5 , ZrV 2 , ZrMn 2 , Mg 2 Ni, Ca 1-x Mg x Ni 2 (0 ≦ x ≦ 0.65), RMg 2 Ni 9. (R is at least one of Y, La, Ce, Pr, Nd, Sm, Gd), La 2 MgNi 9 , La 5 Mg 2 Ni 23 , La 3 MgNi 14 , La 0.7 Mg 3 Ni 2.8 Co 0.5, etc. It is done. Of course, other alloys may be used.
また、本発明の含金属窒化炭素物は、前記した〔Ｉ〕、〔ＩＩ〕の少なくとも一方の特性を有している必要がある。 The metal-containing carbon nitride of the present invention must have at least one of the above-mentioned [I] and [II] characteristics.
本発明の含金属窒化炭素物が、ラマン散乱スペクトルにおいて、１５７０〜１５８０ｃｍ-1のバンドのピークが観察され、且つ、ＩG／ＩDが１以上の場合は含金属窒化炭素物中の窒化炭素部分の結晶性が高くなるために十分な水素吸蔵性能を示さない場合がある。好ましくは、ＩG／ＩDが０．９５未満、或いは１５７０〜１５８０ｃｍ-1のバンドのピークと１３４１〜１３６０ｃｍ-1のバンドのピーク共に観察されない含金属窒化炭素物である。 When the metal-containing carbon nitride of the present invention has a peak of 1570 to 1580 cm −1 in the Raman scattering spectrum and I G / ID is 1 or more, the carbon nitride in the metal-containing carbon nitride In some cases, the crystallinity of the portion is high, so that sufficient hydrogen storage performance is not exhibited. Preferably, an I G / I D is less than 0.95, or band containing metal carbon nitride was not observed in the peak both the peak and 1341～1360Cm -1 band 1570~1580cm -1.
また、本発明の含金属窒化炭素物が、Ｘ線光電子スペクトルにおいて、４０１〜４０３ｅＶのバンドのピークが観察され、且つ、Ｘp／Ｘtが１以上の場合は含金属窒化炭素物中の窒化炭素部分の結晶性が高くなるために十分な水素吸蔵性能を示さない場合がある。好ましくは、Ｘp／Ｘtが０．５以下、或いは３９８〜４００ｅＶのバンドのピークが観察されて、４０１〜４０３ｅＶのバンドのピークが観察されない窒化炭素物である。さらに好ましくは、Ｘp／Ｘtが０．１以下、或いは３９８〜４００ｅＶのバンドのピークが観察されて、４０１〜４０３ｅＶのバンドのピーク、及び３９７〜３９５ｅＶのバンドのピーク共に観察されない窒化炭素物である。 Further, in the metal-containing carbon nitride of the present invention, when a peak of a band of 401 to 403 eV is observed in the X-ray photoelectron spectrum and X p / X t is 1 or more, nitriding in the metal-containing carbon nitride is performed. In some cases, the crystallinity of the carbon portion is high, so that sufficient hydrogen storage performance is not exhibited. Preferred is a carbon nitride in which X p / X t is 0.5 or less, or a peak of a band of 398 to 400 eV is observed, and a peak of a band of 401 to 403 eV is not observed. More preferably, a carbon nitride in which X p / X t is 0.1 or less or a peak of a band of 398 to 400 eV is observed, and a peak of a band of 401 to 403 eV and a peak of a band of 397 to 395 eV is not observed It is.
本発明の含金属窒化炭素物におけるＸp／Ｘtの値は製造条件によって任意に変更することができる。具体的には、原料の種類、原料の濃度、反応時間、複数の原料を使用する場合はその濃度比、製造時の温度、触媒を用いる場合は触媒の種類等が挙げられる。 The value of X p / X t in the metal-containing carbon nitride of the present invention can be arbitrarily changed depending on the production conditions. Specific examples include the type of raw material, the concentration of the raw material, the reaction time, the concentration ratio when a plurality of raw materials are used, the temperature during production, the type of catalyst when a catalyst is used, and the like.
例えば原料としてアセトニトリルを用い、熱分解法で本発明の含金属窒化炭素物を合成する場合は、原料供給速度が高いほどＸp／Ｘtは小さくなる傾向にある。また、反応時間が短いほどＸp／Ｘtは小さくなる傾向にある。しかしながら、これらの反応条件及びその傾向は、原料の種類等の反応条件そのもの以外の条件によって左右される場合がある。従って、ここに記載された条件とは異なった条件でＸp／Ｘtを変更しても何等差し支えない。 For example, when acetonitrile is used as a raw material and the metal-containing carbon nitride of the present invention is synthesized by a thermal decomposition method, X p / X t tends to decrease as the raw material supply rate increases. Further, X p / X t tends to be smaller as the reaction time is shorter. However, these reaction conditions and their tendency may depend on conditions other than the reaction conditions themselves such as the type of raw material. Accordingly, there is no problem even if X p / X t is changed under conditions different from those described here.
本発明の含金属窒化炭素物を製造する方法は、従来公知の方法、すなわち熱分解法、化学蒸着法（ＣＶＤ法）、物理蒸着法（ＰＶＤ法）、イオンプレーティング法、スパッタリング法、分子線エピタキシー法、電気分解法等いずれであっても差し支えない。また、金属を含まない窒化炭素物、及び／または含金属窒化炭素物を熱分解法、化学蒸着法（ＣＶＤ法）、物理蒸着法（ＰＶＤ法）、イオンプレーティング法、スパッタリング法、分子線エピタキシー法、電気分解法等の従来公知の方法で製造した後、金属及び／または金属化合物を物理的混合、蒸着、鍍金、スパッタリング、ディッピング、ＣＶＤ、ＰＶＤ等の従来公知の方法で後処理する方法が用いられる。勿論その他の方法であっても、本発明の含金属窒化炭素物を得ることができればいずれの方法であっても差し支えない。 The method for producing the metal-containing carbon nitride of the present invention is a conventionally known method, that is, thermal decomposition method, chemical vapor deposition method (CVD method), physical vapor deposition method (PVD method), ion plating method, sputtering method, molecular beam. Either an epitaxy method or an electrolysis method may be used. In addition, carbon nitride not containing metal and / or metal-containing carbon nitride is pyrolyzed, chemical vapor deposition (CVD), physical vapor deposition (PVD), ion plating, sputtering, molecular beam epitaxy. A method in which a metal and / or metal compound is post-treated by a conventionally known method such as physical mixing, vapor deposition, plating, sputtering, dipping, CVD, PVD, etc. Used. Of course, any other method can be used as long as the metal-containing carbon nitride of the present invention can be obtained.
好ましくは、含金属窒化炭素物を熱分解法、化学蒸着法（ＣＶＤ法）、イオンプレーティング法、分子線エピタキシー法により得る方法である。さらに好ましくは、熱分解法、ＣＶＤ法であり、特に好ましくは、熱分解法、マイクロ波プラズマＣＶＤ法、電子サイクロトロン共鳴プラズマＣＶＤ法である。 Preferably, the metal-containing carbon nitride is obtained by thermal decomposition, chemical vapor deposition (CVD), ion plating, or molecular beam epitaxy. More preferred are a thermal decomposition method and a CVD method, and particularly preferred are a thermal decomposition method, a microwave plasma CVD method and an electron cyclotron resonance plasma CVD method.
また、金属を含有しない窒化炭素物、及び／または含金属窒化炭素物を金属イオンを含有する水溶液と反応させる方法もまた好ましい。さらに好ましくは、金属を含有しない窒化炭素物、及び／または含金属窒化炭素物を金属水酸化物の水溶液で反応させる方法である。特に好ましくは、金属を含有しない窒化炭素物、及び／または含金属窒化炭素物を金属水酸化物の水溶液で反応させた後、加熱処理等の後処理を行う方法である。 Also preferred is a method of reacting a carbon nitride not containing metal and / or a metal-containing carbon nitride with an aqueous solution containing metal ions. More preferred is a method in which a metal-free carbon nitride and / or a metal-containing carbon nitride is reacted with an aqueous solution of a metal hydroxide. Particularly preferred is a method in which a metal-free carbon nitride and / or a metal-containing carbon nitride is reacted with an aqueous solution of a metal hydroxide, followed by post-treatment such as heat treatment.
本発明の含金属窒化炭素物の形状はいずれであっても差し支えない。好ましくは、膜状、薄片状、繊維状、針状である。 The shape of the metal-containing carbon nitride of the present invention may be any. Preferably, it is a film shape, a flake shape, a fiber shape, or a needle shape.
本発明の含金属窒化炭素物を得る際に、反応速度や反応収率を高くする目的で適宜触媒を添加しても差し支えない。好ましい触媒としては、例えばＦｅ、Ｃｏ、Ｎｉ、Ｖ、Ｎｂ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｌａ等の金属及びこれら金属化合物が挙げられる。勿論、触媒作用を示しさえすればこれら以外の化合物が触媒として使用されても差し支えない。また、触媒を使用する場合は、触媒は１種で用いられても２種以上で用いられてもいずれであっても差し支えない。 When obtaining the metal-containing carbon nitride of the present invention, a catalyst may be appropriately added for the purpose of increasing the reaction rate and reaction yield. Preferred examples of the catalyst include metals such as Fe, Co, Ni, V, Nb, Cr, Mo, W, Mn, Tc, Re, and La, and these metal compounds. Of course, other compounds may be used as the catalyst as long as they exhibit catalytic action. When a catalyst is used, the catalyst may be used alone or in combination of two or more.
本発明の含金属窒化炭素物を得るための原料物質は特に限定されないが、例えば、グラファイト、ダイヤモンド、フラーレン、カーボンナノチューブ、カルビン等の炭素材及びそれ以外の実質的に炭素のみを構成元素とする炭素材、一酸化炭素、二酸化炭素等の炭素酸化物、アルカン、アルケン、アルキン等の炭化水素、ベンゼン、トルエン等の芳香族炭水化物、アルコール、ケトン、カルボン酸等の炭素と水素と酸素を含む化合物、その他有機化合物、窒素ガス、アンモニア、一酸化窒素、二酸化窒素等の窒素酸化物、その他窒素を構成原子として含む化合物、分子中に窒素原子と炭素原子を少なくとも１個以上含有している化合物の中から少なくとも１種が選ばれる。 The raw material for obtaining the metal-containing carbon nitride of the present invention is not particularly limited. For example, carbon materials such as graphite, diamond, fullerene, carbon nanotube, and calvin, and other substantially carbon as a constituent element. Carbon materials, carbon oxides such as carbon monoxide and carbon dioxide, hydrocarbons such as alkanes, alkenes and alkynes, aromatic carbohydrates such as benzene and toluene, compounds containing carbon, hydrogen and oxygen such as alcohols, ketones and carboxylic acids , Other organic compounds, nitrogen gas, ammonia, nitrogen oxides such as nitrogen monoxide and nitrogen dioxide, other compounds containing nitrogen as a constituent atom, compounds containing at least one nitrogen atom and carbon atom in the molecule At least one type is selected from the inside.
好ましくは、分子中に窒素原子と炭素原子を少なくとも１個以上含有している化合物である。具体例としては、飽和脂肪族アミン類、不飽和脂肪族アミン類、芳香族アミン類、環式アミン類、脂環式アミン類、飽和脂肪族イミン類、脂環式イミン類、芳香族イミン類、環式イミン類、飽和脂肪族シアン化物、不飽和脂肪族シアン化物、脂環式シアン化物、芳香族シアン化物、ハロゲン化シアン化物、窒素含有複素環芳香族化合物及びその誘導体、さらに置換ヒドラジンやアゾベンゼンのように窒素窒素結合を有するものも含まれる。さらに好ましくは、アセトニトリル、プロピオニトリル等の飽和脂肪族シアン化物、臭化ニトリル等のハロゲン化シアン化物が挙げられる。 Preferably, it is a compound containing at least one nitrogen atom and carbon atom in the molecule. Specific examples include saturated aliphatic amines, unsaturated aliphatic amines, aromatic amines, cyclic amines, alicyclic amines, saturated aliphatic imines, alicyclic imines, aromatic imines. , Cyclic imines, saturated aliphatic cyanides, unsaturated aliphatic cyanides, alicyclic cyanides, aromatic cyanides, halogenated cyanides, nitrogen-containing heterocyclic aromatic compounds and derivatives thereof, and substituted hydrazines Those having a nitrogen-nitrogen bond such as azobenzene are also included. More preferable examples include saturated aliphatic cyanides such as acetonitrile and propionitrile, and halogenated cyanides such as nitrile bromide.
図１に、本発明の含金属窒化炭素物の製造装置の一例の概略構成図を示す。図中、１は窒素供給源、２は原料供給源、３は配管、４は反応管、５は流量計、６、７は加熱装置、１１は触媒容器、１２は触媒である。 In FIG. 1, the schematic block diagram of an example of the manufacturing apparatus of the metal-containing carbon nitride of this invention is shown. In the figure, 1 is a nitrogen supply source, 2 is a raw material supply source, 3 is piping, 4 is a reaction tube, 5 is a flow meter, 6 and 7 are heating devices, 11 is a catalyst container, and 12 is a catalyst.
図１の装置においては、原料キャリアガス気体としての窒素供給源１と、原料供給源２と、反応管４と、キャリアガス及び原料を反応管４に導入するための配管３と、原料供給源２を加熱するためのヒーター６と、反応管４を加熱するためのヒーター７とで構成されている。原料の供給は、配管３に取り付けられた流量計５及び原料供給源２を加熱するためのヒーター６の温度により制御される。原料を反応管４内に導入し、反応管４を加熱するためのヒーター７の温度が所定の温度になるように制御する。反応管４内には、必要に応じて、図１に示すように、触媒１２を容器１１に入れて配置する。 In the apparatus of FIG. 1, a nitrogen supply source 1 as a raw material carrier gas, a raw material supply source 2, a reaction tube 4, a pipe 3 for introducing the carrier gas and the raw material into the reaction tube 4, and a raw material supply source 2 is composed of a heater 6 for heating 2 and a heater 7 for heating the reaction tube 4. The supply of the raw material is controlled by the flow meter 5 attached to the pipe 3 and the temperature of the heater 6 for heating the raw material supply source 2. The raw material is introduced into the reaction tube 4 and the temperature of the heater 7 for heating the reaction tube 4 is controlled to be a predetermined temperature. In the reaction tube 4, as shown in FIG. 1, a catalyst 12 is placed in a container 11 as necessary.
本発明の含金属窒化炭素物は、良好な水素吸蔵性能を有し、水素吸蔵材として好ましく利用できる。 The metal-containing carbon nitride of the present invention has good hydrogen storage performance and can be preferably used as a hydrogen storage material.
本発明の含金属窒化炭素物のラマン散乱スペクトルにおけるＩG／ＩDの測定方法、Ｘ線光電子スペクトルによるＸp／Ｘt、及びＮ1s／Ｃ1sの測定方法について説明する。 A method for measuring I G / ID in the Raman scattering spectrum of the metal-containing carbon nitride of the present invention, and a method for measuring X p / X t and N 1s / C 1s by the X-ray photoelectron spectrum will be described.
［ラマン散乱スペクトルの測定方法］
日本分光社製ＮＲ−１００を用い、レーザー波長５１４．５ｎｍ、測定電力１５０ｍＷ、測定時間２秒、分析径３００μｍで測定を行う。またピーク強度は、ＮＲ−１００に装備されたピーク面積分割ソフトを用い、１５７０〜１５８０ｃｍ-1にピークを持つバンドと１３４１〜１３６０ｃｍ-1にピークを持つバンドを分割し、算出されたバンドの面積を当該バンドの強度としてＩG／ＩDを算出する。
[Measurement method of Raman scattering spectrum]
Measurement is performed using a NR-100 manufactured by JASCO Corporation with a laser wavelength of 514.5 nm, a measurement power of 150 mW, a measurement time of 2 seconds, and an analysis diameter of 300 μm. The peak intensity is calculated by dividing the band having a peak at 1570 to 1580 cm −1 and the band having a peak at 1341 to 1360 cm −1 by using the peak area dividing software equipped in NR-100. Is calculated as I G / ID .
［Ｘ線光電子スペクトルの測定方法］
パーキン・エルマー社製Ｘ線光電子分光装置ＰＨＩ−５６００を用い、励起Ｘ線としてＡｌＫα１４８６．６ｅＶを用い、Ｘ線出力１０ｋＶ、２０ｍＡ、温度４０℃、真空度１．３３×１０-4Ｐａ、分析径８００μｍで測定を行う。尚、試料は測定前にアルゴンにより１２秒間スパッタ処理を行う。
[Measurement method of X-ray photoelectron spectrum]
Using an X-ray photoelectron spectrometer PHI-5600 manufactured by Perkin Elmer, using AlKα1486.6 eV as excitation X-ray, X-ray output 10 kV, 20 mA, temperature 40 ° C., vacuum 1.33 × 10 −4 Pa, analysis diameter Measurement is performed at 800 μm. The sample is sputtered with argon for 12 seconds before measurement.
また、ピーク強度は、ＰＨＩ−５６００に装備されたピーク面積分割ソフトを用い、所定のバンドを分割し、算出されたバンドの面積を当該バンドの強度としてＸp／Ｘt、及びＮ1s／Ｃ1sを算出する。 Further, the peak intensity is obtained by dividing a predetermined band using the peak area dividing software installed in PHI-5600, and using the calculated band area as the intensity of the band, X p / X t and N 1s / C Calculate 1s .
［水素吸蔵性能の測定］
試料約０．２ｇを用い、レスカ社製カーボン材料水素吸蔵放出評価装置ＰＣＴ−Ｃ０７を用い、ＪＩＳＨ−７２０１に準拠した方法で、３０℃、１３ＭＰａで測定を行う。
[Measurement of hydrogen storage performance]
Using about 0.2 g of a sample, measurement is performed at 30 ° C. and 13 MPa by a method based on JISH-7201 using a carbon material hydrogen storage / release evaluation apparatus PCT-C07 manufactured by Reska.
［金属分析方法］
日立製作所社製原子吸光光度計Ｚ８０００を用いて測定を行う。
[Metal analysis method]
Measurement is performed using an atomic absorption photometer Z8000 manufactured by Hitachi, Ltd.
（実施例）
図１に示す製造装置を用い、本発明の含金属窒化炭素物を堆積させた。反応管４には内径６０ｍｍ、長さ１ｍのアルミナ製円筒炉心管を用い、この炉心管に合う環状炉を加熱装置７として用いた。触媒として安定化ニッケル触媒〔日揮化学社製、商品名：Ｎ１０３Ｆ〕０．２ｇをアルミナ製ボートに入れて使用した。原料としてはアセトニトリルを用い、アセトニトリルを入れた容器を７０℃に加熱した。キャリアガスとして窒素ガスを用い、８０ｍｌ／分の流量で原料を反応管４内に導入した。環状炉を８５０℃に設定し、６時間反応させた。
(Example)
The metal-containing carbon nitride of the present invention was deposited using the production apparatus shown in FIG. As the reaction tube 4, an alumina cylindrical core tube having an inner diameter of 60 mm and a length of 1 m was used, and an annular furnace suitable for the core tube was used as the heating device 7. As a catalyst, 0.2 g of a stabilized nickel catalyst [manufactured by JGC Chemical Co., Ltd., trade name: N103F] was used in an alumina boat. Acetonitrile was used as a raw material, and a container containing acetonitrile was heated to 70 ° C. Nitrogen gas was used as a carrier gas, and the raw material was introduced into the reaction tube 4 at a flow rate of 80 ml / min. The annular furnace was set at 850 ° C. and reacted for 6 hours.
得られた含金属窒化炭素物を触媒ごと製造装置から取り出して二分割し、測定用試料とし、前述した方法により、Ｘ線光電子スペクトル、ラマン散乱スペクトルを測定し、金属分析を行った。 The obtained metal-containing carbon nitride was taken out from the production apparatus together with the catalyst, divided into two, used as a measurement sample, measured for X-ray photoelectron spectrum and Raman scattering spectrum by the methods described above, and subjected to metal analysis.
その結果、ラマン散乱スペクトルにおいて、１５７５ｃｍ-1と１３５５ｃｍ-1にピークが認められ、ＩG／ＩDは０．６７であった。 As a result, in the Raman scattering spectrum, peaks were observed at 1575 cm −1 and 1355 cm −1 , and I G / ID was 0.67.
また、Ｘ線光電子スペクトルにおいて、３９９ｅＶ、４０２ｅＶの２箇所にピークが見られ、Ｘp／Ｘtは３／１００であった。また、Ｎ1s／Ｃ1sは１６／１００であった。 In the X-ray photoelectron spectrum, peaks were observed at two sites of 399 eV and 402 eV, and X p / X t was 3/100. N 1s / C 1s was 16/100.
水素吸蔵性能測定の結果、本例の含金属窒化炭素物の水素吸蔵性能は０．５質量％であった。 As a result of measuring the hydrogen storage performance, the metal storage carbon nitride of this example had a hydrogen storage performance of 0.5% by mass.
また、得られた含金属窒化炭素物０．１ｇを硫酸２０ｍｌで溶解した試料を金属分析した結果、Ｎｉが０．３５質量％検出された。 Further, as a result of metal analysis of a sample obtained by dissolving 0.1 g of the obtained metal-containing carbon nitride in 20 ml of sulfuric acid, 0.35% by mass of Ni was detected.
本発明の含金属窒化炭素物は、常温での水素吸蔵が可能で単位質量あたりの水素吸蔵量が多く優れた水素吸蔵材であり、燃料電池等の水素エネルギー源の燃料貯蔵源として好適に利用できる。 The metal-containing carbon nitride of the present invention is an excellent hydrogen storage material that can store hydrogen at room temperature and has a large amount of hydrogen storage per unit mass, and is suitably used as a fuel storage source for hydrogen energy sources such as fuel cells. it can.
１ 窒素供給源
２ 原料供給源
３ 配管
４ 反応管
５ 流量計
６ 原料供給源加熱装置
７ 反応管加熱装置
１１ 触媒容器
１２ 触媒
DESCRIPTION OF SYMBOLS 1 Nitrogen supply source 2 Raw material supply source 3 Piping 4 Reaction tube 5 Flowmeter 6 Raw material supply source heating device 7 Reaction tube heating device 11 Catalyst container 12 Catalyst
Claims (9)
ラマン散乱スペクトルにおいて、
（Ａ）１５７０〜１５８０ｃｍ-1のバンドのピーク強度（ＩG）と、１３４１〜１３６０ｃｍ-1のバンドのピーク強度（ＩD）の比（ＩG／ＩD）が１未満、
（Ｂ）１５７０〜１５８０ｃｍ-1のバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上であることを特徴とする含金属窒化炭素物。 A metal-containing carbon nitride containing at least metal, nitrogen and carbon as constituent elements,
In the Raman scattering spectrum,
(A) and the peak intensity of the bands of 1570~1580cm -1 (I G), the ratio of the peak intensity of the bands of 1341~1360cm -1 (I D) (I G / I D) is less than 1,
(B) The peak of the band of 1570 to 1580 cm −1 is not observed,
Either
A metal-containing carbon nitride having a relative abundance ratio of N 1s and C 1s (N 1s / C 1s ) in an X-ray photoelectron spectrum of 0.1 / 100 or more.
Ｘ線光電子スペクトルにおいて、
（ａ）３９８〜４００ｅＶのバンドのピーク強度（Ｘt）と４０１〜４０３ｅＶのバンドのピーク強度（Ｘp）の比（Ｘp／Ｘt）が１未満、
（ｂ）３９８〜４００ｅＶのバンドのピークが観察され、４０１〜４０３ｅＶのバンドのピークが観察されない、
のいずれかであり、
Ｘ線光電子スペクトルにおけるＮ1sとＣ1sの相対存在比（Ｎ1s／Ｃ1s）が０．１／１００以上であることを特徴とする含金属窒化炭素物。 A metal-containing carbon nitride containing at least metal, nitrogen and carbon as constituent elements,
In the X-ray photoelectron spectrum,
(A) the ratio of the band peak intensity (X t) and the peak intensity of the bands of 401~403eV of 398~400eV (X p) (X p / X t) is less than 1,
(B) A peak of a band of 398 to 400 eV is observed, and a peak of a band of 401 to 403 eV is not observed,
Either
A metal-containing carbon nitride having a relative abundance ratio of N 1s and C 1s (N 1s / C 1s ) in an X-ray photoelectron spectrum of 0.1 / 100 or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008117855A1 (en) * | 2007-03-28 | 2008-10-02 | Asahi Kasei Chemicals Corporation | Nitrogenous carbon material and process for producing the same |
| US8034976B2 (en) | 2005-09-30 | 2011-10-11 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and method of producing the same |
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| CN104475140A (en) * | 2014-11-07 | 2015-04-01 | 江苏大学 | Silver-modified carbon nitride composite photocatalytic material and preparation method thereof |
| CN108339562A (en) * | 2018-02-11 | 2018-07-31 | 济南大学 | A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping |
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2003
- 2003-09-18 JP JP2003326319A patent/JP2005089264A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8034976B2 (en) | 2005-09-30 | 2011-10-11 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and method of producing the same |
| WO2008117855A1 (en) * | 2007-03-28 | 2008-10-02 | Asahi Kasei Chemicals Corporation | Nitrogenous carbon material and process for producing the same |
| US8092771B2 (en) | 2007-03-28 | 2012-01-10 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and process for producing the same |
| US8486565B2 (en) | 2007-03-28 | 2013-07-16 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
| US8900754B2 (en) | 2007-03-28 | 2014-12-02 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
| CN104475140A (en) * | 2014-11-07 | 2015-04-01 | 江苏大学 | Silver-modified carbon nitride composite photocatalytic material and preparation method thereof |
| CN108339562A (en) * | 2018-02-11 | 2018-07-31 | 济南大学 | A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping |
| CN108339562B (en) * | 2018-02-11 | 2020-07-07 | 济南大学 | Preparation method of iron ion doped carbon nitride nanotube and obtained product |
| CN114260019A (en) * | 2021-11-22 | 2022-04-01 | 上海交通大学 | Method for preparing lithium-doped cobalt-loaded g-C3N4 photocatalyst |
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