JP7232522B2 - Analysis method of carbon material - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act (1) December 5, 2018, Abstracts of the 45th Annual Meeting of the Carbon Society of Japan, p.220, The Carbon Society of Japan (2) December 7, 2018, Article 45th Annual Meeting of the Carbon Society of Japan, National University Corporation Nagoya Institute of Technology (3) June 27, 2019, website: http://carbon2019. org/wp-content/uploads/2019/07/365-ishii. pdf (4) July 15, 2019, Carbon 2019, Lexington (USA)

The present invention relates to a method for analyzing carbon materials.

In Patent Document 1, the total amount of the carbon edge surface of the carbon catalyst is calculated from the quantitative results of the desorption gas of the carbon catalyst obtained using a thermal desorption spectrometer capable of increasing the temperature up to 1600 ° C. It is described that the average carbon network plane size L was calculated from. Non-Patent Document 1 and Non-Patent Document 2 describe that the temperature was raised to 1800° C. in the thermal desorption method.

WO2017/209244

Takafumi Ishii et al. A quantitative analysis of carbon edge sites and an estimation of graphene sheet size in high-temperature treated, non-porous carbons. Carbon 2014; 80: 135-145 Takafumi Ishii et al. Analysis of trace amounts of edge sites in natural graphite, synthetic graphite and high-temperature treated coke for the understanding of their carbon structures molecular. Carbon 2017; 125: 146-155

The thermal desorption method is useful for analyzing the types and amounts of functional groups bonded to the carbon atoms at the edges of the carbon hexagonal mesh plane of carbon materials. However, conventionally, there have been combinations of functional groups that cannot be distinguished by the temperature programmed desorption method.

The present invention has been made in view of the above problems, and one of its objects is to provide a carbon material analysis method capable of effectively analyzing the functional groups contained in the carbon material.

A method for analyzing a carbon material according to an embodiment of the present invention for solving the above problems comprises a first functional group that satisfies the following conditions (a1) to (c1): (a1) the first functional group is carbon; (b1) the first functional group does not contain protic hydrogen atoms, which are hydrogen atoms that can be substituted with deuterium atoms, but contains non-hydrogen atoms; and (c1) the first functional group is thermally decomposed by heating at a first temperature to produce the first compound gas containing the non-hydrogen atom; A second functional group that satisfies the conditions: (a2) the second functional group is bonded to a carbon atom at the edge of the carbon hexagonal network plane; (b2) the second functional group is a protic hydrogen atom; (c2) the second functional group thermally decomposes upon heating at the first temperature to produce the first compound gas; (d2) the second functional group the group thermally decomposes upon heating at said first temperature after said hydrogen atoms have been replaced by deuterium atoms, leaving said deuterium atoms bonded to carbon atoms at the edge of the carbon hexagonal plane; and (e2) the deuterium atoms left in (d2) are desorbed by heating at a second temperature different from the first temperature to produce a second compound gas containing the deuterium atoms; , an edge hydrogen atom that is a hydrogen atom that satisfies the following conditions (x) to (z): (x) the edge hydrogen atom is bonded to a carbon atom at the edge of the carbon hexagonal network plane; and (z) said edge hydrogen atoms are desorbed upon heating at said second temperature to form a hydrogen-containing compound containing said hydrogen atoms and not containing deuterium atoms. generating a gas; and a pretreatment step of subjecting a carbon material to a hydrogen-deuterium substitution treatment, after the pretreatment step, heating the carbon material at the first temperature to remove from the carbon material a first heating step of measuring the produced first compound gas; and after the first heating step, heating the carbon material at the second temperature to produce the second compound gas produced from the carbon material. Based on the second heating step to be measured, the measurement result of the first compound gas, and the measurement result of the second compound gas, the carbon material before the hydrogen-deuterium substitution treatment has the first functional group and whether or not it contained one or more selected from the group consisting of the second functional group, and/or the first functional group contained in the carbon material before the hydrogen-deuterium substitution treatment and the selected from the group consisting of the second functional group and a evaluating step of evaluating one or more quantities to be measured. ADVANTAGE OF THE INVENTION According to this invention, the analysis method of the carbon material which can analyze the functional group contained in a carbon material effectively is provided.

Further, in the second heating step, the hydrogen-containing compound gas generated from the carbon material is further measured, and in the evaluation step, heating at the first temperature is performed based on the measurement result of the hydrogen-containing compound gas. further assessing whether the previous carbon material contained the edge hydrogen atoms and/or the amount of the edge hydrogen atoms contained in the carbon material prior to the hydrogen-deuterium replacement treatment. You can do it.

Moreover, in the method, the non-hydrogen atom may be an oxygen atom. In this case, the first functional group may be a cyclic ether group, and the second functional group may be a phenolic hydroxyl group. Furthermore, in this case, the first compound gas is carbon monoxide, and the second compound gas is one or more selected from the group consisting of hydrogen deuteride, deuterium, semi-heavy water, and heavy water. good too. Moreover, in the method, the hydrogen-containing compound gas may be hydrogen and/or water.

In the above method, the carbon material has a third functional group that satisfies the following conditions (a3) to (e3): (a3) The third functional group is bonded to a carbon atom on the edge of the hexagonal carbon network plane. (b3) the third functional group includes a protic hydrogen atom and the non-hydrogen atom; (c3) the third functional group has the hydrogen atom replaced with a deuterium atom (d3) after the hydrogen atoms are replaced with deuterium atoms, the third functional group is heated at the first temperature and the first compound gas is not generated; By heating at a third temperature different from the two temperatures, it is thermally decomposed to generate a third compound gas containing the non-hydrogen atoms and different from the first compound gas and the second compound gas, and a carbon hexagonal network plane leaving said deuterium atoms bonded to edge carbon atoms; and (e3) said deuterium atoms left in said (d3) are desorbed by heating at said second temperature to form said second compound generating a gas;
and the method for analyzing the carbon material includes, after the hydrogen-deuterium substitution treatment, heating the carbon material at the third temperature to generate the third compound generated from the carbon material Further comprising a third heating step of measuring the gas, and in the evaluation step, based on the measurement result of the first compound gas, the measurement result of the second compound gas, and the measurement result of the third compound gas, whether or not the carbon material before the hydrogen-deuterium substitution treatment contained one or more selected from the group consisting of the first functional group, the second functional group and the third functional group; and/or , an amount of one or more selected from the group consisting of the first functional group, the second functional group, and the third functional group contained in the carbon material before the hydrogen-deuterium substitution treatment. You can do it. In this case, the third functional group may be a carboxy group. Furthermore, in this case, the third compound gas may be carbon dioxide.

ADVANTAGE OF THE INVENTION According to this invention, the analysis method of the carbon material which can analyze the functional group contained in a carbon material effectively is provided.

FIG. 2 is an explanatory diagram showing an example of desorption gas generation by thermal decomposition of functional groups contained in a carbon material; FIG. 4 is an explanatory diagram showing another example of desorption gas generation by thermal decomposition of functional groups contained in a carbon material; FIG. 4 is an explanatory diagram showing still another example of desorption gas generation by thermal decomposition of functional groups contained in carbon materials. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram schematically showing steps included in an example of a carbon material analysis method according to an embodiment of the present invention; FIG. 4 is an explanatory diagram schematically showing steps included in another example of the carbon material analysis method according to one embodiment of the present invention. FIG. 4 is an explanatory diagram showing an example of a temperature programmed desorption spectrum obtained for a carbon material (MSC) not subjected to hydrogen-deuterium replacement treatment in an example according to one embodiment of the present invention. FIG. 4 is an explanatory diagram showing another example of a temperature programmed desorption spectrum obtained for a carbon material (MSC) not subjected to hydrogen-deuterium replacement treatment in an example according to one embodiment of the present invention. FIG. 2 is an explanatory diagram showing an example of a temperature programmed desorption spectrum obtained for a carbon material (MSC(D ₂ O)) subjected to hydrogen-deuterium substitution treatment in an example according to one embodiment of the present invention. FIG. 4 is an explanatory diagram showing another example of the thermal desorption spectrum obtained for a carbon material (MSC(D ₂ O)) subjected to hydrogen-deuterium substitution treatment in an example according to one embodiment of the present invention; be. Explanatory drawing showing an example of a temperature-programmed desorption spectrum obtained for a carbon material (MSC-O ₂ (D ₂ O)) subjected to hydrogen-deuterium substitution treatment in an example according to one embodiment of the present invention. is. 1 shows another example of a temperature-programmed desorption spectrum obtained for a carbon material (MSC-O ₂ (D ₂ O)) subjected to hydrogen-deuterium substitution treatment in an example according to an embodiment of the present invention. It is an explanatory diagram. 1 shows an example of a temperature-programmed desorption spectrum obtained for a carbon material (MSC-H ₂ O ₂ (D ₂ O)) subjected to hydrogen-deuterium substitution treatment in an example according to one embodiment of the present invention. It is an explanatory diagram. Another example of the thermal desorption spectrum obtained for the carbon material (MSC-H ₂ O ₂ (D ₂ O)) subjected to the hydrogen-deuterium substitution treatment in the example according to one embodiment of the present invention It is an explanatory view showing . FIG. 3 is an explanatory diagram showing an example of quantitative results by thermal desorption method obtained in an example according to one embodiment of the present invention. FIG. 4 is an explanatory diagram showing an example of the result of calculating the functional group content of a carbon material from the quantitative result by the thermal desorption method in an example according to one embodiment of the present invention.

An embodiment of the present invention will be described below. Note that the present invention is not limited to the example shown in this embodiment.

The temperature programmed desorption (TPD) method is useful for analyzing the types and amounts of functional groups bonded to the carbon atoms at the edges of the carbon hexagonal network planes of carbon materials. Conventionally, however, it has been difficult to analyze, for example, a cyclic ether group and a phenolic hydroxyl group by distinguishing them by the TPD method.

That is, as shown in FIG. 1A, the cyclic ether groups and phenolic hydroxyl groups bonded to the carbon atoms at the edges of the carbon hexagonal network plane contained in the carbon material are thermally decomposed at the same temperature when heated, and In order to generate the same desorbed gas of carbon oxide (CO), it is possible to distinguish and analyze the cyclic ether group and the phenolic hydroxyl group contained in the carbon material according to the type and amount of the desorbed gas at the temperature. It was difficult.

In this regard, as shown in FIG. 1B, when the phenolic hydroxyl group is thermally decomposed to generate carbon monoxide, the hydrogen atoms contained in the phenolic hydroxyl group are transferred to the carbon atoms at the edges of the carbon hexagonal network surface. It remains in the carbon material as a bonded hydrogen atom.

Therefore, as shown in FIG. 1B, the cyclic ether group and the phenolic hydroxyl group are first thermally decomposed by heating at a first temperature to generate carbon monoxide, and then heated at a second temperature different from the first temperature. By doing so, the hydrogen atoms bonded to the carbon atoms of the edge derived from the phenolic hydroxyl group are detached, and the hydrogen (H ₂ ) containing the detached hydrogen atoms is measured, whereby the cyclic ether group and the phenol It is also conceivable to distinguish from the functional hydroxyl group.

However, as shown in FIG. 1C, when the carbon material contains edge hydrogen atoms bonded to carbon atoms at the edges of the carbon hexagonal plane, heating at the second temperature causes the hydrogen derived from the edge hydrogen atoms ( H ₂ ) is also produced, so it is also difficult to distinguish between cyclic ether groups and phenolic hydroxyl groups by measuring the hydrogen (H ₂ ).

The inventors of the present invention have completed the present invention as a result of extensive studies on technical means for solving the above problems. FIG. 2 schematically shows steps included in an example of the carbon material analysis method (hereinafter referred to as "this method") according to this embodiment.

In this method, a carbon material that can contain a first functional group (a functional group corresponding to the cyclic ether group shown in FIG. 2) and a second functional group (a functional group corresponding to the phenolic hydroxyl group shown in FIG. 2), A pretreatment step of performing hydrogen-deuterium replacement treatment (hereinafter referred to as “HD replacement treatment”) (treatment corresponding to “HD replacement” shown in FIG. 2), and after the pretreatment step, the carbon a first heating step of heating a material to a first temperature to measure a first compound gas produced from the carbon material; Based on the second heating step of heating at two temperatures and measuring the second compound gas generated from the carbon material, the measurement result of the first compound gas, and the measurement result of the second compound gas, Whether or not the carbon material before the HD substitution treatment contained one or more selected from the group consisting of the first functional group and the second functional group, and/or the carbon before the HD substitution treatment evaluating one or more amounts selected from the group consisting of the first functional group and the second functional group contained in the material.

The first functional group satisfies the following conditions (a1) to (c1): (a1) the first functional group is bonded to a carbon atom at the edge of the carbon hexagonal network plane; (b1) the first functional group The group does not contain protic hydrogen atoms, which are hydrogen atoms that can be substituted with deuterium atoms, and contains non-hydrogen atoms (atoms corresponding to the oxygen atoms of the cyclic ether groups shown in FIG. 2); The monofunctional group is thermally decomposed by heating at a first temperature (heating corresponding to "first heating" shown in FIG. 2) to form a first compound gas (cyclic ether shown in FIG. 2) containing the non-hydrogen atom a gas equivalent to carbon monoxide (CO) derived from the radicals).

The second functional group satisfies the following conditions (a2) to (e2): (a2) the second functional group is bonded to a carbon atom at the edge of the carbon hexagonal network plane; (b2) the second functional group The group includes a protic hydrogen atom (a hydrogen atom corresponding to the hydrogen atom of the phenolic hydroxyl group shown in FIG. 2) and a non-hydrogen atom of the same kind as the non-hydrogen atom contained in the first functional group (a phenolic hydrogen atom shown in FIG. 2). (c2) The second functional group is thermally decomposed by heating at the first temperature to form the first compound gas (derived from the phenolic hydroxyl group shown in FIG. (d2) the second functional group is thermally decomposed by heating at the first temperature after the hydrogen atoms are replaced with deuterium atoms; , the deuterium atoms bonded to the carbon atoms at the edges of the carbon hexagonal network plane (deuterium atoms corresponding to the deuterium atoms (D) remaining on the carbon hexagonal network plane after the "first heating" of the phenolic hydroxyl group in FIG. 2 and (e2) the deuterium atoms left in (d2) are heated at a second temperature different from the first temperature (heating corresponding to “second heating” shown in FIG. 2) , desorbs to produce a second compound gas containing the deuterium atom (a gas corresponding to deuterium (HD) and/or deuterium (D ₂ ) generated by “second heating” in FIG. 2) Generate.

In addition, the carbon material may further include edge hydrogen atoms (hydrogen atoms corresponding to the edge hydrogen atoms shown in FIG. 2), which are hydrogen atoms satisfying the following conditions (x) to (z): (x) edge hydrogen atoms. are bonded to carbon atoms at the edges of the carbon hexagonal plane; (y) edge hydrogen atoms are not replaced with deuterium atoms; and (z) edge hydrogen atoms are reduced to , desorbed to produce a hydrogen-containing compound gas containing the edge hydrogen atoms (strictly speaking, hydrogen atoms derived from the edge hydrogen atoms) and not containing deuterium atoms (generated by the “second heating” in FIG. 2, A gas corresponding to hydrogen (H ₂ ) derived from edge hydrogen atoms is produced.

In this method, carbon materials that may contain first functional groups, second functional groups, and edge hydrogen atoms are analyzed. Here, the carbon material that "may contain" the first functional group, the second functional group, and the edge hydrogen atom refers to a carbon material known to contain the first functional group, the second functional group, and the edge hydrogen atom. materials and carbon materials that may contain the first functional group, the second functional group, and the edge hydrogen atoms.

That is, the carbon material to be analyzed may be, for example, a carbon material in which it is unknown whether or not it contains a first functional group, a second functional group, and an edge hydrogen atom. , a carbon material reasonably understood to comprise a first functional group, a second functional group and an edge hydrogen atom, or comprising a first functional group, a second functional group and an edge hydrogen atom is already confirmed, but the content of the first functional group, the second functional group, or the edge hydrogen atom is unknown.

A carbon material is a material mainly composed of carbon. That is, the carbon material may have a carbon atom content of, for example, 70% by weight or more, 75% by weight or more, 80% by weight or more, or 85% by weight or more. may be 90% by weight or more.

The carbon material may have a hydrogen atom content of 15% by weight or less, 10% by weight or less, or 5% by weight or less. The carbon material may have an oxygen atom content of 30% by weight or less, 25% by weight or less, or 20% by weight or less.

The composition of the carbon material is an arbitrary combination of one or more selected from the group consisting of any of the above carbon atom contents, any of the above hydrogen atom contents, and any of the above oxygen atom contents. can be specified. The composition of the carbon material is measured by elemental analysis.

Preferably, the carbon material is an amorphous carbon material. Amorphous carbon materials are carbon materials that contain carbon atoms that are randomly arranged in space in their carbon structure. Also, an amorphous carbon material is a carbon material containing a carbon structure that does not reach a graphite structure. Therefore, an amorphous carbon material is a carbon material with relatively low crystallinity. More specifically, the amorphous carbon material is, for example, a carbon material in which the half width of the 002 diffraction line shows a value of 1 degree or more in X-ray diffraction using Cu—Kα rays as an X-ray source.

The carbon material is preferably a powdery carbon material. The carbon material is preferably a porous carbon material. The BET specific surface ^area of ^the carbon material ^is not particularly limited. Particularly preferably, it is 100 m ² /g or more.

The first functional group and the second functional group are both bonded to the edge carbon atoms of the carbon hexagonal network plane and contain common non-hydrogen atoms. Specifically, in the example shown in FIG. 2, both the cyclic ether group (first functional group) and the phenolic hydroxyl group (second functional group) are bonded to carbon atoms at the edges of the carbon hexagonal network plane, and , contains oxygen atoms (non-hydrogen atoms).

On the other hand, the first functional group does not contain hydrogen atoms (protic hydrogen atoms) that can be substituted with deuterium atoms, whereas the second functional group contains protic hydrogen atoms. Specifically, in the example shown in FIG. 2, the cyclic ether group (first functional group) does not contain protic hydrogen atoms, whereas the phenolic hydroxyl group (second functional group) contains protic hydrogen atoms. include.

A protic hydrogen atom is also called an ionic hydrogen atom. A protic hydrogen atom is a hydrogen atom that can ionize into hydrogen ions in water. Protic hydrogen atoms can be replaced with deuterium atoms, for example, by the hydrogen-deuterium replacement process described below.

The first functional group may also be free of hydrogen atoms (aprotic hydrogen atoms) that are not substituted with deuterium atoms. That is, the first functional group may be free of hydrogen atoms (protic hydrogen atoms and aprotic hydrogen atoms). Specifically, in the example shown in FIG. 2, the cyclic ether group (first functional group) does not contain a hydrogen atom.

The first functional group and the second functional group are bonded to the edge carbon atoms via non-hydrogen atoms contained in the first functional group and the second functional group. That is, the non-hydrogen atoms contained in the first functional group and the second functional group are bonded to the edge carbon atoms. Specifically, in the example shown in FIG. 2, both the cyclic ether group (first functional group) and the phenolic hydroxyl group (second functional group) are attached to the edge carbon atoms via oxygen atoms (non-hydrogen atoms). Combined.

The first functional group and the second functional group are thermally decomposed by heating at a first temperature (hereinafter referred to as "first heating") to generate a first compound gas containing non-hydrogen atoms. That is, the first functional group and the second functional group are thermally decomposed at the same temperature (first temperature) to generate the same kind of desorbed gas (first compound gas).

Therefore, when the carbon material containing the first functional group and the second functional group is heated at the first temperature, the first compound gas derived from the thermal decomposition of the first functional group and the thermal decomposition of the second functional group A first compound gas is generated. Specifically, in the example shown in FIG. 2, both the cyclic ether group (first functional group) and the phenolic hydroxyl group (second functional group) are thermally decomposed by the first heating to produce carbon monoxide (first compound gas ).

After the protic hydrogen atoms contained in the second functional group are replaced with deuterium atoms, the second functional group is thermally decomposed by heating at the first temperature to generate carbon at the edge of the carbon hexagonal network surface Leave the deuterium atom attached to the atom.

That is, when a second functional group in which a protic hydrogen atom is replaced by a deuterium atom (the second functional group containing the deuterium atom and a non-hydrogen atom) is heated at a first temperature, the second functional group is While thermally decomposing to produce the first compound gas, the deuterium atoms contained in the second functional group are bound to the carbon atoms at the edges of the carbon hexagonal mesh plane and remain in the carbon material.

Specifically, in the example shown in FIG. 2, the phenolic hydroxyl group (second functional group) in which the protic hydrogen atom is substituted with the deuterium atom (D) is thermally decomposed by the first heating to form a carbon hexagonal network surface leaving the deuterium atom (D) attached to the edge carbon atom of .

The first temperature is such that the first functional group and the second functional group thermally decompose, the thermal decomposition of the first functional group and the second functional group generates a common first compound gas, and the second functional group It is the temperature at which the deuterium atoms contained in the second functional group due to thermal decomposition remain bonded to the carbon atoms at the edges of the carbon hexagonal network plane.

The first temperature is determined as the temperature at which the first functional group and the second functional group determined to be analyzed in this method generate a common first compound gas by thermal decomposition. That is, the first temperature is, for example, a temperature known in advance as the temperature at which the first functional group and the second functional group generate a common first compound gas by thermal decomposition.

Specifically, in the example shown in FIG. 2 where the first functional group is a cyclic ether group, the second functional group is a phenolic hydroxyl group, and the first compound gas is carbon monoxide (CO), the first temperature is For example, the temperature may be 300° C. or higher and 1100° C. or lower, the temperature may be 400° C. or higher and 1000° C. or lower, or the temperature may be 500° C. or higher and 900° C. or lower.

The deuterium atoms remaining in the carbon material due to the thermal decomposition of the second functional group at the first temperature are heated at a second temperature different from the first temperature (hereinafter referred to as "second heating") to convert the carbon material into to produce a second compound gas containing the deuterium atoms.

That is, the deuterium atoms derived from the second functional group, which are bonded to the edge carbon atoms by the first heating, are desorbed by further heating at a second temperature different from the first temperature to form the second compound produce gas.

Specifically, in the example shown in FIG. 2, the deuterium atoms (D) left in the carbon material due to the thermal decomposition of the phenolic hydroxyl groups (second functional groups) due to the first heating are then heated to a temperature different from the first temperature. A second heating at two temperatures desorbs from the carbon material to produce deuterium (HD) and/or deuterium ( _D2 ) (second compound gas).

The second temperature is a temperature different from the first temperature used to thermally decompose the second functional group, and the second temperature remaining in the carbon material due to the thermal decomposition of the second functional group at the first temperature It is the temperature at which the deuterium atoms derived from the functional groups are desorbed to generate the second compound gas.

The second temperature is, for example, the hydrogen atoms remaining in the carbon material are desorbed by thermally decomposing the second functional group not subjected to the HD substitution treatment at the first temperature, and the compound containing the hydrogen atoms It is determined as the temperature at which the gas is generated. That is, at the second temperature, for example, the hydrogen atoms remaining in the carbon material due to thermal decomposition of the second functional group not subjected to the HD substitution treatment are desorbed to generate a compound gas containing the hydrogen atoms. This is the temperature known in advance as the temperature.

Specifically, as shown in FIG. 1B, the phenolic hydroxyl group (second functional group) in which protic hydrogen atoms are not replaced with deuterium atoms is thermally decomposed to generate carbon monoxide (first compound gas). At this time, the hydrogen atoms contained in the phenolic hydroxyl group are bonded to the carbon atoms at the edge of the carbon hexagonal network plane and remain in the carbon material.

Furthermore, as shown in FIG. 1B, hydrogen atoms derived from phenolic hydroxyl groups remaining in the carbon material are removed from the carbon material by heating at a higher temperature (heating corresponding to the second heating in this method). It desorbs to produce hydrogen (H ₂ ).

Therefore, in this case, the temperature at which hydrogen atoms derived from phenolic hydroxyl groups are eliminated from the carbon material to generate hydrogen (H ₂ ) is determined as the second temperature.

That is, if the temperature at which hydrogen atoms derived from phenolic hydroxyl groups are eliminated from the carbon material to generate hydrogen (H ₂ ) is known in advance, that temperature is adopted as the second temperature in the present method.

Specifically, the first functional group is a cyclic ether group, the second functional group is a phenolic hydroxyl group, and the second compound gas is hydrogen deuteride (HD) and/or deuterium (D ₂ ). 2, the second temperature may be, for example, a temperature of 600° C. or higher and 1600° C. or lower, a temperature of 700° C. or higher and 1500° C. or lower, or a temperature of 800° C. or higher and 1400° C. or lower. may be the temperature of

Here, FIG. 2 shows an example in which the second heating is performed by the TPD method. When the second heating is performed by the TPD method, the second temperature may be higher than the first temperature. On the other hand, in this method, the second heating may be performed by a temperature programmed oxidation (TPO) method. When the second heating is performed by the TPO method, half heavy water (DHO) and/or heavy water ( _D2 O) is generated.

When the second heating is performed by the TPO method, the second temperature may be, for example, a temperature of 300°C or higher and 1000°C or lower, a temperature of 400°C or higher and 900°C or lower, or 500°C. The temperature may be above 800° C. or below.

The non-hydrogen atoms commonly contained in the first functional group and the second functional group are preferably oxygen atoms, as shown in the example of FIG. In this case, the first functional group does not contain a protic hydrogen atom, but contains an oxygen atom. On the other hand, the second functional group contains a protic hydrogen atom and an oxygen atom. Also, both the first functional group and the second functional group may be bonded to the carbon atom of the edge via an oxygen atom.

When the non-hydrogen atoms are oxygen atoms, the first compound gas may contain the oxygen atoms and carbon atoms. Specifically, in the example shown in FIG. 2, carbon monoxide (CO) (first compound gas) produced by the first heating contains oxygen atoms and carbon atoms.

Also, the first compound gas may be free of hydrogen atoms and deuterium atoms. Specifically, in the example shown in FIG. 2, the carbon monoxide (CO) (first compound gas) produced by the first heating does not contain hydrogen atoms and deuterium atoms.

As shown in the example of FIG. 2, the first functional group is preferably a cyclic ether group and the second functional group is preferably a phenolic hydroxyl group. In this case, the first compound gas is carbon monoxide (CO) and the second compound gas is deuterium (HD), deuterium ( _D2 ), semi-heavy water (DHO), and heavy water (D2 ₎ . O) may be one or more selected from the group consisting of.

An edge hydrogen atom is a hydrogen atom bonded to a carbon atom at the edge of the carbon hexagonal plane and is not replaced with a deuterium atom. That is, edge hydrogen atoms are not protic hydrogen atoms. Further, the edge hydrogen atoms are desorbed from the carbon material by heating at the second temperature to generate a hydrogen-containing compound gas containing hydrogen atoms derived from the edge hydrogen atoms and not containing deuterium atoms.

Specifically, in the example shown in FIG. 2, the edge hydrogen atoms are desorbed from the carbon material by heating at the second temperature, and contain hydrogen atoms derived from the edge hydrogen atoms and do not contain deuterium atoms. Hydrogen (H ₂ ) (hydrogen-containing compound gas) is produced.

A hydrogen atom contained in a hydrocarbon group such as an alkyl group is also not a protic hydrogen atom, but the hydrocarbon group generates a hydrocarbon gas by heating at the second temperature. In this regard, the hydrogen-containing compound gas produced by heating the edge hydrogen atoms at the second temperature is not a hydrocarbon gas. The hydrogen-containing compound gas may not contain carbon atoms.

Specifically, the hydrogen-containing compound gas may be hydrogen (H ₂ ) and/or water (H ₂ O). Note that FIG. 2 shows an example in which hydrogen (H ₂ ) is generated as the hydrogen-containing compound gas when the second heating is performed by the TPD method. When the second heating is performed by the TPO method, water (H ₂ O) is produced as the hydrogen-containing compound gas by the second heating in the oxidizing atmosphere.

In the pretreatment step, the carbon material is subjected to HD replacement treatment. The HD replacement treatment is a treatment for replacing protic hydrogen atoms contained in the carbon material with deuterium atoms. By the HD substitution treatment, protic hydrogen atoms contained in the second functional group are substituted with deuterium atoms. That is, the second functional group contained in the carbon material after the HD substitution treatment contains deuterium atoms instead of the protic hydrogen atoms contained before the HD substitution treatment.

The HD replacement treatment of the carbon material is not particularly limited as long as it is a treatment for replacing protic hydrogen atoms with deuterium atoms. and a method of confining the carbon material and heavy water in a sealed container at a temperature above 0 ° C. and leaving it alone, and the carbon material is immersed in heavy water. is particularly preferably used.

Instead of heavy water, an acidic compound containing deuterium (e.g., deuterated hydrogen chloride (DCl), deuterated sulfuric acid (D ₂ SO ₄ ), deuterated perchloric acid (DClO ₄ ), and deuterated nitric acid (DNO ₃ )) may be used, but heavy water is preferably used.

In the first heating step, after the HD substitution treatment, the carbon material is heated at the first temperature, and the first compound gas produced from the carbon material is measured. Specifically, in the example shown in FIG. 2, after the HD substitution treatment, the carbon material is heated at the first temperature, and carbon monoxide (CO) (first compound gas) generated from the carbon material is measured. do.

The method of heating the carbon material at the first temperature in the first heating step is not particularly limited, but for example, the temperature is continuously raised from a temperature lower than the first temperature to a temperature higher than the first temperature. A method of heating while heating is preferably used.

The method of heating at the first temperature (first heating) in the first heating step and the method of measuring the first compound gas are not particularly limited, but the TPD method is preferably used. The first heating is performed under vacuum (for example, under a high vacuum of 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less) or an inert atmosphere (for example, selected from the group consisting of nitrogen gas and argon gas under one or more inert gas atmospheres).

In addition, the first heating is performed, for example, from a predetermined temperature lower than the first temperature to a predetermined temperature higher than the first temperature at a predetermined temperature increase rate (for example, 2 ° C./min or more and 50 ° C./min or less). It is carried out by heating the carbon material while increasing the temperature at . In this case, the first compound gas produced from the carbon material is measured while the temperature is increased by the first heating.

The first compound gas is preferably measured using a thermal desorption spectrometer (TPD spectrometer) equipped with a mass spectrometer. A quadrupole mass spectrometer (QMS) is preferably used as the mass spectrometer.

In the second heating step, the carbon material after the first heating is heated at the second temperature, and the second compound gas generated from the carbon material is measured. Specifically, in the example shown in FIG. 2, the carbon material after the first heating is heated at the second temperature, and deuterated hydrogen (HD) and/or deuterium (D ₂ ) generated from the carbon material is (Second compound gas) is measured. As described above, when the second heating is performed by the TPO method, semi-heavy water (DHO) and/or heavy water (D ₂ O) are measured as the second compound gas.

The method of heating the carbon material at the second temperature in the second heating step is not particularly limited, but for example, the temperature is continuously raised from a temperature lower than the second temperature to a temperature higher than the second temperature. A method of heating while heating is preferably used.

The method of performing the second heating in the second heating step and the method of measuring the second compound gas are not particularly limited, but the TPD method or the TPO method is preferably used. When using the TPD method, the second heating is performed under vacuum (for example, under a high vacuum of 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less) or an inert atmosphere (for example, nitrogen gas and argon under one or more inert gas atmospheres selected from the group consisting of gases). On the other hand, when using the TPO method, the second heating is preferably performed in an oxygen atmosphere (for example, an atmosphere with an oxygen partial pressure of 1 kPa or more and 200 kPa or less).

In addition, the second heating is performed, for example, from a predetermined temperature lower than the second temperature to a predetermined temperature higher than the second temperature at a predetermined temperature increase rate (for example, 2 ° C./min or more and 50 ° C./min or less). It is carried out by heating the carbon material while increasing the temperature at . In this case, the second compound gas produced from the carbon material is measured while the temperature is increased by the second heating.

Note that when the carbon material contains edge hydrogen atoms, a hydrogen-containing compound gas derived from the edge hydrogen atoms is also generated by the second heating of the carbon material, but the hydrogen-containing compound gas contains deuterium atoms. Therefore, it is distinguished from the second compound gas derived from the second functional group.

Specifically, in the example shown in FIG. 2, hydrogen (H ₂ ) derived from edge hydrogen atoms ( Hydrogen-containing compound gases) are readily distinguished from deuterium (HD) and/or deuterium (D ₂ ) derived from phenolic hydroxyl groups (second compound gases). In addition, water (H ₂ O) (hydrogen-containing compound gas) derived from edge hydrogen atoms generated by the second heating in an oxidizing atmosphere (for example, the second heating by the TPO method) is also converted into phenolic hydroxyl groups. It is easily distinguished from semi-heavy water (DHO) and/or heavy water ( _D2O ) (second compound gas) from which it originates.

In this method, the first heating step and the second heating step may be performed by the TPD method, or the first heating step may be performed by the TPD method and the second heating step may be performed by the TPO method. Although good, it is preferable to carry out the first heating step and the second heating step by the TPD method. When the first heating step and the second heating step are performed by the TPD method, the first heating step and the second heating step may be performed continuously using one TPD analyzer.

That is, when the first heating step and the second heating step are performed by the TPD method, after the HD replacement treatment, under vacuum or in an inert atmosphere, from a predetermined temperature lower than the first temperature, While heating the carbon material while increasing the temperature to a predetermined temperature higher than the second temperature, the first compound gas generated from the carbon material is measured, and then from a predetermined temperature lower than the second temperature to the second temperature The carbon material is heated while increasing the temperature to a predetermined high temperature, and the second compound gas produced from the carbon material is measured. In this case, a temperature higher than the first temperature is used as the second temperature.

Further, when the second heating step is performed by the TPO method, after the HD replacement treatment, from a predetermined temperature lower than the first temperature to a predetermined temperature higher than the first temperature under vacuum or in an inert atmosphere. , heating the carbon material while increasing the temperature, measuring the first compound gas generated from the carbon material, and then, under an oxidizing atmosphere, from a predetermined temperature lower than the second temperature, to a temperature higher than the second temperature The carbon material is heated while increasing the temperature to a predetermined high temperature, and the second compound gas produced from the carbon material is measured. In this case, the first heating step may be performed by the TPD method. Moreover, as the second temperature, a temperature lower than the first temperature is used.

In the evaluation step, based on the measurement results of the first compound gas obtained in the first heating step and the measurement results of the second compound gas obtained in the second heating step, carbon before the HD replacement treatment Whether the material contained one or more selected from the group consisting of a first functional group and a second functional group, and/or the first functional group contained in the carbon material before the HD substitution treatment. and an amount of one or more selected from the group consisting of a second functional group.

That is, in the evaluation step, for example, based on the measurement result of the first compound gas and the measurement result of the second compound gas, the carbon material before the HD substitution treatment is divided from the first functional group and the second functional group. It is determined whether or not one or more selected from the group of is included.

Specifically, for example, when the second compound gas is measured in the second heating step, it is determined that the carbon material before the first heating contained the second functional group. That is, in the example shown in FIG. 2, when deuterium (HD) and/or deuterium (D ₂ ) produced by the second heating (second compound gas) is measured, HD substitution It is determined that the carbon material before treatment contained phenolic hydroxyl groups (second functional groups). On the other hand, when the second compound gas is not measured in the second heating step, it is determined that the carbon material before the first heating did not contain the second functional group.

Further, when the second compound gas is measured in the second heating step, the first compound gas measured in the first heating step is all derived from the second functional group, and the first compound gas is measured in the first heating step. When the amount of the second functional group calculated from the amount of the first compound gas is larger than the amount of the second functional group calculated from the amount of the second compound gas measured in the second heating step, It is determined that the carbon material before the first heating further contained the first functional group.

Specifically, in the example shown in FIG. 2, assuming that all carbon monoxide (CO) (first compound gas) generated by the first heating is derived from phenolic hydroxyl groups (second functional groups), the monoxide The amount of the phenolic hydroxyl group calculated from the amount of carbon is calculated from the amount of deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) generated by the second heating. If the amount is greater than the amount of phenolic hydroxyl groups, it is determined that the carbon material before the HD substitution treatment further contained a cyclic ether group (first functional group).

On the other hand, assuming that the first compound gas measured in the first heating step is all derived from the second functional group, the second functional group calculated from the amount of the first compound gas measured in the first heating step If the amount of groups is not greater than the amount of the second functional group calculated from the amount of the second compound gas measured in the second heating step, the carbon material before the first heating contains the first functional group. It is judged that it was not.

Further, when the first compound gas is measured in the first heating step and the second compound gas is not measured in the second heating step, the carbon material before the HD replacement treatment has the first functional group. judged to contain.

Specifically, in the example shown in FIG. 2, the first heating produces carbon monoxide (CO) (the first compound gas), and the second heating produces hydrogen deuteride (HD) and deuterium ( _D2 ) (second compound gas) is not generated, it is determined that the carbon material before the HD substitution treatment contained a cyclic ether group (first functional group).

In the evaluation step, for example, based on the measurement result of the first compound gas and the measurement result of the second compound gas, the first functional group and the second functional group contained in the carbon material before the HD replacement treatment One or more quantities selected from the group consisting of groups are calculated.

Specifically, for example, the amount of the second functional group contained in the carbon material before the HD replacement treatment is calculated from the amount of the second compound gas measured in the second heating step. That is, in the example shown in FIG. 2, from the amount of deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) generated by the second heating, carbon Calculate the amount of phenolic hydroxyl groups (second functional groups) contained in the material.

On the other hand, when the first compound gas was measured in the first heating step and the second compound gas was not measured in the second heating step, the first compound gas measured in the first heating step From the amount, the amount of the first functional group contained in the carbon material before the HD substitution treatment is calculated.

Specifically, in the example shown in FIG. 2, the first heating produces carbon monoxide (CO) (the first compound gas), and the second heating produces hydrogen deuteride (HD) and deuterium ( _D2 ) (second compound gas) was not generated, the cyclic ether group (second The amount of monofunctional groups) is calculated.

Further, the second functional group calculated from the amount of the first compound gas measured in the first heating step on the assumption that all the first compound gas measured in the first heating step is derived from the second functional group is greater than the amount of the second functional group calculated from the amount of the second compound gas measured in the second heating step, from the amount of the first compound gas corresponding to the difference, H- Calculate the amount of the first functional group contained in the carbon material before the D substitution treatment.

Specifically, in the example shown in FIG. 2, assuming that all carbon monoxide (CO) (first compound gas) generated by the first heating is derived from phenolic hydroxyl groups (second functional The amount of phenolic hydroxyl groups calculated from the amount of carbon monoxide produced by heating is deuterated hydrogen (HD) and / or deuterium (D ₂ ) produced by the second heating (second compound gas) If the amount of phenolic hydroxyl groups calculated from the amount is larger than the amount of carbon monoxide corresponding to the difference, the cyclic ether group (first functional base) is calculated.

Thus, according to this method, the first functional group and the second functional group contained in the carbon material can be distinguished and analyzed. Specifically, in the example shown in FIG. 2, first, in the pretreatment step, H— By performing the D substitution treatment, the protic hydrogen atom of the phenolic hydroxyl group is substituted with a deuterium atom (D).

Next, in the first heating step, by heating the carbon material after the HD substitution treatment at the first temperature, the cyclic ether group and the phenolic hydroxyl group containing the deuterium atom are thermally decomposed, and the generated Carbon oxide (CO) (first compound gas) is measured.

Furthermore, in the second heating step, the carbon material after the first heating is heated at a second temperature to desorb deuterium atoms derived from the thermal decomposition of the phenolic hydroxyl groups after the HD substitution treatment from the carbon material. to measure the deuterium (HD) and/or deuterium (D ₂ ) produced (second compound gas).

After that, in the evaluation step, the carbon monoxide (CO) measurement result obtained in the first heating step, and the deuterated hydrogen (HD) and / or deuterium ( _D2 ), whether or not the carbon material before the HD substitution treatment contained one or more selected from the group consisting of a cyclic ether group and a phenolic hydroxyl group, and/or the HD substitution treatment Evaluate the amount of one or more selected from the group consisting of cyclic ether groups and phenolic hydroxyl groups contained in the previous carbon material.

In this method, in the second heating step, the hydrogen-containing compound gas generated from the carbon material by the second heating (hydrogen (H ₂ ) derived from edge hydrogen atoms, generated by the “second heating” in FIG. 2) corresponding gas) is further measured, and in the evaluation step, based on the measurement results of the hydrogen-containing compound gas, whether or not the carbon material before the HD heat treatment contained edge hydrogen atoms, and/or The amount of edge hydrogen atoms contained in the carbon material before the HD heat treatment may be further evaluated.

That is, as described above, when the carbon material contains edge hydrogen atoms, the second heating of the carbon material produces a hydrogen-containing compound gas that contains hydrogen atoms derived from the edge hydrogen atoms and does not contain deuterium atoms. be.

Therefore, in the second heating step, the hydrogen-containing compound gas derived from the edge hydrogen atoms is measured. Specifically, when the second heating step is performed by the TPD method, as shown in FIG. 2, hydrogen (H ₂ ) is measured as the hydrogen-containing compound gas. Moreover, when implementing a 2nd heating process by TPO method, water ( _H2O ) is measured as hydrogen-containing compound gas.

In the evaluation step, for example, based on the measurement result of the hydrogen-containing compound gas, it is determined whether or not the carbon material before the HD replacement treatment contained edge hydrogen atoms. Specifically, for example, when a hydrogen-containing compound gas is measured in the second heating step, it is determined that the carbon material before the HD replacement treatment contained edge hydrogen atoms. That is, in the example shown in FIG. 2, when hydrogen (H ₂ ) (hydrogen-containing compound gas) is generated after the second heating, it is assumed that the carbon material before the HD replacement treatment contained edge hydrogen atoms. to decide. On the other hand, if the hydrogen-containing compound gas is not measured in the second heating step, it is determined that the carbon material before the first heating did not contain edge hydrogen atoms.

Also, the amount of edge hydrogen atoms contained in the carbon material before the HD replacement treatment is calculated from the amount of the hydrogen-containing compound gas measured in the second heating step. Specifically, in the example shown in FIG. 2, from the amount of hydrogen (H ₂ ) (hydrogen-containing compound gas) generated by the second heating, the edge hydrogen atoms contained in the carbon material before the HD replacement treatment Calculate the amount of

Thus, by measuring the hydrogen-containing compound gas generated by the second heating, edge hydrogen atoms contained in the carbon material can also be analyzed separately from the first functional group and the second functional group.

Figure 3 schematically illustrates the steps involved in another example of the method. The carbon material to be analyzed in this method may further contain a third functional group (a functional group corresponding to the carboxy group shown in FIG. 3) that satisfies the following conditions (a3) to (e3): (a3) the third functional group is bonded to a carbon atom at the edge of the carbon hexagonal network plane; (b3) the third functional group is a protic hydrogen atom and (c3) the third functional group is such that the protic hydrogen atom is a deuterium atom (d3) the third functional group is subjected to the first temperature and the second By being heated at a third temperature different from the temperature, it is thermally decomposed, and the third compound gas containing the non-hydrogen atoms and different from the first compound gas and the second compound gas (derived from the carboxy group shown in FIG. 3 gas equivalent to carbon dioxide (CO ₂ )), and the deuterium atoms bonded to the carbon atoms at the edge of the carbon hexagonal network plane (in FIG. 3, after the "third heating" of the carboxy group, and (e3) the deuterium atoms left in (d3) are desorbed by the second heating to form a second compound produce gas.

In this case, the method further includes a third heating step of heating the carbon material at a third temperature after the HD substitution treatment and measuring a third compound gas produced from the carbon material. Then, in the evaluation step, based on the measurement result of the first compound gas, the measurement result of the second compound gas, and the measurement result of the third compound gas, the carbon material before the HD replacement treatment is the first functional group, a second functional group and a third functional group, and/or the first functional group contained in the carbon material before the HD substitution treatment. , an amount of one or more selected from the group consisting of the second functional group and the third functional group.

The third functional group is attached to the edge carbon atoms of the carbon hexagonal network plane and includes protic hydrogen atoms and non-hydrogen atoms. Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) is bonded to the carbon atoms at the edge of the carbon hexagonal network plane and includes protic hydrogen atoms and oxygen atoms (non-hydrogen atoms). .

The number of non-hydrogen atoms in the third functional group may differ from that in the second functional group. That is, the number of non-hydrogen atoms contained in the third functional group may be greater than that of the second functional group. Specifically, in the example shown in FIG. 3, the number of oxygen atoms (non-hydrogen atoms) contained in the carboxy group (third functional group) is greater than that of the phenolic hydroxyl group (second functional group).

The third functional group may further contain other non-hydrogen atoms different from the non-hydrogen atoms contained in the second functional group. Other non-hydrogen atoms not included in the second functional group but included in the third functional group are, for example, one or more selected from the group consisting of a carbon atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a boron atom. , preferably a carbon atom.

Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) includes carbon atoms (other non-hydrogen atoms) not included in the second functional group. Also, when the second functional group does not contain a nitrogen atom, the third functional group may be an amino group. If the second functional group does not contain a phosphorus atom, the third functional group may be a phosphate group. If the second functional group does not contain a sulfur atom, the third functional group may be a sulfonic acid group. If the second functional group does not contain a boron atom, the third functional group may be a boric acid group.

The third functional group may be attached to the edge carbon atom via a non-hydrogen atom not included in the second functional group. Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) is connected to the edge carbon via a carbon atom (other non-hydrogen atom) not included in the phenolic hydroxyl group (second functional group) Bonded to an atom.

The third functional group does not produce a first compound gas when heated at the first temperature after the protic hydrogen atoms are replaced with deuterium atoms. Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) in which the protic hydrogen atom was replaced with a deuterium atom (D) by the HD substitution treatment was converted to carbon monoxide by the first heating. (first compound gas) is not generated.

The third functional group is thermally decomposed by heating at the third temperature (hereinafter referred to as "third heating") after the protic hydrogen atoms contained in the third functional group are replaced with deuterium atoms. This produces a third compound gas while leaving the deuterium atoms bonded to the carbon atoms at the edges of the carbon hexagonal network plane.

That is, when a third functional group in which a protic hydrogen atom is replaced by a deuterium atom (a third functional group containing the deuterium atom and a non-hydrogen atom) is heated at a third temperature, the third functional group is While thermally decomposing to produce the third compound gas, the deuterium atoms contained in the third functional group are bound to the carbon atoms at the edges of the carbon hexagonal network surface and remain in the carbon material.

Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) in which the protic hydrogen atom is substituted by the deuterium atom (D) is thermally decomposed by the third heating to form carbon dioxide (CO ₂ ) (third compound gas), while leaving the deuterium atoms (D) bonded to the carbon atoms at the edges of the carbon hexagonal plane.

Further, when the third functional group is an amino group, the third heating produces ammonia as the third compound gas. When the third functional group is a phosphate group, the third heating produces carbon monoxide as the third compound gas. When the third functional group is a sulfonic acid group, the third heating produces sulfur dioxide as the third compound gas. When the third functional group is a boric acid group, the third heating produces carbon monoxide as the third compound gas.

The third temperature is such that the third functional group is thermally decomposed, the third compound gas is generated by the thermal decomposition of the third functional group, and the third functional group is contained in the thermal decomposition of the third functional group. It is the temperature at which deuterium atoms remain bound to the carbon atoms at the edges of the carbon hexagonal plane. The third temperature may be a temperature lower than the second temperature. The third temperature may be a temperature lower than the first temperature. The third temperature may be a temperature at which the first functional group and the second functional group do not thermally decompose.

The third temperature is determined, for example, as the temperature at which the third functional group determined to be analyzed in this method generates a third compound gas by thermal decomposition. That is, the third temperature is, for example, a temperature known in advance as the temperature at which the third functional group generates the third compound gas by thermal decomposition.

Specifically, in the example shown in FIG. 3 in which the third functional group is a carboxy group and the third compound gas is carbon dioxide (CO ₂ ), the third temperature is, for example, a temperature of 0° C. or higher and 600° C. or lower. and the temperature may be 100° C. or higher and 500° C. or lower, or the temperature may be 200° C. or higher and 400° C. or lower.

In this method, the third heating step may be performed before the second heating step. That is, the deuterium atoms remaining in the carbon material due to the thermal decomposition of the third functional group at the third temperature are heated to a second temperature different from the third temperature (e.g., higher than the third temperature) in the second heating step. Heating at a second temperature desorbs from the carbon material to produce a second compound gas containing the deuterium atoms.

That is, the deuterium atoms derived from the third functional group, which are bonded to the edge carbon atoms by heating at the third temperature, are then desorbed by further heating at the second temperature to form the second compound gas. Generate.

Moreover, in this method, the third heating step may be performed before the first heating step. Also, the third temperature may be lower than the first temperature.

Specifically, in the example shown in FIG. 3, the deuterium atoms (D) left in the carbon material by thermal decomposition of the carboxy group (third functional group) by the third heating at the third temperature lower than the first temperature are , then desorbed from the carbon material by a second heating at a second temperature higher than the third temperature to desorb deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) Generate.

The non-hydrogen atoms commonly contained in the first functional group, the second functional group and the third functional group are preferably oxygen atoms as shown in the example of FIG. In this case, the third functional group contains a protic hydrogen atom and an oxygen atom.

Also, the third functional group may further include other non-hydrogen atoms not included in the first functional group and the second functional group. That is, the third functional group may contain carbon atoms, as shown in the example of FIG. In this case, the third functional group contains a protic hydrogen atom, an oxygen atom and a carbon atom.

As shown in the example of FIG. 3, the third functional group is preferably a carboxy group. In this case, the third compound gas may be carbon dioxide (CO ₂ ).

In the third heating step, the carbon material after the HD replacement treatment is heated at a third temperature, and the third compound gas produced from the carbon material is measured. Specifically, in the example shown in FIG. 3, the carbon material after the HD substitution treatment is heated at a third temperature lower than the first temperature, and carbon dioxide (CO ₂ ) (second tri-compound gas).

The method of heating the carbon material at the third temperature in the third heating step is not particularly limited, but for example, the temperature is continuously raised from a temperature lower than the third temperature to a temperature higher than the third temperature. A method of heating while heating is preferably used.

The method of performing the third heating in the third heating step and the method of measuring the third compound gas are not particularly limited, but the TPD method is preferably used. The third heating is performed under vacuum (for example, under a high vacuum of 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less) or an inert atmosphere (for example, selected from the group consisting of nitrogen gas and argon gas under one or more inert gas atmospheres).

Further, the third heating is performed, for example, from a predetermined temperature lower than the third temperature to a predetermined temperature higher than the third temperature at a predetermined temperature increase rate (for example, 2 ° C./min or more and 50 ° C./min or less). The carbon material is heated while increasing the temperature in , and the third compound gas generated from the carbon material is measured while the temperature is increasing.

In this method, the first heating step, the second heating step and the third step may be performed by the TPD method, the first heating step and the third heating step may be performed by the TPD method, and the second heating step may be carried out by the TPO method, but it is preferable to carry out the first heating step, the second heating step and the third heating step by the TPD method. When the first heating step, the second heating step and the third heating step are performed by the TPD method, the first heating step, the second heating step and the third heating step are performed continuously using one TPD analyzer. may be

That is, when the first heating step, the second heating step, and the third step are performed by the TPD method, after the HD replacement treatment, under vacuum or in an inert atmosphere, from a predetermined temperature lower than the third temperature, the The carbon material is heated while increasing the temperature to a predetermined temperature higher than the third temperature, and the amount of the third compound gas generated from the carbon material is measured, and then from the predetermined temperature lower than the first temperature , heating the carbon material while increasing the temperature to a predetermined temperature higher than the first temperature, measuring the amount of the first compound gas generated from the carbon material, and then heating the carbon material to a predetermined temperature lower than the second temperature The carbon material is heated while increasing the temperature from the temperature to a predetermined temperature higher than the second temperature, and the amount of the second compound gas generated from the carbon material is measured. In this case, a temperature higher than the first temperature is used as the second temperature.

Further, when the second heating step is performed by the TPO method, after the HD replacement treatment, from a predetermined temperature lower than the third temperature to a predetermined temperature higher than the third temperature under vacuum or in an inert atmosphere. , while increasing the temperature, the carbon material is heated, the amount of the third compound gas generated from the carbon material is measured, and then from a predetermined temperature lower than the first temperature, a predetermined While heating the carbon material while increasing the temperature to the temperature of, measuring the amount of the first compound gas generated from the carbon material, and then, in an oxidizing atmosphere, from a predetermined temperature lower than the second temperature, The carbon material is heated while increasing the temperature to a predetermined temperature higher than the second temperature, and the amount of the second compound gas generated from the carbon material is measured. In this case, the first heating step may be performed by the TPD method. Moreover, you may implement a 3rd heating process by TPD method. Moreover, as the second temperature, a temperature lower than the first temperature is used.

In the evaluation step, the measurement results of the first compound gas obtained in the first heating step, the measurement results of the second compound gas obtained in the second heating step, and the third compound gas obtained in the third heating step whether the carbon material before the HD substitution treatment contained one or more selected from the group consisting of a first functional group, a second functional group, and a third functional group, based on gas measurement results; And/or the amount of one or more selected from the group consisting of the first functional group, the second functional group and the third functional group contained in the carbon material before the HD substitution treatment is evaluated.

That is, in the evaluation step, for example, based on the measurement result of the first compound gas, the measurement result of the second compound gas, and the measurement result of the third compound gas, the carbon material before the HD replacement treatment is the first It is determined whether or not one or more selected from the group consisting of one functional group, second functional group and third functional group is included.

Specifically, for example, when the third compound gas is measured in the third heating step, it is determined that the carbon material before the HD replacement treatment contained the third functional group. That is, in the example shown in FIG. 3, when carbon dioxide (CO ₂ ) (third compound gas) is generated by the third heating, the carbon material before the HD replacement treatment has a carboxy group (third functional group ) was included. On the other hand, when the third compound gas is not measured in the third heating step, it is determined that the carbon material before the HD replacement treatment did not contain the third functional group.

Further, when the third compound gas is measured in the third heating step, the second compound gas measured in the second heating step is all derived from the third functional group, and the second compound gas measured in the second heating step is If the amount of the third functional group calculated from the amount of the second compound gas is greater than the amount of the third functional group calculated from the amount of the third compound gas measured in the third heating step, It is determined that the carbon material before the HD substitution treatment further contained the second functional group.

Specifically, in the example shown in FIG. 3, all deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) generated by the second heating are carboxy groups (third functional groups) The amount of carboxy groups calculated from the amount of deuterium (HD) and/or deuterium ( _D ) measured in the second heating step assuming that the If the amount of carboxyl groups calculated from the amount of carbon dioxide (CO ₂ ) (third compound gas) obtained is larger than the amount of carboxyl groups, the carbon material before the HD substitution treatment further has phenolic hydroxyl groups (second functional groups). judged to contain.

On the other hand, assuming that the second compound gas measured in the second heating step is all derived from the third functional group, the third functional group calculated from the amount of the second compound gas measured in the second heating step If the amount of groups is not greater than the amount of the third functional group calculated from the amount of the third compound gas measured in the third heating step, the carbon material before the HD substitution treatment has the second functional group. determined that it did not contain

Further, when the third compound gas is not measured in the third heating step and the second compound gas is measured in the second heating step, the carbon material before the HD replacement treatment has the second functional group. judged to contain.

Specifically, in the example shown in FIG. 3, the third heating does not produce carbon dioxide (CO ₂ ) (third compound gas), and the second heating produces hydrogen deuteride (HD) and/or deuterium When (D ₂ ) (second compound gas) is produced, it is determined that the carbon material before the HD substitution treatment contained a phenolic hydroxyl group (second functional group).

In addition, when the second compound gas is measured in the second heating step, assuming that the first compound gas measured in the first heating step is all derived from the second functional group, When the amount of the second functional group calculated from the amount of the first compound gas measured in the second heating step is larger than the amount of the second functional group calculated from the amount of the second compound gas measured in the second heating step , it is determined that the carbon material before the HD substitution treatment further contained the first functional group.

Specifically, in the example shown in FIG. 3, assuming that all carbon monoxide (CO) (first compound gas) generated by the first heating is derived from phenolic hydroxyl groups (second functional groups), the monoxide The amount of the phenolic hydroxyl group calculated from the amount of carbon is calculated from the amount of deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) generated by the second heating. If the amount is greater than the amount of phenolic hydroxyl groups, it is determined that the carbon material before the HD substitution treatment further contained a cyclic ether group (first functional group).

On the other hand, assuming that the first compound gas measured in the first heating step is all derived from the second functional group, the second functional group calculated from the amount of the first compound gas measured in the first heating step If the amount of groups is not greater than the amount of the second functional group calculated from the amount of the second compound gas measured in the second heating step, the carbon material before the HD substitution treatment has the first functional group determined that it did not contain

Further, when the first compound gas is measured in the first heating step and the second compound gas is not measured in the second heating step, the carbon material before the HD replacement treatment has the first functional group. judged to contain.

Specifically, in the example shown in FIG. 3, the first heating produces carbon monoxide (CO) (the first compound gas), and the second heating produces hydrogen deuteride (HD) and deuterium ( _D2 ) (second compound gas) is not generated, it is determined that the carbon material before the HD substitution treatment contained a cyclic ether group (first functional group).

In the evaluation step, for example, based on the measurement result of the first compound gas, the measurement result of the second compound gas, and the measurement result of the third compound, the carbon material contained in the carbon material before the HD replacement treatment One or more amounts selected from the group consisting of the first functional group, the second functional group and the third functional group are calculated.

Specifically, for example, the amount of the third functional group contained in the carbon material before the HD replacement treatment is calculated from the amount of the third compound gas measured in the third heating step. That is, in the example shown in FIG. 3, from the amount of carbon dioxide (CO ₂ ) (third compound gas) generated by the third heating, the carboxy groups (second Calculate the amount of trifunctional groups).

On the other hand, when the third compound gas was not measured in the third heating step and the second compound gas was measured in the second heating step, the second compound gas measured in the second heating step From the amount, the amount of the second functional group contained in the carbon material before the HD substitution treatment is calculated.

Specifically, in the example shown in FIG. 3, the third heating produces carbon dioxide (CO ₂ ) (third compound gas), and the second heating produces hydrogen deuteride (HD) and/or deuterium ( D ₂ ) (second compound gas) is generated, the amount of hydrogen deuteride (HD) and/or deuterium (D ₂ ) generated by the second heating is used for the HD replacement process. Calculate the amount of phenolic hydroxyl groups (second functional groups) contained in the previous carbon material.

Further, the third functional group calculated from the amount of the second compound gas measured in the second heating step assuming that the second compound gas measured in the second heating step is all derived from the third functional group is greater than the amount of the third functional group calculated from the amount of the third compound gas measured in the third heating step, from the amount of the second compound gas corresponding to the difference, H- Calculate the amount of the second functional group contained in the carbon material before the D substitution treatment.

Specifically, in the example shown in FIG. 3, all deuterium (HD) and/or deuterium (D ₂ ) (second compound gas) generated by the second heating are carboxy groups (third functional groups) The amount of carboxy groups calculated from the amount of deuterium (HD) and/or deuterium (D ₂ ) produced by the second heating assuming that it originates from the dioxide produced by the third heating If the amount of carboxyl groups calculated from the amount of carbon (CO ₂ ) (third compound gas) is greater than the amount of carbon monoxide corresponding to the difference, the amount of carbon monoxide contained in the carbon material before the HD replacement treatment is calculated. Calculate the amount of phenolic hydroxyl groups (second functional groups) that were present.

Further, when the third compound gas is measured in the third heating step and the second compound gas is measured in the second heating step, all the first compound gases measured in the first heating step are the second functional The amount of the second functional group calculated from the amount of the first compound gas measured in the first heating step assuming that it is derived from the group is the amount of the second compound gas and the amount of the third compound gas as described above. If it is larger than the amount of the second functional group calculated from the amount of the first compound gas corresponding to the difference, the amount of the first functional group contained in the carbon material before the HD substitution treatment Calculate

Specifically, in the example shown in FIG. 3, the third heating produces carbon dioxide (CO ₂ ) (third compound gas), and the second heating produces hydrogen deuteride (HD) and/or deuterium ( D ₂ ) (second compound gas) is generated, assuming that all carbon monoxide (C) (first compound gas) generated by the first heating is derived from phenolic hydroxyl groups (second functional groups) Then, the amount of phenolic hydroxyl groups calculated from the amount of carbon monoxide generated by the first heating is hydrogen deuteride (HD) and / or deuterium ( _D ) as described above, and carbon dioxide If the amount of phenolic hydroxyl groups calculated from the amount of (CO ₂ ) is greater than the amount of carbon monoxide corresponding to the difference, the cyclic ether groups contained in the carbon material before the HD substitution treatment Calculate the amount of (first functional group).

Thus, according to this method, even when the carbon material contains the third functional group, the first functional group and the second functional group contained in the carbon material can be distinguished for analysis. . Specifically, in the example shown in FIG. 3, first, in the pretreatment step, a cyclic ether group (first functional group), a phenolic hydroxyl group (second functional group), a carboxy group (third functional group), and an edge hydrogen By subjecting the carbon material which may contain atoms to HD substitution treatment, the protic hydrogen atoms of the phenolic hydroxyl group and the protic hydrogen atoms of the carboxy group are respectively substituted with deuterium atoms (D).

Next, in the third heating step, the carbon material after the HD substitution treatment is heated at a third temperature to thermally decompose the carboxy group, and the generated carbon dioxide (CO ₂ ) (third compound gas) is Measure.

Furthermore, in the first heating step, by heating the carbon material after the third heating at the first temperature, the cyclic ether group and the phenolic hydroxyl group containing the deuterium atom are thermally decomposed to generate carbon monoxide (CO) (first compound gas) is measured.

Furthermore, in the second heating step, the carbon material after the first heating is heated at a second temperature, deuterium atoms derived from thermal decomposition of the phenolic hydroxyl groups after the HD substitution treatment, and the HD substitution treatment Deuterium (HD) and/or deuterium (D ₂ ) produced (second compound gas) is measured by desorbing each deuterium atom from the subsequent thermal decomposition of the carboxy group.

After that, in the evaluation step, the measurement result of carbon dioxide (CO ₂ ) obtained in the third heating step, the measurement result of carbon monoxide (CO) obtained in the first heating step, and the measurement result of carbon monoxide (CO) obtained in the second heating step Based on the measurement results of deuterium (HD) and / or deuterium (D ₂ ) obtained, the carbon material before the HD substitution treatment is selected from the group consisting of a cyclic ether group, a phenolic hydroxyl group, and a carboxy group. 1 selected from the group consisting of a cyclic ether group, a phenolic hydroxyl group, and a carboxy group contained in the carbon material before the HD substitution treatment, and/or whether or not it contained one or more selected More than the amount, evaluate.

Further, in the second heating step, hydrogen (H ₂ ) derived from edge hydrogen atoms (hydrogen-containing compound gas) generated by the second heating is further measured, and in the evaluation step, the hydrogen (H ₂ ) is measured. Based on the results, whether or not the carbon material before the HD replacement treatment contained edge hydrogen atoms and/or the amount of edge hydrogen atoms contained in the carbon material before the HD replacement treatment, may be further evaluated.

Next, specific examples according to this embodiment will be described.

[Preparation of carbon material (hydrogen-deuterium substitution treatment)]
As the carbon material, commercially available activated carbon (MSC30, Kansai Coke & Chemicals Co., Ltd.) (hereinafter referred to as "MSC") was used.

In addition, MSC was heat-treated at 425° C. for 8 hours in a stream of dehydrated air to obtain oxygen-treated MSC (hereinafter referred to as “MSC-O ₂ ”). In addition, by immersing MSC in a 30 w/v% hydrogen peroxide (H ₂ O ₂ ) aqueous solution at 80 ° C. for 2 hours, hydrogen peroxide-treated MSC (hereinafter referred to as “MSC-H ₂ O ₂ ”) ).

Then, these three types of carbon materials were subjected to HD replacement treatment. That is, each carbon material was placed in a vacuum-sealable vial and vacuum-dried. Next, while the vial was vacuum-sealed, a syringe was used to introduce heavy water (D ₂ O) into the vial, thereby suspending the carbon material in the heavy water within the vial. After that, the heavy water suspension containing the carbon material was placed in the sample stage of the TPD analyzer, and the suspension was freeze-dried in the TPD analyzer.

Thus, MSC (hereinafter referred to as “MSC (D ₂ O)”) subjected to HD replacement treatment, MSC-O ₂ (hereinafter referred to as “MSC-O ₂ (D ₂ O)”), and MSC-H ₂ O ₂ (hereinafter referred to as “MSC-H ₂ O ₂ (D ₂ O)”) was obtained.

[Thermal desorption method]
In a TPD analyzer in which the freeze-dried carbon material is placed on a sample stage, the temperature is raised from 0 ° C. to 1600 ° C. at a temperature increase rate of 10 ° C./min under a high vacuum of 1 × 10 ^-3 Pa or less. while heating the carbon material, and the desorption gas (specifically, CO, CO ₂ , H ₂ , HD, and D ₂ ) generated during the period in which the temperature rises from 0 ° C. to 1600 ° C. measured by For comparison, the desorption gas was also measured by the TPD method for the MSC not subjected to the HD replacement treatment.

[result]
Figures 4A and 4B show the CO and _CO2 TPD spectra and _H2 TPD spectra obtained for the MSC, respectively. Figures 5A and 5B show the CO and _CO2 TPD spectra and the _H2 , HD and _D2 TPD spectra obtained for MSC ( _D2O ), respectively. FIG. 6A and FIG. 6B show the TPD spectra of CO and CO ₂ and TPD spectra of H ₂ , HD and D ₂ obtained for MSC-O ₂ (D ₂ O), respectively. FIG. 7A and FIG. 7B show the TPD spectra of CO and CO ₂ and TPD spectra of H ₂ , HD and D ₂ obtained for MSC-H ₂ O ₂ (D ₂ O), respectively.

As shown in FIGS. 5B, 6B, and 7B, in the TPD spectra of MSC(D ₂ O), MSC-O ₂ (D ₂ O), and MSC-H ₂ O ₂ (D ₂ O), D ₂ and Desorption of HD was confirmed, but desorption of H ₂ O was not.

FIG. 8 shows the results of measurement by the TPD method for each of MSC, MSC(D ₂ O), MSC-O ₂ (D ₂ O), and MSC-H ₂ O ₂ (D ₂ O). In addition, the amount of carbon monoxide (CO) produced (mmol/g), the total amount of deuterium (D) atoms (mmol/g), the total amount of hydrogen (H) atoms (mmol/g), and carbon dioxide ( _CO2 shows the production amount (mmol/g) of

Also, FIG. 9 shows the quantitative results shown in FIG. 8 for each of MSC, MSC(D ₂ O), MSC-O ₂ (D ₂ O) and MSC-H ₂ O ₂ (D ₂ O). The amount of carboxy groups (mmol/g), the amount of cyclic ether groups (mmol/g), the amount of phenolic hydroxyl groups (mmol/g), and the amount of edge hydrogen atoms (mmol/g) obtained by .

The contents of carboxy groups, cyclic ether groups, phenolic hydroxyl groups, and edge hydrogen atoms in each carbon material shown in FIG. 9 were calculated as follows. That is, the sum of the amount of cyclic ether groups and the amount of phenolic hydroxyl groups was obtained from the amount of carbon monoxide (P: see FIG. 8) generated by the first heating. The total amount of deuterium atoms (Q: see FIG. 8) was obtained from the amount of deuterium generated by the second heating and the amount of deuterium compounds. The total amount of hydrogen atoms (R: see FIG. 8) was obtained from the amount of hydrogen generated by the second heating and the amount of deuterium compounds. The amount of carboxy groups was obtained from the amount of carbon dioxide (S: see FIG. 8) generated by the third heating.

Then, the amount of phenolic hydroxyl groups was obtained by subtracting the value of S from the value of Q. Furthermore, the amount of cyclic ether was determined by subtracting the amount of phenolic hydroxyl groups from the value of P. As the amount of edge hydrogen atoms and the amount of carboxyl groups, the value of R and the value of S were used, respectively.

As shown in FIG. 9, for MSC not subjected to the HD substitution treatment, no deuterium compounds and deuterium were produced, so it was not possible to distinguish between phenolic hydroxyl groups and cyclic ethers. had to be obtained as a range including errors.

On the other hand, for MSC(D ₂ O), MSC-O ₂ (D ₂ O), and MSC-H ₂ O ₂ (D ₂ O) subjected to HD substitution treatment, deuterium compounds and deuterium Since the production of was confirmed, the total amount of deuterium atoms could be determined from the production amount of the deuterium compound and deuterium, and as a result, the phenolic hydroxyl group and the cyclic ether could be quantified separately.

Claims (9)

A first functional group that satisfies the following conditions (a1) to (c1):
(a1) the first functional group is bonded to a carbon atom at the edge of the carbon hexagonal network;
(b1) the first functional group does not contain protic hydrogen atoms, which are hydrogen atoms that can be substituted with deuterium atoms, and contains non-hydrogen atoms; and (c1) the first functional group contains a first temperature thermally decomposing to produce a first compound gas comprising said non-hydrogen atoms;
A second functional group that satisfies the following conditions (a2) to (e2):
(a2) the second functional group is attached to a carbon atom on the edge of the carbon hexagonal network;
(b2) the second functional group comprises a protic hydrogen atom and the non-hydrogen atom;
(c2) the second functional group is thermally decomposed by heating at the first temperature to produce the first compound gas;
(d2) the second functional group is thermally decomposed by heating at the first temperature after the protic hydrogen atom is replaced with a deuterium atom, and is bonded to the carbon atom at the edge of the carbon hexagonal network plane; and (e2) the deuterium atoms left in (d2) are desorbed by heating at a second temperature different from the first temperature to contain the deuterium atoms. producing a second compound gas; and
An edge hydrogen atom that is a hydrogen atom that satisfies the following conditions (x) to (z):
(x) the edge hydrogen atoms are bonded to the edge carbon atoms of the carbon hexagonal plane;
(y) said edge hydrogen atoms are not replaced with deuterium atoms; and (z) said edge hydrogen atoms are desorbed upon heating at said second temperature to desorb deuterium atoms including said edge hydrogen atoms. producing a hydrogen-containing compound gas that is free of
A pretreatment step of subjecting a carbon material that may contain a hydrogen-deuterium substitution treatment to
After the pretreatment step, a first heating step of heating the carbon material at the first temperature to measure the first compound gas generated from the carbon material;
After the first heating step, a second heating step of heating the carbon material at the second temperature and measuring the second compound gas generated from the carbon material;
A group in which the carbon material before the hydrogen-deuterium substitution treatment comprises the first functional group and the second functional group, based on the measurement result of the first compound gas and the measurement result of the second compound gas. and/or from the group consisting of the first functional group and the second functional group contained in the carbon material before the hydrogen-deuterium substitution treatment an evaluating step of evaluating one or more selected quantities;
A method for analyzing carbon materials, comprising: Further measuring the hydrogen-containing compound gas generated from the carbon material in the second heating step,
In the evaluation step, based on the measurement results of the hydrogen-containing compound gas, whether or not the carbon material before heating at the first temperature contained the edge hydrogen atoms and/or the hydrogen-heavy further evaluating the amount of the edge hydrogen atoms contained in the carbon material before the hydrogen replacement treatment;
The method for analyzing a carbon material according to claim 1. wherein the non-hydrogen atom is an oxygen atom;
The method for analyzing a carbon material according to claim 1 or 2. The first functional group is a cyclic ether group,
The second functional group is a phenolic hydroxyl group,
The method for analyzing a carbon material according to claim 3. The first compound gas is carbon monoxide,
The second compound gas is one or more selected from the group consisting of hydrogen deuteride, deuterium, semi-heavy water, and heavy water.
The method for analyzing a carbon material according to claim 4. The hydrogen-containing compound gas is hydrogen and/or water,
The method for analyzing a carbon material according to any one of claims 1 to 5. The carbon material has a third functional group that satisfies the following conditions (a3) to (e3):
(a3) the third functional group is attached to a carbon atom on the edge of the carbon hexagonal plane;
(b3) the third functional group comprises a protic hydrogen atom and the non-hydrogen atom;
(c3) the third functional group does not produce the first compound gas upon heating at the first temperature after the protic hydrogen atoms are replaced with deuterium atoms;
(d3) The third functional group is thermally decomposed by heating at a third temperature different from the first temperature and the second temperature after the protic hydrogen atom is replaced with a deuterium atom, resulting in the and (e3 ) the deuterium atoms left in (d3) are desorbed by heating at the second temperature to produce the second compound gas;
A carbon material that can further include
The method for analyzing the carbon material includes a third heating step of heating the carbon material at the third temperature after the hydrogen-deuterium substitution treatment and measuring the third compound gas generated from the carbon material. further includes
In the evaluation step, the carbon material before the hydrogen-deuterium replacement treatment is based on the measurement result of the first compound gas, the measurement result of the second compound gas, and the measurement result of the third compound gas. contains one or more selected from the group consisting of the first functional group, the second functional group and the third functional group, and/or the carbon before the hydrogen-deuterium substitution treatment evaluating the amount of one or more selected from the group consisting of the first functional group, the second functional group, and the third functional group contained in the material;
The method for analyzing a carbon material according to any one of claims 1 to 6. The third functional group is a carboxy group,
The method for analyzing a carbon material according to claim 7. wherein the third compound gas is carbon dioxide;
The method for analyzing a carbon material according to claim 8.

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