JP2021018190A - Method for analyzing carbon material - Google Patents

Abstract

To provide a method for analyzing a carbon material, capable of effectively analyzing functional groups included in the carbon material.SOLUTION: The method for analyzing a carbon material comprises: a pretreatment step of subjecting a carbon material that may include a first functional group connected with carbon atoms at the edges of a carbon hexagon net surface, a second functional group and an edge hydrogen atom to hydrogen-deuterium substitution; a first heating step of heating the carbon material at a first temperature after the hydrogen-deuterium substitution to measure a first compound gas formed of the carbon material; a second heating step of heating the carbon material at a second temperature to measure a second compound gas formed of the carbon material; and an evaluation step of evaluating whether or not the carbon material before the hydrogen-deuterium substitution includes one or more functional groups selected from a group consisting of the first and second functional groups on the basis of the measurement results of the first and second compound gases and/or the amount of the one or more functional groups selected from the group consisting of the first and second functional groups included in the carbon material before the hydrogen-deuterium substitution.SELECTED DRAWING: Figure 2

Description

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

In Patent Document 1, the total amount of the carbon edge surface of the carbon catalyst is calculated from the quantification result of the desorbed gas of the carbon catalyst obtained by using a temperature raising desorption analyzer capable of raising the temperature up to 1600 ° C. It is described that the average carbon mesh surface size L was calculated from. Non-Patent Document 1 and Non-Patent Document 2 describe that the temperature has been raised to 1800 ° C. by the temperature desorption method.

International Publication No. 2017/209244

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 molecular structures. Carbon 2017; 125: 146-155

The thermal desorption method is useful for analyzing the type and amount of functional groups bonded to carbon atoms at the edges of the carbon hexagonal network surface of carbon materials. However, conventionally, there have been combinations of functional groups that cannot be distinguished by the thermal desorption method.

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

The method for analyzing a carbon material according to an embodiment of the present invention for solving the above problems is a first functional group satisfying the following conditions (a1) to (c1): (a1) The first functional group is carbon. It is bonded to a carbon atom at the edge of the hexagonal network; (b1) The first functional group does not contain a protonic hydrogen atom, which is a hydrogen atom that can be replaced with a heavy hydrogen atom, but contains a non-hydrogen atom; And (c1) the first functional group is thermally decomposed by heating at the first temperature to produce the first compound gas containing the non-hydrogen atom; and (a2) to (e2) below. Second functional group satisfying the conditions: (a2) The second functional group is bonded to a carbon atom at the edge of the carbon hexagonal network; (b2) The second functional group is a protonic hydrogen atom and Including 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. After the hydrogen atom is replaced with a deuterium atom, the group is thermally decomposed by heating at the first temperature to leave the deuterium atom bonded to the carbon atom at the edge of the carbon hexagonal network ;, And (e2) the deuterium atoms left in (d2) are desorbed by heating at a second temperature different from the first temperature to generate a second compound gas containing the deer hydrogen atoms; Edge hydrogen atom which is a hydrogen atom satisfying the following conditions (x) to (z): (x) The edge hydrogen atom is bonded to the carbon atom at the edge of the carbon hexagonal network;, (y) The edge hydrogen atom is not replaced with a deuterium; and (z) the edge hydrogen atom is desorbed by heating at the second temperature, and the hydrogen-containing compound containing the hydrogen atom and not containing the deuterium atom. A pretreatment step of applying a hydrogen-hydrogen substitution treatment to a carbon material which may contain gas; and, and after the pretreatment step, the carbon material is heated at the first temperature to be removed from the carbon material. After the first heating step of measuring the generated first compound gas and the first heating step, the carbon material is heated at the second temperature to generate the second compound gas generated 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-heavy hydrogen substitution treatment is 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-hydrohydro atom substitution treatment and the said. Select from the group consisting of second functional groups Includes an evaluation step of evaluating one or more quantities to be made. According to the present invention, there is provided an analysis method for a carbon material capable of effectively analyzing a functional group contained in the carbon material.

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. Whether or not the previous carbon material contained the edge hydrogen atom and / or the amount of the edge hydrogen atom contained in the carbon material before the hydrogen-hydrohydrogen substitution treatment is further evaluated. It may be that.

Further, in the above 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. Further, 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, semiheavy water, and heavy water. May be good. Further, in the above method, the hydrogen-containing compound gas may be hydrogen and / or water.

Further, in the method, the carbon material is a third functional group satisfying the following conditions (a3) to (e3): (a3) The third functional group is bonded to a carbon atom at an edge of a carbon hexagonal network surface. ;, (b3) The third functional group contains a protonic hydrogen atom and the non-hydrogen atom; (c3) The third functional group has the hydrogen atom replaced with a deuterium atom. Later, heating at the first temperature does not produce the first compound gas; (d3) the third functional group is the first temperature and the first after the hydrogen atom is replaced with a deuterium atom. By heating at a third temperature different from the second temperature, it is thermally decomposed to generate the first compound gas containing the non-hydrogen atom and the third compound gas different from the second compound gas, and the carbon hexagonal network surface. The deuterium atom bonded to the carbon atom of the edge is left; and (e3) the deuterium atom left in the (d3) is desorbed by heating at the second temperature, and the second compound. Produces gas;
The third compound produced from the carbon material is obtained by heating the carbon material at the third temperature after the hydrogen-hydrohydrogen substitution treatment. A third heating step for measuring the gas is further included, 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-hydrohydrogen 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 , One or more amounts 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-hydrohydrogen substitution treatment are evaluated. It may be that. In this case, the third functional group may be a carboxy group. Further, in this case, the third compound gas may be carbon dioxide.

According to the present invention, there is provided an analysis method for a carbon material capable of effectively analyzing a functional group contained in the carbon material.

It is explanatory drawing which shows an example of the desorption gas generation by thermal decomposition of a functional group contained in a carbon material. It is explanatory drawing which shows another example of the desorption gas generation by the thermal decomposition of the functional group contained in a carbon material. It is explanatory drawing which shows still another example of the desorption gas generation by the thermal decomposition of a functional group contained in a carbon material. It is explanatory drawing which shows typically the process included in the example of the analysis method of the carbon material which concerns on one Embodiment of this invention. It is explanatory drawing which shows schematic | process included in another example of the analysis method of carbon material which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the temperature desorption spectrum obtained about the carbon material (MSC) which has not been subjected to the hydrogen-deuterium substitution treatment in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows the other example of the temperature desorption spectrum obtained about the carbon material (MSC) which has not been subjected to the hydrogen-deuterium substitution treatment in the Example which concerns on one Embodiment of this invention. In the embodiment according to one embodiment of the present invention, the hydrogen - is an explanatory diagram showing an example of the obtained Atsushi Nobori spectrum of the deuterium replacement process performed carbon material _{(MSC (D 2 O))} . In the embodiment according to one embodiment of the present invention, the hydrogen - an explanatory view showing another example of Atsushi Nobori spectra obtained for deuterium replacement process performed carbon material (MSC (D 2 _O)) is there. In the embodiment according to one embodiment of the present invention, the hydrogen - explanatory view showing an example of the obtained Atsushi Nobori spectrum of the deuterium replacement process performed carbon material (MSC-O 2 (D 2 O)) Is. In the embodiment according to one embodiment of the present invention, the hydrogen - shows another example of Atsushi Nobori spectra obtained for the carbon material to deuterium substitution process is performed (MSC-O 2 (D 2 O)) It is explanatory drawing. In the example according to the embodiment of the present invention, an example of the temperature desorption spectrum obtained for the carbon material (MSC-H ₂ O ₂ (D ₂ O)) subjected to the hydrogen-deuterium substitution treatment is shown. It is explanatory drawing. Another example of the thermal desorption spectrum obtained for a carbon material (MSC-H ₂ O ₂ (D ₂ O)) subjected to a hydrogen-deuterium substitution treatment in an example according to an embodiment of the present invention. It is explanatory drawing which shows. It is explanatory drawing which shows an example of the quantitative result by the temperature desorption method obtained in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the result of having calculated the functional group content of a carbon material from the quantitative result by the temperature desorption method in the Example which concerns on one Embodiment of this invention.

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

The thermal desorption (TPD) method is useful for analyzing the type and amount of functional groups bonded to carbon atoms at the edges of the carbon hexagonal network of carbon materials. However, conventionally, for example, it has been difficult to distinguish and analyze a cyclic ether group and a phenolic hydroxyl group by the TPD method.

That is, as shown in FIG. 1A, the cyclic ether group and the phenolic hydroxyl group bonded to the carbon atom at the edge of the carbon hexagonal network contained in the carbon material are thermally decomposed at the same temperature when heated, and one. Since the same desorbed gas called carbon oxide (CO) is generated, it is not possible to distinguish between 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 atom contained in the phenolic hydroxyl group is converted into a carbon atom at the edge of the carbon hexagonal network surface. It is left 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 the first temperature to generate carbon monoxide, and then heated at a second temperature different from the first temperature. Thereby, the hydrogen atom bonded to the carbon atom of the edge derived from the phenolic hydroxyl group is desorbed, and the hydrogen (H ₂ ) containing the desorbed hydrogen atom is measured to obtain the cyclic ether group and phenol. It is also possible to distinguish it from the sex hydroxyl group.

However, as shown in FIG. 1C, when the carbon material contains an edge hydrogen atom bonded to a carbon atom at the edge of the carbon hexagonal network, hydrogen derived from the edge hydrogen atom by heating at the second temperature ( Since H ₂ ) is also produced, it is difficult to distinguish between the cyclic ether group and the phenolic hydroxyl group by measuring the hydrogen (H ₂ ).

The inventors of the present invention have completed the present invention as a result of diligent studies on technical means for solving the above problems. FIG. 2 schematically shows a step included in an example of the carbon material analysis method (hereinafter, referred to as “the present method”) according to the present 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 a phenolic hydroxyl group shown in FIG. 2) can be added to a carbon material. A pretreatment step of performing a hydrogen-hydrohydrogen substitution treatment (hereinafter referred to as "HD substitution treatment") (a treatment corresponding to "HD substitution" shown in FIG. 2), and after the pretreatment step, the carbon. A first heating step in which the material is heated at the first temperature and the first compound gas produced from the carbon material is measured, and after heating at the first temperature, the carbon material is different from the first temperature. 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. It comprises an evaluation step of evaluating one or more amounts selected from the group consisting of primary and secondary functional groups 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 surface; (b1) first functional group. The group does not contain a protonic hydrogen atom, which is a hydrogen atom that can be replaced with a heavy hydrogen atom, but contains a non-hydrogen atom (an atom corresponding to the oxygen atom of the cyclic ether group shown in FIG. 2); and (c1) th. The monofunctional group is thermally decomposed by heating at the first temperature (heating corresponding to the "first heating" shown in FIG. 2), and the first compound gas containing the non-hydrogen atom (cyclic ether shown in FIG. 2). A gas corresponding to carbon monoxide (CO) derived from an atom) is produced.

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;, (b2) the second functional group. The groups are a protonic 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 type as the non-hydrogen atom contained in the primary functional group (phenolic property shown in FIG. 2). Includes (atom corresponding to the oxygen atom of the hydroxyl); (c2) The second functional group is thermally decomposed by heating at the first temperature and is derived from the first compound gas (derived from the phenolic hydroxyl atom shown in FIG. 2). (Gas corresponding to carbon monoxide (CO)); (d2) The second functional group is thermally decomposed by heating at the first temperature after the hydrogen atom is replaced with a deuterium atom. , The dear hydrogen atom bonded to the carbon atom at the edge of the carbon hexagonal network (heavy hydrogen corresponding to the deuterium atom (D) remaining on the carbon hexagonal network after "first heating" of the phenolic hydroxyl group in FIG. 2). Atomic atoms); and (e2) The dehydrogen atoms left in (d2) are heated at a second temperature different from the first temperature (heating corresponding to the "second heating" shown in FIG. 2). , Desorbed and desorbed a second compound gas containing the dehydrogen atom (a gas corresponding to dehydrogenated hydrogen (HD) and / or deuterium (D ₂ ) generated by "second heating" in FIG. 2). Generate.

Further, the carbon material may further contain an edge hydrogen atom (a hydrogen atom corresponding to the edge hydrogen atom shown in FIG. 2) which is a hydrogen atom satisfying the following conditions (x) to (z): (x) edge hydrogen atom. Is bonded to the carbon atom at the edge of the carbon hexagonal network; (y) the edge hydrogen atom is not replaced by the deuterium; and (z) the edge hydrogen atom is heated at the second temperature. Desorbed, a hydrogen-containing compound gas containing the edge hydrogen atom (strictly speaking, a hydrogen atom derived from the edge hydrogen atom) and not containing a heavy hydrogen atom (produced by "second heating" in FIG. 2). Edge A gas corresponding to hydrogen (H ₂ ) derived from a hydrogen atom) is generated.

In this method, carbon materials that may contain a primary functional group, a secondary functional group, and an edge hydrogen atom are analyzed. Here, the carbon material that "can contain" the first functional group, the second functional group, and the edge hydrogen atom is a carbon known to contain the first functional group, the second functional group, and the edge hydrogen atom. Includes materials and carbon materials that may contain the primary, secondary, and edge hydrogen atoms.

That is, the carbon material to be analyzed may be, for example, a carbon material for which it is unknown whether or not it contains a first functional group, a second functional group, and an edge hydrogen atom, and theoretically or empirically. , A carbon material reasonably understood to contain a primary functional group, a secondary functional group, and an edge hydrogen atom, or a primary functional group, a secondary functional group, and an edge hydrogen atom. May be a carbon material whose content of the first functional group, the second functional group, or the edge hydrogen atom is unknown, although the above has already been confirmed.

The carbon material is a material mainly composed of carbon. That is, for example, the carbon material may have a carbon atom content of 70% by weight or more, 75% by weight or more, 80% by weight or more, or 85% by weight or more. It 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. May be specified. The composition of the carbon material is measured by elemental analysis.

The carbon material is preferably an amorphous carbon material. Amorphous carbon material is a carbon material containing carbon atoms having an irregular spatial arrangement in its carbon structure. The amorphous carbon material is a carbon material containing a carbon structure that does not reach the graphite structure. Therefore, the amorphous carbon material is a carbon material having 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 ray as an X-ray source.

The carbon material is preferably a powdered carbon material. The carbon material is preferably a porous carbon material. The BET specific surface area of the carbon material is not particularly limited, but may be, for example, 10 m ² / g or more, preferably 50 m ² / g or more, and more preferably 70 m ² / g or more. It is particularly preferable that it is 100 m ² / g or more.

Both the first functional group and the second functional group are bonded to the carbon atom at the edge of the carbon hexagonal network surface and contain a common non-hydrogen atom. 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 the carbon atom at the edge of the carbon hexagonal network surface, and , Contains oxygen atoms (non-hydrogen atoms).

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

Protic hydrogen atoms are also called ionic hydrogen atoms. A protic hydrogen atom is a hydrogen atom that can be ionized in water to become a hydrogen ion. The protonated hydrogen atom can be replaced with a deuterium atom by, for example, a hydrogen-deuterium substitution treatment described later.

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 not contain a hydrogen atom (protic hydrogen atom and aprotic hydrogen atom). 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 carbon atom of the edge via the non-hydrogen atom contained in the first functional group and the second functional group. That is, the non-hydrogen atom contained in the first functional group and the second functional group is bonded to the carbon atom of the edge. Specifically, in the example shown in FIG. 2, both the cyclic ether group (first functional group) and the phenolic hydroxyl group (second functional group) become carbon atoms at the edges via oxygen atoms (non-hydrogen atoms). It is combined.

The first functional group and the second functional group are thermally decomposed by heating at the first temperature (hereinafter referred to as "first heating") to generate a first compound gas containing a non-hydrogen atom. That is, the first functional group and the second functional group are thermally decomposed at the same temperature (first temperature) to produce 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 first compound gas derived from the thermal decomposition of the second functional group are derived. First compound gas is produced. 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 and carbon monoxide (first compound gas). ) Is generated.

The second functional group is thermally decomposed by heating at the first temperature after the protic hydrogen atom contained in the second functional group is replaced with the deuterium atom, and the carbon at the edge of the carbon hexagonal network surface is carbon. The deuterium atom bonded to the atom is left.

That is, when a second functional group in which a protonic hydrogen atom is replaced with a deuterium atom (a second functional group containing the deuterium atom and a non-hydrogen atom) is heated at the first temperature, the second functional group becomes While thermally decomposing to produce the first compound gas, the deuterium atom contained in the second functional group is bonded to the carbon atom at the edge of the carbon hexagonal network surface and remains 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 replaced with the deuterium atom (D) is thermally decomposed by the first heating, and the carbon hexagonal network surface. The deuterium atom (D) bonded to the carbon atom at the edge of is left.

At the first temperature, the first functional group and the second functional group are thermally decomposed, and the common first compound gas is generated by the thermal decomposition of the first functional group and the second functional group, and the second functional group This is the temperature at which the heavy hydrogen atom contained in the second functional group by thermal decomposition is bonded to the carbon atom at the edge of the carbon hexagonal network surface and remains.

The first temperature is determined as the temperature at which the first and second functional groups 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 a 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, 400 ° C. or higher and 1000 ° C. or lower, or 500 ° C. or higher and 900 ° C. or lower.

The deuterium atoms left 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"). Deuterium to produce a second compound gas containing the deuterium atom.

That is, the deuterium atom derived from the second functional group bonded to the carbon atom of the edge by the first heating is desorbed by further heating at a second temperature different from the first temperature, and the second compound. Produces gas.

Specifically, in the example shown in FIG. 2, the deuterium atom (D) left in the carbon material by the thermal decomposition of the phenolic hydroxyl group (second functional group) by the first heating is subsequently different from the first temperature. Second heating at two temperatures desorbs from the carbon material to produce hydrogen deuteride (HD) and / or deuterium (D ₂ ) (second compound gas).

The second temperature is a temperature different from the first temperature used for the thermal decomposition of the second functional group, and the second temperature left in the carbon material by the thermal decomposition of the second functional group at the first temperature. It is a temperature at which a deferred hydrogen atom derived from a functional group is eliminated to generate a second compound gas.

The second temperature is, for example, a compound containing hydrogen atoms in which hydrogen atoms remaining in the carbon material are desorbed by thermally decomposing the second functional group that has not been subjected to the HD substitution treatment at the first temperature. Determined as the temperature at which the gas is produced. That is, at the second temperature, for example, hydrogen atoms remaining in the carbon material are eliminated by thermal decomposition of the second functional group that has not been subjected to the HD substitution treatment, and a compound gas containing the hydrogen atoms is generated. A temperature previously known as temperature.

Specifically, as shown in FIG. 1B, a phenolic hydroxyl group (second functional group) in which a protonic hydrogen atom is not substituted with a deuterium atom is thermally decomposed to generate carbon monoxide (first compound gas). At that time, the hydrogen atom contained in the phenolic hydroxyl group is bonded to the carbon atom at the edge of the carbon hexagonal network surface and remains in the carbon material.

Further, as shown in FIG. 1B, the hydrogen atom derived from the phenolic hydroxyl group remaining in the carbon material is removed from the carbon material by heating at a higher temperature (heating corresponding to the second heating in this method). Desorb to produce hydrogen (H ₂ ).

Therefore, in this case, the temperature at which the hydrogen atom derived from the phenolic hydroxyl group is desorbed from the carbon material to generate hydrogen (H ₂ ) is determined as the second temperature.

That is, if the temperature at which a hydrogen atom derived from a phenolic hydroxyl group is desorbed from a carbon material to generate hydrogen (H ₂ ) is known in advance, that temperature is adopted as the second temperature in this method.

Specifically, the figure in which 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 deuteride (D ₂ ). In the example shown in 2, the second temperature may be, for example, 600 ° C. or higher and 1600 ° C. or lower, 700 ° C. or higher and 1500 ° C. or lower, 800 ° C. or higher and 1400 ° C. or lower. It may be the temperature of.

Here, FIG. 2 shows an example in which the second heating is carried out by the TPD method. When the second heating is carried out 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 carried out by a temperature-rising oxidation (TPO) method. When the second heating is carried out by the TPO method, the second heating of the carbon material is carried out in an oxidizing atmosphere after the first heating, so that the second compound gas is semi-heavy water (DHO) and / or heavy water (D _2). O) is generated.

When the second heating is carried out by the TPO method, the second temperature may be, for example, 300 ° C. or higher and 1000 ° C. or lower, 400 ° C. or higher and 900 ° C. or lower, or 500 ° C. As mentioned above, the temperature may be 800 ° C. or lower.

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

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

Further, the first compound gas may not contain hydrogen atoms and deuterium atoms. Specifically, in the example shown in FIG. 2, 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 hydrogen deuteride (HD), deuteride (D ₂ ), semiheavy water (DHO), and heavy water (D ₂ ). It may be 1 or more selected from the group consisting of O).

The edge hydrogen atom is a hydrogen atom bonded to the carbon atom at the edge of the carbon hexagonal network surface and is not replaced with the deuterium atom. That is, the edge hydrogen atom is not a protonic hydrogen atom. Further, the edge hydrogen atom is desorbed from the carbon material by heating at the second temperature to generate a hydrogen-containing compound gas containing a hydrogen atom derived from the edge hydrogen atom and not containing a deuterium atom.

Specifically, in the example shown in FIG. 2, the edge hydrogen atom is desorbed from the carbon material by heating at the second temperature and contains a hydrogen atom derived from the edge hydrogen atom and does not contain a heavy hydrogen atom. Produces hydrogen (H ₂ ) (hydrogen-containing compound gas).

A hydrogen atom contained in a hydrocarbon group such as an alkyl group is also not a protonic hydrogen atom, but the hydrocarbon group produces a hydrocarbon gas by heating at a second temperature. In this respect, the hydrogen-containing compound gas generated by heating the edge hydrogen atom 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 a hydrogen-containing compound gas when the second heating is carried out by the TPD method. When the second heating is carried out by the TPO method, water (H ₂ O) is generated as a hydrogen-containing compound gas by the second heating in an oxidizing atmosphere.

In the pretreatment step, the carbon material is subjected to HD substitution treatment. The HD substitution treatment is a treatment for replacing a protonic hydrogen atom contained in a carbon material with a deuterium atom. By the HD substitution treatment, the protic hydrogen atom contained in the second functional group is replaced with a deuterium atom. That is, the second functional group contained in the carbon material after the HD substitution treatment contains a deuterium atom in place of the protonic hydrogen atom contained before the HD substitution treatment.

The HD substitution treatment of the carbon material is not particularly limited as long as it is a treatment of substituting a protonic hydrogen atom with a deuterium atom. One or more selected from the group consisting of a method of contacting with deuterium and a method of confining the carbon material and heavy water in a closed container and leaving them at a temperature of more than 0 ° C. is preferably used, and the carbon material is immersed in heavy water. The method used is particularly preferably used.

Instead of the heavy water, acidic compounds containing deuterium (e.g., deuterated hydrogen chloride (DCl), deuterated sulfuric acid (D ₂ SO _4), deuterated perchlorate (DClO _4), And one or more selected from the group consisting of deuterated nitric acid (DNO ₃ )), but heavy water is preferred.

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) produced from the carbon material is measured. To 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. The method of heating while heating is preferably used.

The method of performing 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 selected from the group consisting of vacuum (for example, 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less, high vacuum) or an inert atmosphere (for example, nitrogen gas and argon gas). It is preferable to carry out in an atmosphere of one or more kinds of inert gases.

Further, 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 heating rate (for example, 2 ° C./min or more, 50 ° C./min or less). This is done by heating the carbon material while raising the temperature with. In this case, the first compound gas produced from the carbon material is measured while the temperature rises due to the first heating.

The measurement of the first compound gas is preferably carried out using a temperature rise desorption analyzer (TPD analyzer) equipped with a mass spectrometer. As the mass spectrometer, it is preferable to use a quadrupole mass spectrometer (QMS).

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, hydrogen deuteride (HD) and / or deuterium (D ₂ ) produced from the carbon material by heating the carbon material after the first heating at the second temperature. (Second compound gas) is measured. Incidentally, as described above, when the second heating is carried out by TPO method, as the second compound gas, measuring the half-heavy water (DHO) and / or heavy water (D 2 _O).

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. The method of heating while heating is preferably used.

The method of carrying out 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 the TPD method is used, the second heating is carried out under vacuum (eg, under high vacuum of 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less) or under an inert atmosphere (eg, nitrogen gas and argon). It is preferably carried out in an atmosphere of one or more inert gases selected from the group consisting of gases. On the other hand, when the TPO method is used, the second heating is preferably performed in an oxygen atmosphere (for example, an atmosphere in which the oxygen partial pressure is 1 kPa or more and 200 kPa or less).

Further, 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 heating rate (for example, 2 ° C./min or more, 50 ° C./min or less). This is done by heating the carbon material while raising the temperature with. In this case, the second compound gas produced from the carbon material is measured while the temperature rises due to the second heating.

When the carbon material contains an edge hydrogen atom, the hydrogen-containing compound gas derived from the edge hydrogen atom is also generated by the second heating of the carbon material, but the hydrogen-containing compound gas contains a deuterium atom. 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 an edge hydrogen atom produced by the second heating (for example, the second heating by the TPD method) under a vacuum or an inert atmosphere (H ₂ ) ( Hydrogen-containing compound gas) is easily distinguished from deuterated hydrogen (HD) and / or deuterium (D ₂ ) (second compound gas) derived from phenolic hydroxyl groups. The second heating in an oxidizing atmosphere (e.g., a second heating by TPO method) is generated by water from the edges hydrogen atom (H 2 _O) (hydrogen containing compound gas) is also a phenolic hydroxyl group It is readily distinguished from the origin to a half deuterium oxide (DHO) and / or heavy water _(D 2 O) (second compound gas).

In this method, the first heating step and the second heating step may be carried out by the TPD method, or the first heating step may be carried out by the TPD method and the second heating step may be carried out by the TPO method. However, 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 carried out by the TPD method, the first heating step and the second heating step may be carried out continuously by using one TPD analyzer.

That is, when the first heating step and the second heating step are carried out by the TPD method, after the HD substitution treatment, from a predetermined temperature lower than the first temperature under a vacuum or an inert atmosphere, from the first temperature. The carbon material is heated while raising the temperature to a high predetermined temperature, and the first compound gas produced 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 raising the temperature to a high predetermined temperature, and 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.

When the second heating step is carried out by the TPO method, after the HD substitution treatment, from a predetermined temperature lower than the first temperature to a predetermined temperature higher than the first temperature under vacuum or an inert atmosphere. The carbon material is heated while raising the temperature, and the first compound gas generated from the carbon material is measured. Then, in an oxidizing atmosphere, from a predetermined temperature lower than the second temperature to the second temperature. The carbon material is heated while raising the temperature to a high predetermined temperature, and the second compound gas generated from the carbon material is measured. In this case, the first heating step may be carried out by the TPD method. Further, as the second temperature, a temperature lower than the first temperature is used.

In the evaluation step, the carbon before the HD substitution treatment is based on the measurement result of the first compound gas obtained in the first heating step and the measurement result of the second compound gas obtained in the second heating step. Whether or not the material contained one or more selected from the group consisting of primary and secondary functional groups, and / or the primary functional group contained in the carbon material before the HD substitution treatment. And one or more amounts selected from the group consisting of second functional groups.

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 separated from the first functional group and the second functional group. It is determined whether or not one or more selected from the group of

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 contains a second functional group. That is, in the example shown in FIG. 2, when hydrogen deuteride (HD) and / or deuterium (D ₂ ) (second compound gas) produced by the second heating is measured, it is replaced with HD. It is judged that the carbon material before the treatment contained a phenolic hydroxyl group (second functional group). 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 does not contain the second functional group.

Further, when the second compound gas is measured in the second heating step, it is measured in the first heating step assuming that all the first compound gas measured in the first heating step is derived from the second functional group. 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, it is assumed that all the carbon monoxide (CO) (first compound gas) generated by the first heating is derived from the phenolic hydroxyl group (second functional group). The amount of the phenolic hydroxyl group calculated from the amount of carbon is calculated from the amount of hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) (second compound gas) produced by the second heating. If it is larger 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 (primary functional group).

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

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 substitution treatment contains the first functional group. Judge that it was included.

Specifically, in the example shown in FIG. 2, carbon monoxide (CO) (first compound gas) is generated by the first heating, and hydrogen deuteride (HD) and deuteride (D ₂ ) are produced by the second heating. ) (Second compound gas) was not produced, 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 substitution treatment Calculate one or more quantities selected from the group consisting of groups.

Specifically, for example, the amount of the second functional group contained in the carbon material before the HD substitution 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 hydrogen deuteride (HD) and / or deuterium (D ₂ ) (second compound gas) produced by the second heating, the carbon before the HD substitution treatment Calculate the amount of phenolic hydroxyl group (second functional group) contained in the material.

On the other hand, 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 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, carbon monoxide (CO) (first compound gas) is produced by the first heating, and hydrogen deuteride (HD) and deuteride (D ₂ ) are produced by the second heating. ) (Second compound gas) was not generated, based on the amount of carbon monoxide generated by the first heating, the cyclic ether group (the second compound gas) contained in the carbon material before the HD substitution treatment. Calculate the amount of monofunctional group).

Further, assuming that all the first compound gas measured in the first heating step is 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. When the amount of 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, the amount of the first compound gas corresponding to the difference is determined from H-. The amount of the first functional group contained in the carbon material before the D substitution treatment is calculated.

Specifically, in the example shown in FIG. 2, it is assumed that all the carbon monoxide (CO) (first compound gas) generated by the first heating is derived from the phenolic hydroxyl group (second functional group). The amount of phenolic hydroxyl groups calculated from the amount of carbon monoxide produced by heating is the amount of hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) (second compound gas) produced by the second heating. If it is larger than the amount of phenolic hydroxyl groups calculated from the amount of, the amount of carbon monoxide corresponding to the difference indicates that the cyclic ether group (primary functional group) contained in the carbon material before the HD substitution treatment. Calculate the amount of base).

As described above, according to this method, the primary functional group and the secondary functional group contained in the carbon material can be analyzed separately. Specifically, in the example shown in FIG. 2, first, in the pretreatment step, H- is added to the carbon material which may contain a cyclic ether group (first functional group), a phenolic hydroxyl group (second functional group), and an edge hydrogen atom. By performing the D substitution treatment, the protonic hydrogen atom of the phenolic hydroxyl group is replaced with a deuterium atom (D).

Next, in the first heating step, the carbon material after the HD substitution treatment was heated at the first temperature to thermally decompose the cyclic ether group and the phenolic hydroxyl group containing a deuterium atom, and the one produced. Measure carbon oxide (CO) (first compound gas).

Further, in the second heating step, the carbon material after the first heating is heated at the second temperature to deuterium atoms derived from the thermal decomposition of the phenolic hydroxyl group after the HD substitution treatment from the carbon material. Thereby, the produced deuterium hydrogen (HD) and / or deuterium (D ₂ ) (second compound gas) is measured.

After that, in the evaluation step, the measurement result of carbon monoxide (CO) obtained in the first heating step, and the hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) obtained in the second heating step. ), Based on the measurement result, whether or not the carbon material before the HD substitution treatment contained one or more selected from the group consisting of cyclic ether groups and phenolic hydroxyl groups, and / or the HD substitution treatment. One or more amounts selected from the group consisting of cyclic ether groups and phenolic hydroxyl groups contained in the previous carbon material are evaluated.

In this method, in the second heating step, the hydrogen-containing compound gas produced from the carbon material by the second heating (hydrogen (H ₂ ) derived from the edge hydrogen atom produced by the "second heating" in FIG. ₂ ) is used. (Corresponding gas) was further measured, and in the evaluation step, based on the measurement result 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 an edge hydrogen atom, the second heating of the carbon material produces a hydrogen-containing compound gas containing a hydrogen atom derived from the edge hydrogen atom and not containing a deuterium atom. To.

Therefore, in the second heating step, the hydrogen-containing compound gas derived from this edge hydrogen atom is measured. Specifically, when the second heating step is carried out by the TPD method, hydrogen (H ₂ ) is measured as the hydrogen-containing compound gas as shown in FIG. Further, when the second heating step carried out by TPO method, as the hydrogen containing compound gas, measuring the water (H 2 _O).

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 substitution treatment contains an edge hydrogen atom. Specifically, for example, when the hydrogen-containing compound gas is measured in the second heating step, it is determined that the carbon material before the HD substitution treatment contains edge hydrogen atoms. That is, in the example shown in FIG. 2, when hydrogen (H ₂ ) (hydrogen-containing compound gas) was generated after the second heating, it was said that the carbon material before the HD substitution treatment contained edge hydrogen atoms. to decide. On the other hand, when the hydrogen-containing compound gas was not measured in the second heating step, it is determined that the carbon material before the first heating did not contain edge hydrogen atoms.

Further, the amount of edge hydrogen atoms contained in the carbon material before the HD substitution 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 atom contained in the carbon material before the HD substitution treatment Calculate the amount of.

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

FIG. 3 schematically shows the steps included in other examples of this method. The carbon material to be analyzed in this method may further contain a third functional group (functional group corresponding to the carboxy group shown in FIG. 3) satisfying the following conditions (a3) to (e3): (A3) The third functional group is bonded to the carbon atom at the edge of the carbon hexagonal network; (b3) The third functional group is a protonic hydrogen atom and the first and second functional groups. The contained non-hydrogen atom includes a non-hydrogen atom of the same type (an atom corresponding to the oxygen atom of the carboxy group shown in FIG. 3); (c3) In the third functional group, the protonic hydrogen atom is a deuterium atom. After being replaced with, the first heating does not produce the first compound gas; (d3) the third functional group is the first temperature and the second after the protonic hydrogen atom is replaced with a deuterium atom. By being heated at a third temperature different from the temperature, it is thermally decomposed, and the first compound gas containing the non-hydrogen atom and the third compound gas different from the second compound gas (derived from the carboxy group shown in FIG. 3). A gas corresponding to carbon dioxide (CO ₂ ) is generated, and the deuterium atom bonded to the carbon atom at the edge of the carbon hexagonal network surface (in FIG. 3, after the "third heating" of the carboxy group, the carbon hexagonal network surface is formed. A dehydrogen atom corresponding to the remaining deuterium atom (D)) is left; and (e3) the deuterium atom left in the (d3) is desorbed by the second heating to be the second compound. Produces 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 the tertiary compound gas produced from the carbon material. Then, in the evaluation step, the carbon material before the HD substitution treatment is first functionalized 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 it contained one or more selected from the group consisting of a 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. , One or more amounts selected from the group consisting of secondary and tertiary functional groups.

The third functional group is bonded to a carbon atom at the edge of the carbon hexagonal network surface and contains a protonic hydrogen atom and a non-hydrogen atom. Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) is bonded to the carbon atom at the edge of the carbon hexagonal network surface and contains a protonic hydrogen atom and an oxygen atom (non-hydrogen atom). ..

The number of non-hydrogen atoms contained in the third functional group may be different from that of the second functional group. That is, the number of non-hydrogen atoms contained in the third functional group may be larger 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 larger than that of the phenolic hydroxyl group (second functional group).

The third functional group may further contain another non-hydrogen atom different from the non-hydrogen atom contained in the second functional group. The other non-hydrogen atom contained in the third functional group, which is not contained in the second functional group, is one or more selected from the group consisting of, for example, a carbon atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a boron atom. This may be a carbon atom, preferably a carbon atom.

Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) contains a carbon atom (another non-hydrogen atom) that is not contained in the second functional group. Further, 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 bonded to the carbon atom of the edge via a non-hydrogen atom not contained in the second functional group. Specifically, in the example shown in FIG. 3, the carboxy group (third functional group) is an edge carbon via a carbon atom (another non-hydrogen atom) not contained in the phenolic hydroxyl group (second functional group). It is bonded to an atom.

The third functional group does not produce the first compound gas even when heated at the first temperature after the protic hydrogen atom is replaced with the deuterium atom. Specifically, in the example shown in FIG. 3, the carboxy group (tertiary functional group) in which the protonic hydrogen atom is replaced with the deuterium atom (D) by the HD substitution treatment is carbon monoxide even by the first heating. Does not produce (first compound gas).

The third functional group is thermally decomposed by heating at a third temperature (hereinafter referred to as "third heating") after the protic hydrogen atom contained in the third functional group is replaced with a deuterium atom. This produces a tertiary compound gas and leaves the deuterium atom bonded to the carbon atom at the edge of the carbon hexagonal network.

That is, when a third functional group in which a protonic hydrogen atom is replaced with 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 becomes While the tertiary compound gas is produced by thermal decomposition, the deuterium atom contained in the third functional group is bonded to the carbon atom at the edge of the carbon hexagonal network surface and remains 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 replaced with the deuterium atom (D) is thermally decomposed by the third heating and carbon dioxide (CO _2). ) (Third compound gas), while leaving the deuterium atom (D) bonded to the carbon atom at the edge of the carbon hexagonal network.

When the tertiary functional group is an amino group, ammonia is generated as a tertiary compound gas by the tertiary heating. When the tertiary functional group is a phosphoric acid group, carbon monoxide is produced as a tertiary compound gas by the tertiary heating. When the tertiary functional group is a sulfonic acid group, sulfur dioxide is produced as a tertiary compound gas by the tertiary heating. When the tertiary functional group is a boric acid group, carbon monoxide is produced as a tertiary compound gas by the tertiary heating.

At the third temperature, the third functional group is thermally decomposed, the third functional group is thermally decomposed to generate a third compound gas, and the third functional group is thermally decomposed to be contained in the third functional group. It is the temperature at which the heavy hydrogen atom is bonded to the carbon atom at the edge of the carbon hexagonal network surface and remains. The third temperature may be lower than the second temperature. The third temperature may be lower than the first temperature. The third temperature may be a temperature at which the first functional group and the second functional group are not thermally decomposed.

The third temperature is determined, for example, as the temperature at which the tertiary functional group determined to be analyzed in this method produces a tertiary compound gas by thermal decomposition. That is, the third temperature is, for example, a temperature known in advance as a temperature at which the third functional group produces a 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. The temperature may be 100 ° C. or higher and 500 ° C. or lower, or 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 atom left in the carbon material by the thermal decomposition of the third functional group at the third temperature is higher than the third temperature (for example, higher than the third temperature) in the second heating step. By heating at (second temperature), it is desorbed from the carbon material to generate a second compound gas containing the deuterium atom.

That is, the deuterium atom derived from the third functional group bonded to the carbon atom of the edge by heating at the third temperature is then desorbed by further heating at the second temperature to release the second compound gas. Generate.

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

Specifically, in the example shown in FIG. 3, the deuterium atom (D) left in the carbon material due to the thermal decomposition of the carboxy group (third functional group) by the third heating at the third temperature lower than the first temperature is After that, deuterium hydrogen (HD) and / or deuterium (D ₂ ) (second compound gas) is desorbed from the carbon material by the second heating at the second temperature higher than the third temperature. Generate.

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

Further, the tertiary functional group may further contain other non-hydrogen atoms not contained in the primary functional group and the secondary functional group. That is, the third functional group may contain a carbon atom as shown in the example of FIG. In this case, the tertiary functional group contains a protonic 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 tertiary compound gas may be carbon dioxide (CO ₂ ).

In the third heating step, the carbon material after the HD substitution treatment is heated at the third temperature, and the third compound gas generated 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 ) produced from the carbon material (the first). Three compound gas) is measured.

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. The method of heating while heating is preferably used.

The method of carrying out 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 selected from the group consisting of vacuum (for example, 1 × 10 ^-1 Pa or less, preferably 1 × 10 ^-3 Pa or less, high vacuum) or an inert atmosphere (for example, nitrogen gas and argon gas). It is preferable to carry out in an atmosphere of one or more kinds of inert gases.

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 heating rate (for example, 2 ° C./min or more, 50 ° C./min or less). The carbon material is heated while raising the temperature with, and the third compound gas generated from the carbon material is measured while the temperature rises.

In this method, the first heating step, the second heating step and the third step may be carried out by the TPD method, or the first heating step and the third heating step may be carried out by the TPD method and the second heating step. Although it may be carried out by the TPO method, 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 step are carried out by the TPD method, the first heating step, the second heating step and the third heating step are continuously carried out using one TPD analyzer. May be.

That is, when the first heating step, the second heating step and the third step are carried out by the TPD method, after the HD substitution treatment, the temperature is lower than the third temperature under vacuum or in an inert atmosphere. The carbon material is heated while raising the temperature to a predetermined temperature higher than the third temperature, the amount of the third compound gas produced from the carbon material is measured, and then from a predetermined temperature lower than the first temperature. The carbon material is heated while raising the temperature to a predetermined temperature higher than the first temperature, the amount of the first compound gas produced from the carbon material is measured, and then the predetermined temperature lower than the second temperature is measured. The carbon material is heated while raising the temperature from the temperature to a predetermined temperature higher than the second temperature, and the amount of 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.

When the second heating step is carried out by the TPO method, after the HD substitution treatment, from a predetermined temperature lower than the third temperature to a predetermined temperature higher than the third temperature under vacuum or an inert atmosphere. , The carbon material is heated while raising the temperature, and 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 to a predetermined temperature higher than the first temperature. The carbon material is heated while raising the temperature to the above temperature, and the amount of the first compound gas produced from the carbon material is measured. Then, in an oxidizing atmosphere, from a predetermined temperature lower than the second temperature, The carbon material is heated while raising 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 carried out by the TPD method. Further, the third heating step may be carried out by the TPD method. Further, as the second temperature, a temperature lower than the first temperature is used.

In the evaluation step, the measurement result of the first compound gas obtained in the first heating step, the measurement result of the second compound gas obtained in the second heating step, and the third compound obtained in the third heating step. Whether or not the carbon material before the HD substitution treatment contained one or more selected from the group consisting of a primary functional group, a secondary functional group and a tertiary functional group based on the measurement result of the gas. And / or an amount of one or more selected from the group consisting of the primary functional group, the secondary functional group and the tertiary 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 substitution treatment is the first. It is determined whether or not one or more selected from the group consisting of a monofunctional group, a second functional group and a tertiary functional group was contained.

Specifically, for example, when the tertiary compound gas is measured in the third heating step, it is determined that the carbon material before the HD substitution treatment contains the tertiary 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 substitution treatment is a carboxy group (third functional group). ) Was included. On the other hand, when the tertiary compound gas is not measured in the third heating step, it is determined that the carbon material before the HD substitution treatment does not contain the tertiary functional group.

Further, when the third compound gas is measured in the third heating step, it is measured in the second heating step on the assumption that all the second compound gas measured in the second heating step is derived from the third functional group. When the amount of the third functional group calculated from the amount of the second compound gas is larger 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 a second functional group.

Specifically, in the example shown in FIG. 3, hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) (second compound gas) generated by the second heating are all carboxy groups (third functional groups). the amount of carboxy group is calculated from the amount of assuming the second measured at the heating step was the hydrogen deuteride and derived (HD) and / or deuterium (D ₂₎ in is generated by the third heating If it is larger than the amount of carboxy group calculated from the amount of carbon dioxide (CO ₂ ) (third compound gas), the carbon material before the HD substitution treatment further adds a phenolic hydroxyl group (second functional group). Judge that it was included.

On the other hand, assuming that all the second compound gas measured in the second heating step is derived from the third functional group, the third functionality 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 tertiary functional groups calculated from the amount of tertiary compound gas measured in the third heating step, the carbon material before the HD substitution treatment is the secondary functional groups. It is judged 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 substitution treatment contains the second functional group. Judge that it was included.

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

Further, when the second compound gas is measured in the second heating step, it is assumed that all the first compound gas measured in the first heating step is derived from the second functional group, and the measurement is performed in the first heating step. When the amount of the second functional group calculated from the amount of the first compound gas obtained 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 primary functional group.

Specifically, in the example shown in FIG. 3, it is assumed that all the carbon monoxide (CO) (first compound gas) generated by the first heating is derived from the phenolic hydroxyl group (second functional group). The amount of the phenolic hydroxyl group calculated from the amount of carbon is calculated from the amount of hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) (second compound gas) produced by the second heating. If it is larger 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 (primary functional group).

On the other hand, assuming that all the first compound gas measured in the first heating step is derived from the second functional group, the second functionality 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 second functional groups calculated from the amount of second compound gas measured in the second heating step, the carbon material before the HD substitution treatment is the first functional groups. It is judged that it did not contain.

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 substitution treatment contains the first functional group. Judge that it was included.

Specifically, in the example shown in FIG. 3, carbon monoxide (CO) (first compound gas) is produced by the first heating, and hydrogen deuteride (HD) and deuteride (D ₂ ) are produced by the second heating. ) (Second compound gas) was not produced, 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, it was contained in the carbon material before the HD substitution treatment 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 amount of one or more selected from the group consisting of the first functional group, the second functional group and the third functional group is calculated.

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

On the other hand, 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 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, carbon dioxide (CO ₂ ) (third compound gas) is generated by the third heating, and hydrogen deuteride (HD) and / or hydrogen deuteride (HD) and / or deuteride (the third compound gas) is generated by the second heating. When D ₂ ) (second compound gas) is generated, HD substitution treatment is performed from the amount of hydrogen deuteride (HD) and / or deuteride (D ₂ ) generated by the second heating. Calculate the amount of phenolic hydroxyl group (second functional group) contained in the previous carbon material.

Further, assuming that all the second compound gas measured in the second heating step is 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. When the amount of the third functional group is larger 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- The amount of the second functional group contained in the carbon material before the D substitution treatment is calculated.

Specifically, in the example shown in FIG. 3, hydrogen dehydride (HD) and / or dehydrogen (D ₂ ) (second compound gas) generated by the second heating are all carboxy groups (third functional groups). The amount of carboxy group calculated from the amount of hydrogen dehydrogenated (HD) and / or dehydrogen (D ₂ ) produced by the second heating, assuming that it is derived from If it is larger than the amount of carboxy group calculated from the amount of carbon (CO ₂ ) (third compound gas), it is included in the carbon material before HD substitution treatment from the amount of carbon monoxide corresponding to the difference. Calculate the amount of phenolic hydroxyl group (second functional group).

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 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 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 functional group contained in the carbon material before the HD substitution treatment is taken from the amount of the first compound gas corresponding to the difference. Is calculated.

Specifically, in the example shown in FIG. 3, carbon dioxide (CO ₂ ) (third compound gas) is generated by the third heating, and hydrogen peroxide (HD) and / or phenol (hydrogen) is generated by the second heating. When D ₂ ) (second compound gas) is generated, it is assumed that all carbon monoxide (C) (first compound gas) generated by the first heating is derived from a phenolic hydroxyl group (second functional group). The amount of phenolic hydroxyl groups calculated from the amount of carbon monoxide produced by the first heating is hydrogen dehydride (HD) and / or dehydrogen (D ₂ ), and carbon dioxide as described above. If it is larger than the amount of phenolic hydroxyl group calculated from the amount of (CO ₂ ), the cyclic ether group contained in the carbon material before the HD substitution treatment is determined from the amount of carbon monoxide corresponding to the difference. Calculate the amount of (first functional group).

As described above, according to this method, even when the carbon material contains a tertiary functional group, the primary functional group and the secondary functional group contained in the carbon material can be distinguished and analyzed. .. 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 a carbon material containing an atom to an HD substitution treatment, the protonal hydrogen atom of the phenolic hydroxyl group and the protonic hydrogen atom of the carboxy group are each replaced with a heavy hydrogen atom (D).

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

Further, 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.

Further, in the second heating step, the carbon material after the first heating is heated at the second temperature, and the deuterium atom derived from the thermal decomposition of the phenolic hydroxyl group after the HD substitution treatment and the HD substitution treatment Deuterium hydrogen (HD) and / or deuterium (D ₂ ) (second compound gas) produced is measured by desorbing deuterium atoms derived 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 the second heating step were obtained. Based on the measurement results of dehydrogenated hydrogen (HD) and / or dehydrogenated hydrogen (D ₂ ), the carbon material before the HD substitution treatment was composed of a cyclic ether group, a phenolic hydroxyl group, and a carboxy group. Whether or not it contained one or more selected, and / or selected from the group consisting of cyclic ether groups, phenolic hydroxyl groups, and carboxy groups contained in the carbon material before the HD substitution treatment. Evaluate the above amount.

Further, in the second heating step, hydrogen (H ₂ ) (hydrogen-containing compound gas) derived from the edge hydrogen atom 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 substitution treatment contained edge hydrogen atoms and / or the amount of edge hydrogen atoms contained in the carbon material before the HD substitution treatment, May be further evaluated.

Next, a specific embodiment according to the present embodiment will be described.

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

Further, the MSCs were heat-treated at 425 ° C. for 8 hours under the flow of dehydrated air to obtain oxygen-treated MSCs (hereinafter referred to as "MSC-O ₂ "). Further, the MSC is treated with hydrogen peroxide by immersing the MSC in a 30 w / v% hydrogen peroxide (H ₂ O ₂ ) aqueous solution at 80 ° C. for 2 hours (hereinafter referred to as “MSC-H ₂ O ₂ ”). .) Was obtained.

Then, these three types of carbon materials were subjected to HD substitution treatment. That is, each carbon material was placed in a vacuum-sealable vial and vacuum dried. Then, in a state in which the vial vacuum sealing, using a syringe, by introducing heavy water (D 2 _O) to the vial and suspended carbon material in the heavy water in the vial. Then, a suspension of heavy water containing a carbon material was placed on a sample table of the TPD analyzer, and the suspension was freeze-dried in the TPD analyzer.

Thus, MSC where H-D replacement process is performed (hereinafter, referred to as "MSC _(D 2 O)".), _{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.

[Hot temperature desorption method]
In the TPD analyzer installed on the sample table, the carbon material after freeze-drying is raised in temperature from 0 ° C. to 1600 ° C. at a heating rate of 10 ° C./min under a high vacuum of 1 × 10 ^-3 Pa or less. While heating the carbon material, the desorbed gas (specifically, CO, CO ₂ , H ₂ , HD, and D ₂ ) generated during the period when the temperature rises from 0 ° C. to 1600 ° C. is used as QMS. Was measured. For comparison, the desorbed gas was also measured by the TPD method for the MSCs that had not been subjected to the HD substitution treatment.

[result]
4A and 4B show the TPD spectra of CO and CO ₂ obtained for MSCs and the TPD spectra of H ₂ , respectively. 5A and 5B show the TPD spectra of CO and CO ₂ obtained for MSC (D ₂ O) and the TPD spectra of H ₂ , HD and D ₂ , respectively. 6A and 6B show the TPD spectra of CO and CO ₂ obtained for MSC-O ₂ (D ₂ O) and the TPD spectra of H ₂ , HD and D ₂ , respectively. 7A and 7B show the TPD spectra of CO and CO ₂ obtained for MSC-H ₂ O ₂ (D ₂ O) and the TPD spectra of H ₂ , HD and D ₂ , 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 elimination of HD has been confirmed, but the elimination of H 2 _O was not confirmed.

In FIG. 8, each of MSC, MSC (D ₂ O), MSC-O ₂ (D ₂ O), and MSC-H ₂ O ₂ (D ₂ O) was obtained based on the measurement results by the TPD method. 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 (CO ₂ ). The amount of production (mmol / g) is shown.

Further, in FIG. _{9, MSC, MSC (D 2 O} ), for each of the _{MSC-O 2 (D 2 O} ), and _{MSC-H 2 O 2 (D} 2 O), based on the quantitation result shown in FIG. 8 The amount of the carboxy group (mmol / g), the amount of the cyclic ether group (mmol / g), the amount of the phenolic hydroxyl group (mmol / g), and the amount of the edge hydrogen atom (mmol / g) obtained are shown. ..

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

Then, the amount of phenolic hydroxyl group was determined by subtracting the value of S from the value of Q. Further, the amount of cyclic ether was determined by subtracting the amount of phenolic hydroxyl group from the value of P. Further, as the amount of edge hydrogen atom and the amount of carboxy group, the value of R and the value of S were adopted, respectively.

As shown in FIG. 9, in the MSC not subjected to the HD substitution treatment, the formation of deuterium compounds and deuterium was not confirmed, so that the phenolic hydroxyl group and the cyclic ether could not be distinguished, and the amounts thereof. Had no choice but to find it as a range including the error.

On the other hand, for MSC (D ₂ O), MSC-O ₂ (D ₂ O), and MSC-H ₂ O ₂ (D ₂ O) that have undergone HD substitution treatment, deuterium compounds and deuterium Since the formation of deuterium was confirmed, the total amount of deuterium atoms could be obtained from the amount of the deuterium compound and the amount of deuterium produced, and as a result, the phenolic hydroxyl group and the cyclic ether could be distinguished and quantified.

Claims (9)

First functional group satisfying 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 surface;
(B1) The first functional group does not contain a protonic hydrogen atom, which is a hydrogen atom that can be replaced with a heavy hydrogen atom, and contains a non-hydrogen atom; and (c1) the first functional group has a first temperature. The first compound gas containing the non-hydrogen atom is produced by thermal decomposition in the above;
Second functional group satisfying 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;
(B2) The second functional group contains a protonic 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 protonic hydrogen atom is replaced with a heavy hydrogen atom, and is bonded to the carbon atom at the edge of the carbon hexagonal network surface. The deuterium atom left in (e2) is desorbed by heating at a second temperature different from the first temperature, and contains the deuterium atom. Produces a second compound gas;
Edge hydrogen atom which is a hydrogen atom satisfying the following conditions (x) to (z):
(X) The edge hydrogen atom is bonded to the carbon atom at the edge of the carbon hexagonal network;
(Y) The edge hydrogen atom is not replaced with a deuterium atom; and (z) the edge hydrogen atom is desorbed by heating at the second temperature to contain the deuterium atom. Produces a hydrogen-containing compound gas that does not contain;
A pretreatment step of applying a hydrogen-deuterium substitution treatment to a carbon material that may contain
After the pretreatment step, the carbon material is heated at the first temperature, and the first compound gas produced from the carbon material is measured.
After the first heating step, the carbon material is heated at the second temperature, and the second heating step of measuring the second compound gas generated from the carbon material, and the second heating step.
Based on the measurement result of the first compound gas and the measurement result of the second compound gas, the group in which the carbon material before the hydrogen-hydrogen substitution treatment comprises the first functional group and the second functional group. From the group consisting of the first functional group and the second functional group contained in the carbon material before the hydrogen-hydrohydrogen substitution treatment, whether or not it contained one or more selected from the above. An evaluation process that evaluates one or more quantities selected, and
Methods for analyzing carbon materials, including. In the second heating step, the hydrogen-containing compound gas produced from the carbon material is further measured.
In the evaluation step, based on the measurement result of the hydrogen-containing compound gas, whether or not the carbon material before heating at the first temperature contained the edge hydrogen atom and / or the hydrogen-deuterium. Further evaluating the amount of the edge hydrogen atoms contained in the carbon material before the hydrogen substitution treatment.
The method for analyzing a carbon material according to claim 1. 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 and
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, semiheavy 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 is a third functional group satisfying 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 surface;
(B3) The third functional group contains a protonic hydrogen atom and the non-hydrogen atom;
(C3) The third functional group does not produce the first compound gas by heating at the first temperature after the protic hydrogen atom is replaced with a deuterium atom;
(D3) The third functional group is thermally decomposed by heating at the first temperature and a third temperature different from the second temperature after the protonal hydrogen atom is replaced with a deuterium atom. The first compound gas containing a non-hydrogen atom and a third compound gas different from the second compound gas are generated, and the heavy hydrogen atom bonded to the carbon atom at the edge of the carbon hexagonal network remains; and (e3). ) The heavy hydrogen atom left in (d3) is desorbed by heating at the second temperature to produce the second compound gas;
Is a carbon material that can further contain
The method for analyzing a carbon material is a third heating step in which the carbon material is heated at the third temperature after the hydrogen-deuterium substitution treatment, and the third compound gas produced from the carbon material is measured. Including more
In the evaluation step, the carbon material before the hydrogen-heavy hydrogen substitution 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. Did contain 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-heavy hydrogen substitution treatment. 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 is evaluated.
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. The third compound gas is carbon dioxide.
The method for analyzing a carbon material according to claim 8.

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