阅读说明：本技术 一种1，4-双（苯基乙炔基）苯衍生的氢气浓度检测方法 (Method for detecting concentration of hydrogen derived from 1, 4-bis (phenylethynyl) benzene ) 是由 余磊 敖银勇 孟宪福 朱芳锐 伍晓利 石建敏 蹇源 于 2020-08-25 设计创作，主要内容包括：本发明公开了一种基于1,4-双(苯基乙炔基)苯衍生结合色谱质谱检测氢气的方法。在密闭空间内,1,4-双(苯基乙炔基)苯与氢气在钯碳催化作用下发生加成反应,然后将反应后的固体物质溶解、过滤,滤液进入到气相色谱质谱中分析。本发明既能利用1,4-双(苯基乙炔基)苯消除密闭空间内的氢气,又能利用1,4-双(苯基乙炔基)苯对密闭空间内的氢气浓度进行检测,解决了密闭空间内氢气检测的难题。而且,该方法使用气相色谱质谱分析,具有检测灵敏度高和分离能力强等特点。本发明在复杂重大装置密闭系统内的氢气检测中具有很大的应用前景。(The invention discloses a method for detecting hydrogen based on 1, 4-bis (phenylethynyl) benzene derivation combined with chromatography mass spectrometry. In a closed space, 1, 4-bis (phenylethynyl) benzene and hydrogen are subjected to addition reaction under the catalytic action of palladium-carbon, then the reacted solid substances are dissolved and filtered, and the filtrate enters a gas chromatography mass spectrum for analysis. The invention can not only eliminate hydrogen in the closed space by using 1, 4-bis (phenylethynyl) benzene, but also detect the hydrogen concentration in the closed space by using 1, 4-bis (phenylethynyl) benzene, thereby solving the problem of hydrogen detection in the closed space. In addition, the method uses gas chromatography-mass spectrometry, and has the characteristics of high detection sensitivity, strong separation capacity and the like. The invention has wide application prospect in hydrogen detection in a closed system of a complex and important device.)

1. A method for detecting the concentration of hydrogen derived from 1, 4-bis (phenylethynyl) benzene is characterized by comprising the following steps:

(1) preparing a hydrogen absorption material containing 1, 4-bis (phenylethynyl) benzene, and placing the hydrogen absorption material and a material to be detected in a closed container;

(2) placing the closed container in a specific environment until the material to be detected releases hydrogen;

(3) 1, 4-bis (phenylethynyl) benzene in the material to be subjected to hydrogen absorption and hydrogen released by the material to be detected are subjected to addition reaction;

(4) dissolving the solid reaction product reacted in the step (3) in a normal hexane solution, and injecting the dissolved solution into a gas chromatography mass spectrometry to obtain the peak area of the reaction product;

(5) reacting standard hydrogen with different concentrations with a hydrogen absorption material, and dissolving a reaction product by using n-hexane; detecting the reaction product by using a gas chromatography-mass spectrometer to obtain peak areas of the reaction product under hydrogen with different concentrations; establishing a quantitative working curve of the hydrogen by utilizing the relation between the hydrogen concentration and the peak area of the reaction product;

(6) and (5) substituting the peak area obtained in the step (4) into the quantitative working curve obtained in the step (5) to obtain the concentration of the hydrogen released by the material to be measured.

2. The method according to claim 1, wherein the preparation of the hydrogen absorption material in the step (1) is specifically that 1, 4-bis (phenylethynyl) benzene and palladium carbon catalyst in a certain mass ratio are weighed and put in a mortar for grinding.

3. The method according to claim 1, wherein the specific environment in the step (2) is any one of a high temperature environment, a normal temperature environment or a radiation environment.

4. The method according to claim 1, wherein the step (4) is specifically that a certain mass of the solid reaction product after the reaction in the step (3) is weighed and dissolved in a chromatographically pure n-hexane solution, the solution is filtered by using a needle filter, the filtered solution is injected into a chromatographic column to separate the reaction product, and the mass spectrum is used to detect the reaction product, so as to obtain the peak area of the reaction product; establishing the relation between the hydrogen concentration and the peak area of the reaction product.

Technical Field

The invention belongs to the field of gas detection, and particularly relates to a method for detecting hydrogen concentration derived from 1, 4-bis (phenylethynyl) benzene.

Background

Due to factors such as natural aging of materials, various gases such as hydrogen, carbon dioxide, alkane and the like can be slowly released from materials such as organic polymers and the like in a closed system of a complex and important device in the processes of storage and use. Research shows that there is a very close relationship between the concentration of gas in the closed space and the material performance. The gas concentration in the closed system is detected and analyzed, data in the aspect of material performance change can be obtained, and the method has important significance for stable operation of the device. At present, for different kinds of gases, corresponding analytical means such as a sensor method and a gas chromatography method are developed to be applied to the detection of the gas concentration in a closed system.

In the gas generated by a complex and important device closed system, the accumulation of hydrogen can not only cause the failure of a vacuum device or cause the influence of circuit welding spots and metal components, but also can cause serious safety accidents such as hydrogen explosion and the like when the hydrogen is accumulated to a certain concentration. The hydrogen in the closed system is eliminated in time, so that the service life of the device can be prolonged, and the safety of the device in the using process can be ensured. The catalytic hydrogenation of noble metal by utilizing the acetylene-type carbon-carbon triple bond of the organic hydrogen absorption material is a good way for removing hydrogen in a closed environment, and has important significance for treating the hydrogen concentration in a closed space. Currently, the most commonly used hydrogen-absorbing material is a mixture of 1, 4-bis (phenylethynyl) benzene (1, 4-bis (phenylethynyl) benzene, DEB) and palladium on carbon (Pd-C). Each DEB molecule contains 2 acetylene bonds which can perform addition reaction with hydrogen under the catalysis of palladium-carbon. 1mol of DEB can react with 4mol of hydrogen, thereby eliminating the hydrogen in the closed system. The widespread use of hydrogen-absorbing materials ensures the safety of complex and significant devices. However, under the action of the hydrogen absorption material, the current detection means cannot accurately obtain the true hydrogen concentration generated by the material in the closed system, cannot correlate the material performance change with the hydrogen concentration, and cannot diagnose the material performance.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention provides a method for detecting the concentration of hydrogen derived from 1, 4-bis (phenylethynyl) benzene, which is suitable for detecting the concentration of hydrogen released by a hydrogen absorbing material when the hydrogen absorbing material exists in a closed container, and has the advantages of high accuracy and high sensitivity.

The technical scheme provided by the invention is as follows:

a method for detecting the concentration of hydrogen derived from 1, 4-bis (phenylethynyl) benzene, which comprises the following steps:

(1) preparing a hydrogen absorption material containing 1, 4-bis (phenylethynyl) benzene, and placing the hydrogen absorption material and a material to be detected in a closed container;

(2) placing the closed container in a specific environment for a certain time, and releasing a certain content of hydrogen from the material to be detected;

(3) 1, 4-bis (phenylethynyl) benzene in the material to be subjected to hydrogen absorption and hydrogen released by the material to be detected are subjected to addition reaction;

(4) dissolving the solid reaction product reacted in the step (3) in a normal hexane solution, and injecting the dissolved solution into a gas chromatography mass spectrometry to obtain the peak area of the reaction product;

(5) reacting standard hydrogen with different concentrations with a hydrogen absorption material, and dissolving reaction products by using n-hexane. And detecting the reaction product by using a gas chromatography-mass spectrometer to obtain peak areas of the product under hydrogen with different concentrations. And establishing a quantitative working curve of the hydrogen by utilizing the relation between the hydrogen concentration and the peak area of the reaction product.

(6) And (5) substituting the peak area obtained in the step (4) into a quantitative working curve to obtain the concentration of the hydrogen released by the material to be detected.

Further, the preparation of the hydrogen absorption material in the step (1) is specifically that 1, 4-bis (phenylethynyl) benzene and palladium carbon catalyst in a certain mass ratio are weighed and put in a mortar, and ground.

Further, in the step (4), the solid matter reacted in the container is taken out, a certain mass of the solid matter is weighed and dissolved in a chromatographic pure n-hexane solution, the dissolved solution after the reaction is filtered by using a needle filter membrane, the filtered dissolved solution is injected into a chromatographic column to separate the reaction product, the reaction product is detected by using a mass spectrum, and the peak area of the reaction product is obtained, so that the relation between the hydrogen concentration and the peak area of the reaction product is established.

The invention utilizes the reaction product of the reaction of 1, 4-bis (phenylethynyl) benzene and hydrogen to detect the concentration of the hydrogen in the closed system. Specifically, 1, 4-bis (phenylethynyl) benzene and hydrogen are subjected to addition reaction under the catalytic action of palladium-carbon in a closed space, then the reacted solid substances are dissolved and filtered, and the filtrate enters a gas chromatography mass spectrum for analysis. The method realizes the detection of the hydrogen concentration in the closed space by utilizing the derivation of 1, 4-bis (phenylethynyl) benzene and the gas chromatography, and has the advantages of strong separation capability, high detection sensitivity and the like.

The invention can not only eliminate hydrogen in the closed space by using 1, 4-bis (phenylethynyl) benzene, but also detect the hydrogen concentration in the closed space by using 1, 4-bis (phenylethynyl) benzene, thereby solving the problem of hydrogen detection in the closed space. In addition, the method uses gas chromatography-mass spectrometry, and has the characteristics of high detection sensitivity, strong separation capacity and the like. The invention has wide application prospect in hydrogen detection in a closed system of a complex and important device.

Detailed Description

The technical solution of the present invention is further described below with reference to specific examples. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.