CN111398330A - In-situ electron paramagnetic resonance test reaction device and test method thereof - Google Patents
In-situ electron paramagnetic resonance test reaction device and test method thereof Download PDFInfo
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Abstract
The application discloses an in-situ electron paramagnetic resonance test reaction device and a test method thereof, which consist of nine parts, namely an air inlet pipe, an air inlet valve, an air outlet pipe, an air outlet valve, a spherical reactor, a sample introduction guide pipe, a quartz test pipe, a rubber sealing plug and a sample introduction guide rod. By controlling the gas inlet pipe, the gas inlet valve, the gas outlet pipe, the gas outlet valve and the sample introduction guide rod, the continuous reaction under the condition of steady flow reaction gas can be realized, the in-situ tracking and detection of free radicals, transition metal complex valence states, configuration changes and the like in the reaction process of different atmospheres can be realized, and the chemical reaction mechanism under different atmospheres is clarified. The device and the test method are easy to operate and wide in application field.
Description
Technical Field
The application relates to the technical field of paramagnetic resonance, in particular to an in-situ electron paramagnetic resonance test reaction device and a test method thereof.
Background
The Electron Paramagnetic Resonance (EPR) technology is based on the principle that unpaired electrons absorb electromagnetic radiation in a direct current magnetic field and jump from a low energy level to a high energy level, can realize nondestructive detection and research on the structure and space distribution of paramagnetic substances and the dynamics and reaction mechanism in physical and chemical reactions, and effectively analyzes the content and properties of paramagnetic centers such as free radicals, transition metal elements, lattice defects and the like contained in the substances. Therefore, electron paramagnetic resonance technology has been widely applied to many scientific fields such as physics, chemistry, biology, medicine, environmental science, and geological science.
For electron paramagnetic resonance detection technology, most research and test means are to detect under the air atmosphere, however, a considerable part of research and test needs to be performed under a special reaction atmosphere. At present, a common method in this field is to tie a balloon containing a reaction gas above a quartz test tube, and test a sample to be tested after the sample is contacted and reacted with the reaction gas. However, this approach has significant disadvantages: 1. Reaction gas in the balloon has poor fluidity, cannot be fully contacted with a sample, and is easy to have incomplete reaction, and if other gases are generated in the reaction, the concentration of the reaction gas is influenced, so that the normal operation of the reaction is influenced, and the test result is inaccurate; 2. This mode is used for single reaction gas more, when needing to switch two kinds and above reaction gas, need to change different gaseous balloons, and reaction is discontinuous and residual gas can't arrange to the greatest extent in the quartzy test tube, and the sample easily receives oxygen, steam influence in the air when changing the balloon, causes the inaccurate sample of test result and even the sample is rotten, receives very big restriction in practical application.
Content of application
The technical problem to be solved is as follows:
the technical problems to be solved by the application are that in the prior art, gas fluidity is poor, reaction is not thorough, and the like methods cannot meet experimental conditions for atmosphere switching, and the like, and an in-situ electron paramagnetic resonance test reaction device and a test method thereof are provided, which can realize sufficient reaction test under stable gas flow and can realize in-situ tracking detection of conversion of free radicals and metal valence states under the switching conditions among different atmospheres.
The technical scheme is as follows:
an in-situ electron paramagnetic resonance test reaction device consists of a gas reaction device and a sample injection control device, wherein the gas reaction device comprises six parts, namely a group of gas inlet pipes, a gas inlet valve, a gas outlet pipe, a gas outlet valve, a spherical reactor and a sample injection guide pipe, the group of gas inlet pipes comprises three same gas inlet pipes, and the three gas inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor; the front end of the air inlet pipe is in a necking form; each air inlet pipe is provided with an air inlet valve, and the air inlet valve is arranged between the necking form of the air inlet pipe and the spherical reactor; the sample introduction conduit is connected with the bottom of the spherical reactor; the air outlet pipe is connected with the lower middle part of the spherical reactor, and the tail part of the air outlet pipe is in a necking form; the gas outlet pipe is provided with a gas outlet valve which is arranged between the necking form of the gas outlet pipe and the spherical reactor; the sample injection control device comprises a quartz test tube, a rubber sealing plug and a sample injection guide rod, wherein one end of the quartz test tube is opened, and the other end of the quartz test tube is connected with one side of the rubber sealing plug in a sealing manner; the other side of the rubber sealing plug is connected with a sample introduction guide rod, the outer diameter of the rubber sealing plug is the same as the inner diameter of the sample introduction guide pipe, and the sample introduction control device is connected with the sample introduction guide pipe of the gas reaction device through the rubber sealing plug.
As a preferred technical scheme of the application: the group of air inlet pipes comprise three identical air inlet pipes, the three air inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor, the three air inlet pipes are connected with an air inlet latex pipe through a necking form, the air inlet latex pipe is respectively connected with a single air cylinder, an air inlet valve of one air inlet pipe is opened, when the air inlet valves of the other two air inlet pipes are kept closed, reaction conditions of a single atmosphere are provided, the air inlet valves of the two or three air inlet pipes can also be opened according to experiment requirements, and switching of various reaction atmosphere conditions is realized through opening and closing of the air inlet valves on the three air inlet pipes.
As a preferred technical scheme of the application: the sampling control device is a quartz test tube, a rubber sealing plug and a sampling guide rod integrated rigid design, the quartz test tube is moved by the up-and-down movement of the sampling guide rod in the sampling guide tube, the outer diameter of the rubber sealing plug is equal to the inner diameter of the sampling guide tube, and the sealing state of the spherical reactor and the sampling guide tube is realized.
As a preferred technical scheme of the application: the gas reaction device and the sampling control device are combined flexibly, the sampling control device can move in the sampling guide pipe, the sampling guide rod is provided with scales, the position where the sampling guide rod is fixed is judged through the scales, the sampling guide rod is moved during reaction, the rubber sealing plug is positioned between the spherical reactor and the sampling guide pipe to ensure the sealing state in the spherical reactor, and a sample is positioned in the center of the paramagnetic resonant cavity during testing so as to obtain the optimal testing signal.
As a preferred technical scheme of the application: the diameter of the air inlet pipe and the diameter of the air outlet pipe are 10-15 mm, the diameter of the necking form is 5-10 mm, the diameter of the quartz test tube is 4-8 mm, the diameter of the spherical reactor is 50-60 mm, the diameter of the sample injection guide pipe is 10-15 mm, and the diameter of the sample injection guide rod is 3-6 mm.
As a preferred technical scheme of the application: the device can realize the in-situ tracking and detection of free radicals, transition metal complex valence states and configuration changes in different atmosphere reaction processes, and elucidate chemical reaction mechanisms in different atmospheres.
A test method of an in-situ electron paramagnetic resonance test reaction device comprises the following steps:
the first step is as follows: vertically upwards arranging the in-situ electron paramagnetic resonance test reaction device, and placing a sample introduction conduit into a paramagnetic resonance cavity; vertically upwards placing a quartz test tube, and adding 10-50 mg of a sample to be tested; placing a quartz test tube into the sample introduction guide pipe from the lower part of the sample introduction guide pipe, moving the quartz test tube through the sample introduction guide rod to enable the quartz test tube to enter the spherical reactor, and positioning the rubber sealing plug between the spherical reactor and the sample introduction guide pipe;
respectively connecting a group of air inlet pipes and air outlet pipes with a latex pipe, introducing different reaction gases according to the reaction requirements of the sample, and opening an air inlet valve and an air outlet valve, introducing the reaction gases with stable flow rate from the air inlet pipes, controlling the flow rate to be 5-100 m L/min, fully reacting the sample to be detected and the reaction gases in a spherical reactor, adjusting the position of a sample introduction guide rod after the reaction is finished, enabling the sample to be positioned in the center of a paramagnetic resonant cavity, and then closing the air inlet valve and the air outlet valve to ensure that the gases are not exchanged with the outside;
the third step: carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the sample to be detected after reaction;
the fourth step: if a plurality of gas reactions or reaction results under the changed atmosphere are needed, the sample introduction guide rod can be adjusted to enable the quartz test tube to enter the spherical reactor again, and the second step and the third step are repeated.
As a preferred technical scheme of the application: in the second step, if gas experiments are not carried out, the gas inlet valve and the gas outlet valve can be closed.
Has the advantages that:
compared with the prior art, the in-situ electron paramagnetic resonance test reaction device and the test method thereof have the following technical effects:
1. through the in-situ electron paramagnetic resonance test reaction device, the continuous reaction under the condition of steady-flow reaction gas can be realized by controlling the flow rate of the reaction gas accessed by the gas inlet pipe, the gas inlet valve and the gas outlet valve, and compared with the prior method of bundling a balloon above a quartz test tube, the in-situ electron paramagnetic resonance test reaction device has the advantages of good gas circulation, stable gas concentration and more thorough and more sufficient reaction;
2. by changing the types of the reaction gases accessed to the gas inlet pipe, the random switching of various reaction gases can be realized, the problems that the similar methods can only carry out measurement under a single gas atmosphere and cannot meet the experimental conditions of atmosphere switching and the like in the prior art are solved, and the electron paramagnetic resonance can continuously carry out detection with traceability and real-time performance on some characteristics of molecules under the conditions of two or more gas atmospheres;
3. the integral device realizes the flexible combination of the spherical reactor and the quartz test tube, can realize the sealed preservation of the internal environment through the control of the air inlet valve, the air outlet valve and the sample introduction guide rod, avoids the influence of oxygen and water vapor in the air on a sample to be tested in the transfer process after reaction, achieves the purpose of in-situ test, and simultaneously provides possibility for the stable preservation of active samples during the interval of two tests;
4. the reaction device is ingenious in design, the test method is simple and easy to operate, changes of free radicals, transition metal complex valence states and configurations in reaction processes of different atmospheres can be tracked in situ, chemical reaction mechanisms under different atmospheres are clarified, the device and the test method are wide in application field, and the device and the test method are beneficial to popularization and application in other catalytic reaction systems with different atmosphere switching, for example, the device can be used for researching reaction mechanisms of hydrogen production catalyzed by transition metal complexes under different atmospheres.
Drawings
FIG. 1: is a schematic structural diagram of a gas reaction device in the in-situ electron paramagnetic resonance test reaction device.
FIG. 2: is a structural schematic diagram of a sample introduction control device in the in-situ electron paramagnetic resonance test reaction device.
FIG. 3: is a schematic diagram of the in-situ reaction of the in-situ electron paramagnetic resonance test reaction device in the resonant cavity.
FIG. 4: is a schematic diagram of the in-situ testing of the in-situ electron paramagnetic resonance testing reaction device in the resonant cavity.
Description of reference numerals: 1. The device comprises an air inlet pipe, 2 an air inlet valve, 3 an air outlet pipe, 4 an air outlet valve, 5 a spherical reactor, 6 a sample introduction guide pipe, 7 a quartz test tube, 8 a rubber sealing plug, 9 a sample introduction guide rod.
Detailed Description
The following examples further illustrate the content of the present application but should not be construed as limiting the application. Modifications and substitutions to methods, steps or conditions of the present application are intended to be within the scope of the present application without departing from the spirit and substance of the present application.
Example 1:
as shown in fig. 1 and fig. 2, an in-situ electron paramagnetic resonance test reaction device is composed of a gas reaction device and a sample injection control device, wherein the gas reaction device comprises six parts, i.e. a group of gas inlet pipes 1, gas inlet valves 2, gas outlet pipes 3, gas outlet valves 4, a spherical reactor 5 and a sample injection guide pipe 6, the group of gas inlet pipes 1 comprises three same gas inlet pipes, the three gas inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor 5, the three gas inlet pipes are connected with gas inlet emulsion pipes in a necking manner, the gas inlet emulsion pipes are respectively connected with a single gas cylinder, the gas inlet valve of one gas inlet pipe is opened, the gas inlet valves of the other two gas inlet pipes are kept closed, a single atmosphere reaction condition is provided, and the gas inlet valves 2 of two or three gas inlet pipes 1 can be opened according to experimental requirements, the switching of various reaction atmosphere conditions is realized by opening and closing the air inlet valves 2 on the three air inlet pipes 1; the front end of the air inlet pipe 1 is in a necking form; each air inlet pipe 1 is provided with an air inlet valve 2, and the air inlet valve 2 is arranged between the necking form of the air inlet pipe 1 and the spherical reactor 5; the sample introduction conduit 6 is connected with the bottom of the spherical reactor 5; the gas outlet pipe 3 is connected with the lower middle part of the spherical reactor 5, and the tail part of the gas outlet pipe 3 is in a necking form; an air outlet valve 4 is arranged on the air outlet pipe 3, and the air outlet valve 4 is arranged between the necking form of the air outlet pipe 3 and the spherical reactor 5; the sample introduction control device comprises a quartz test tube 7, a rubber sealing plug 8 and a sample introduction guide rod 9, wherein one end of the quartz test tube 7 is opened, and the other end of the quartz test tube is connected with one side of the rubber sealing plug 8 in a sealing manner; another survey of rubber sealing plug 8 links to each other with advance kind guide arm 9, the external diameter of rubber sealing plug 8 is the same with advance kind guide 6 internal diameter of pipe, advances kind controlling means and links to each other with gas reaction unit's advance kind guide 6 through rubber sealing plug 8, advance kind controlling means and be quartz test tube 7, rubber sealing plug 8 and advance kind guide arm 9 integration rigid design, through advance kind guide arm 9 reciprocate in advancing kind guide 6 and realize quartz test tube 7's removal, rubber sealing plug 8 external diameter equals with advance kind guide 6 internal diameter, realizes spherical reactor 5 and advances kind guide 6's encapsulated situation.
The gas reaction device is flexibly combined with the sampling control device, the sampling control device can move in the sampling guide pipe 6, the sampling guide rod 9 is provided with scales, the position where the sampling guide rod 9 is fixed is judged through the scales, the sampling guide rod 9 is moved during reaction, the rubber sealing plug 8 is positioned between the spherical reactor 5 and the sampling guide pipe 6 to ensure the sealing state in the spherical reactor 5, and a sample is positioned in the center of the paramagnetic resonant cavity during testing so as to obtain an optimal testing signal.
The diameter of the air inlet pipe 1 and the diameter of the air outlet pipe 3 are 10-15 mm, the diameter of a necking form is 5-10 mm, the diameter of the quartz test tube 7 is 4-8 mm, the diameter of the spherical reactor 5 is 50-60 mm, the diameter of the sample introduction guide pipe 6 is 10-15 mm, and the diameter of the sample introduction guide rod 9 is 3-6 mm.
The device can realize the in-situ tracking and detection of free radicals, transition metal complex valence states and configuration changes in different atmosphere reaction processes, and elucidate chemical reaction mechanisms in different atmospheres.
A method for realizing real atmosphere control test by an in-situ electron paramagnetic resonance test reaction device comprises the following steps:
the first step is as follows: vertically upwards placing the in-situ electron paramagnetic resonance test reaction device and placing the sample introduction conduit 6 into a paramagnetic resonance cavity; vertically placing a quartz test tube 7 upwards, and adding 40 mg of a sample to be tested; putting a quartz test tube 7 into the sample introduction guide tube 6 from the lower part of the sample introduction guide tube;
the second step is that: adjusting the position of a sample introduction guide rod 7 without performing a gas experiment to enable a sample to be positioned at the center of the paramagnetic resonant cavity, and closing the air inlet valve 2 and the air outlet valve 4;
the third step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the sample to be detected.
Example 2:
as shown in fig. 1 and fig. 2, an in-situ electron paramagnetic resonance test reaction device is composed of a gas reaction device and a sample injection control device, wherein the gas reaction device comprises six parts, i.e. a group of gas inlet pipes 1, gas inlet valves 2, gas outlet pipes 3, gas outlet valves 4, a spherical reactor 5 and a sample injection guide pipe 6, the group of gas inlet pipes 1 comprises three same gas inlet pipes, the three gas inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor 5, the three gas inlet pipes are connected with gas inlet emulsion pipes in a necking manner, the gas inlet emulsion pipes are respectively connected with a single gas cylinder, the gas inlet valve of one gas inlet pipe is opened, the gas inlet valves of the other two gas inlet pipes are kept closed, a single atmosphere reaction condition is provided, and the gas inlet valves 2 of two or three gas inlet pipes 1 can be opened according to experimental requirements, the switching of various reaction atmosphere conditions is realized by opening and closing the air inlet valves 2 on the three air inlet pipes 1; the front end of the air inlet pipe 1 is in a necking form; each air inlet pipe 1 is provided with an air inlet valve 2, and the air inlet valve 2 is arranged between the necking form of the air inlet pipe 1 and the spherical reactor 5; the sample introduction conduit 6 is connected with the bottom of the spherical reactor 5; the gas outlet pipe 3 is connected with the lower middle part of the spherical reactor 5, and the tail part of the gas outlet pipe 3 is in a necking form; an air outlet valve 4 is arranged on the air outlet pipe 3, and the air outlet valve 4 is arranged between the necking form of the air outlet pipe 3 and the spherical reactor 5; the sample introduction control device comprises a quartz test tube 7, a rubber sealing plug 8 and a sample introduction guide rod 9, wherein one end of the quartz test tube 7 is opened, and the other end of the quartz test tube is connected with one side of the rubber sealing plug 8 in a sealing manner; another survey of rubber sealing plug 8 links to each other with advance kind guide arm 9, the external diameter of rubber sealing plug 8 is the same with advance kind guide 6 internal diameter of pipe, advances kind controlling means and links to each other with gas reaction unit's advance kind guide 6 through rubber sealing plug 8, advance kind controlling means and be quartz test tube 7, rubber sealing plug 8 and advance kind guide arm 9 integration rigid design, through advance kind guide arm 9 reciprocate in advancing kind guide 6 and realize quartz test tube 7's removal, rubber sealing plug 8 external diameter equals with advance kind guide 6 internal diameter, realizes spherical reactor 5 and advances kind guide 6's encapsulated situation.
The gas reaction device is flexibly combined with the sampling control device, the sampling control device can move in the sampling guide pipe 6, the sampling guide rod 9 is provided with scales, the position where the sampling guide rod 9 is fixed is judged through the scales, the sampling guide rod 9 is moved during reaction, the rubber sealing plug 8 is positioned between the spherical reactor 5 and the sampling guide pipe 6 to ensure the sealing state in the spherical reactor 5, and a sample is positioned in the center of the paramagnetic resonant cavity during testing so as to obtain an optimal testing signal.
The diameter of the air inlet pipe 1 and the diameter of the air outlet pipe 3 are 10-15 mm, the diameter of a necking form is 5-10 mm, the diameter of the quartz test tube 7 is 4-8 mm, the diameter of the spherical reactor 5 is 50-60 mm, the diameter of the sample introduction guide pipe 6 is 10-15 mm, and the diameter of the sample introduction guide rod 9 is 3-6 mm.
The device can realize the in-situ tracking and detection of free radicals, transition metal complex valence states and configuration changes in different atmosphere reaction processes, and elucidate chemical reaction mechanisms in different atmospheres.
A method for realizing real atmosphere control test by an in-situ electron paramagnetic resonance test reaction device comprises the following steps:
the first step is as follows: vertically upwards placing the in-situ electron paramagnetic resonance test reaction device and placing the sample introduction conduit 6 into a paramagnetic resonance cavity; vertically placing a quartz test tube 7 upwards, and adding 30 mg of a sample to be tested; putting a quartz test tube 7 into the sample introduction guide pipe 6 from the lower part of the sample introduction guide pipe, moving the quartz test tube 7 through a sample introduction guide rod 9 to enable the quartz test tube 7 to enter the spherical reactor 5, and positioning a rubber sealing plug 8 between the spherical reactor 5 and the sample introduction guide pipe 6;
secondly, connecting the gas inlet pipe 1 and the gas outlet pipe 3 with the latex tube respectively, introducing single atmosphere reaction gas according to the reaction requirement of the sample, opening the gas inlet valve 2 and the gas outlet valve 4, introducing the reaction gas with stable flow rate from the gas inlet pipe 1, and controlling the flow rate to be 70 m L/min so that the sample to be detected and the reaction gas fully react in the spherical reactor 5;
the third step: adjusting the position of the sample introduction guide rod 9 to enable the sample to be positioned at the center of the paramagnetic resonant cavity, closing the air inlet valve 2 and the air outlet valve 4 to ensure that the gas is not exchanged with the outside any more, and performing electron paramagnetic resonance detection to obtain an electron paramagnetic resonance wave spectrogram of the sample to be detected after reaction.
Example 3:
as shown in fig. 1 and fig. 2, an in-situ electron paramagnetic resonance test reaction device is composed of a gas reaction device and a sample injection control device, wherein the gas reaction device comprises six parts, i.e. a group of gas inlet pipes 1, gas inlet valves 2, gas outlet pipes 3, gas outlet valves 4, a spherical reactor 5 and a sample injection guide pipe 6, the group of gas inlet pipes 1 comprises three same gas inlet pipes, the three gas inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor 5, the three gas inlet pipes are connected with gas inlet emulsion pipes in a necking manner, the gas inlet emulsion pipes are respectively connected with a single gas cylinder, the gas inlet valve of one gas inlet pipe is opened, the gas inlet valves of the other two gas inlet pipes are kept closed, a single atmosphere reaction condition is provided, and the gas inlet valves 2 of two or three gas inlet pipes 1 can be opened according to experimental requirements, the switching of various reaction atmosphere conditions is realized by opening and closing the air inlet valves 2 on the three air inlet pipes 1; the front end of the air inlet pipe 1 is in a necking form; each air inlet pipe 1 is provided with an air inlet valve 2, and the air inlet valve 2 is arranged between the necking form of the air inlet pipe 1 and the spherical reactor 5; the sample introduction conduit 6 is connected with the bottom of the spherical reactor 5; the gas outlet pipe 3 is connected with the lower middle part of the spherical reactor 5, and the tail part of the gas outlet pipe 3 is in a necking form; an air outlet valve 4 is arranged on the air outlet pipe 3, and the air outlet valve 4 is arranged between the necking form of the air outlet pipe 3 and the spherical reactor 5; the sample introduction control device comprises a quartz test tube 7, a rubber sealing plug 8 and a sample introduction guide rod 9, wherein one end of the quartz test tube 7 is opened, and the other end of the quartz test tube is connected with one side of the rubber sealing plug 8 in a sealing manner; another survey of rubber sealing plug 8 links to each other with advance kind guide arm 9, the external diameter of rubber sealing plug 8 is the same with advance kind guide 6 internal diameter of pipe, advances kind controlling means and links to each other with gas reaction unit's advance kind guide 6 through rubber sealing plug 8, advance kind controlling means and be quartz test tube 7, rubber sealing plug 8 and advance kind guide arm 9 integration rigid design, through advance kind guide arm 9 reciprocate in advancing kind guide 6 and realize quartz test tube 7's removal, rubber sealing plug 8 external diameter equals with advance kind guide 6 internal diameter, realizes spherical reactor 5 and advances kind guide 6's encapsulated situation.
The gas reaction device is flexibly combined with the sampling control device, the sampling control device can move in the sampling guide pipe 6, the sampling guide rod 9 is provided with scales, the position where the sampling guide rod 9 is fixed is judged through the scales, the sampling guide rod 9 is moved during reaction, the rubber sealing plug 8 is positioned between the spherical reactor 5 and the sampling guide pipe 6 to ensure the sealing state in the spherical reactor 5, and a sample is positioned in the center of the paramagnetic resonant cavity during testing so as to obtain an optimal testing signal.
The diameter of the air inlet pipe 1 and the diameter of the air outlet pipe 3 are 10-15 mm, the diameter of a necking form is 5-10 mm, the diameter of the quartz test tube 7 is 4-8 mm, the diameter of the spherical reactor 5 is 50-60 mm, the diameter of the sample introduction guide pipe 6 is 10-15 mm, and the diameter of the sample introduction guide rod 9 is 3-6 mm.
The device can realize the in-situ tracking and detection of free radicals, transition metal complex valence states and configuration changes in different atmosphere reaction processes, and elucidate chemical reaction mechanisms in different atmospheres.
A method for realizing real atmosphere control test by an in-situ electron paramagnetic resonance test reaction device comprises the following steps:
the first step is as follows: vertically upwards placing the in-situ electron paramagnetic resonance test reaction device and placing the sample introduction conduit 6 into a paramagnetic resonance cavity; vertically placing a quartz test tube 7 upwards, and adding 20 mg of a sample to be tested; putting a quartz test tube 7 into the sample introduction guide pipe 6 from the lower part of the sample introduction guide pipe, moving the quartz test tube 7 through a sample introduction guide rod 9 to enable the quartz test tube 7 to enter the spherical reactor 5, and positioning a rubber sealing plug 8 between the spherical reactor 5 and the sample introduction guide pipe 6;
secondly, respectively connecting an air inlet pipe 1 and an air outlet pipe 3 with the latex tube, introducing a single reaction gas A according to the reaction requirement of the sample, opening an air inlet valve 2 and an air outlet valve 4, introducing the reaction gas with stable flow rate from the air inlet pipe 1, and controlling the flow rate to be 30 m L/min so that the sample to be detected and the reaction gas fully react in a spherical reactor 5;
the third step: adjusting the position of a sample introduction guide rod 9 to enable the sample to be positioned at the center of the paramagnetic resonant cavity, closing an air inlet valve 2 and an air outlet valve 4 to ensure that gas is not exchanged with the outside any more, and performing electron paramagnetic resonance detection to obtain an electron paramagnetic resonance wave spectrogram of the sample to be detected under the atmosphere A condition;
and fourthly, adjusting the position of the sample introduction guide rod 9 again to enable the quartz test tube to enter the spherical reactor 5 again, enabling the rubber sealing plug 8 to be located between the spherical reactor 5 and the sample introduction guide tube 6 and externally connected with reaction gas B, opening the gas inlet valve 2 and the gas outlet valve 4, introducing the reaction gas with stable flow rate from the gas inlet pipe 1, controlling the flow rate to be 50 m L/min, enabling the sample and the reaction gas to fully react in the spherical reactor 5, adjusting the position of the sample introduction guide rod 9 after the reaction is finished to enable the sample to be located at the center of the paramagnetic resonant cavity, closing the gas inlet valve 2 and the gas outlet valve 4, ensuring that the gas is not exchanged with the outside, and performing electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the sample to be tested after the second reaction.
Claims (8)
1. An in-situ electron paramagnetic resonance test reaction device is characterized in that: the in-situ electron paramagnetic resonance test reaction device consists of a gas reaction device and a sample injection control device, wherein the gas reaction device comprises six parts, namely a group of gas inlet pipes (1), a gas inlet valve (2), a gas outlet pipe (3), a gas outlet valve (4), a spherical reactor (5) and a sample injection guide pipe (6), the group of gas inlet pipes (1) comprises three same gas inlet pipes, and the three gas inlet pipes are uniformly distributed on an upper hemisphere of the spherical reactor (5); the front end of the air inlet pipe (1) is in a necking form; each air inlet pipe (1) is provided with an air inlet valve (2), and the air inlet valve (2) is arranged between the necking form of the air inlet pipe (1) and the spherical reactor (5); the sample introduction conduit (6) is connected with the bottom of the spherical reactor (5); the gas outlet pipe (3) is connected with the lower middle part of the spherical reactor (5), and the tail part of the gas outlet pipe (3) is in a necking form; an air outlet valve (4) is arranged on the air outlet pipe (3), and the air outlet valve (4) is arranged between the necking form of the air outlet pipe (3) and the spherical reactor (5); the sample introduction control device comprises a quartz test tube (7), a rubber sealing plug (8) and a sample introduction guide rod (9), wherein one end of the quartz test tube (7) is opened, and the other end of the quartz test tube is connected with one side of the rubber sealing plug (8) in a sealing manner; the other side of the rubber sealing plug (8) is connected with a sample introduction guide rod (9), the outer diameter of the rubber sealing plug (8) is the same as the inner diameter of the sample introduction guide pipe (6), and the sample introduction control device is connected with the sample introduction guide pipe (6) of the gas reaction device through the rubber sealing plug (8).
2. The in-situ electron paramagnetic resonance test reaction device according to claim 1, wherein: a set of intake pipe (1) contains three the same intake pipe, three intake pipe evenly distributed is on spherical reactor (5), three intake pipe passes through the throat form and links to each other with the emulsion tube that admits air, the emulsion tube that admits air links to each other with single gas cylinder respectively, open the air inlet valve of one of them intake pipe, when the air inlet valve of two other intake pipes keeps closing, provide the reaction condition of single atmosphere, also can open air inlet valve (2) of two or three intake pipe (1) according to the experiment demand, through the opening of air inlet valve (2) on three intake pipe (1), close, realize the switching of multiple reaction atmosphere condition.
3. The in-situ electron paramagnetic resonance test reaction device according to claim 1, wherein: advance kind controlling means and be quartz test tube (7), rubber sealing plug (8) and advance a kind guide arm (9) integration rigidity design, through advance the removal that the reciprocating of a kind guide arm (9) in advancing kind pipe (6) realized quartz test tube (7), rubber sealing plug (8) external diameter equals with advance kind pipe (6) internal diameter, realizes spherical reactor (5) and advances the encapsulated situation of kind pipe (6).
4. The in-situ electron paramagnetic resonance test reaction device according to claim 1, wherein: the gas reaction device is flexibly combined with the sampling control device, the sampling control device can move in the sampling guide pipe (6), the sampling guide rod (9) is provided with scales, the position where the sampling guide rod (9) is fixed is judged through the scales, the sampling guide rod (9) is moved during reaction, the rubber sealing plug (8) is positioned between the spherical reactor (5) and the sampling guide pipe (6) to ensure the sealing state in the spherical reactor (5), and a sample is positioned at the center of a paramagnetic resonant cavity during testing so as to obtain the best testing signal.
5. The in-situ electron paramagnetic resonance test reaction device according to claim 1, wherein: the diameter of the air inlet pipe (1) and the diameter of the air outlet pipe (3) are 10-15 mm, the diameter of a necking form is 5-10 mm, the diameter of the quartz test tube (7) is 4-8 mm, the diameter of the spherical reactor (5) is 50-60 mm, the diameter of the sample introduction guide pipe (6) is 10-15 mm, and the diameter of the sample introduction guide rod (9) is 3-6 mm.
6. The in-situ electron paramagnetic resonance test reaction device according to claim 1, wherein: the device can realize the in-situ tracking and detection of free radicals, transition metal complex valence states and configuration changes in different atmosphere reaction processes, and elucidate chemical reaction mechanisms in different atmospheres.
7. A method for testing the in-situ electron paramagnetic resonance test reaction device of any one of claims 1 to 6, which comprises the following steps:
the first step is as follows: vertically upwards arranging the in-situ electron paramagnetic resonance test reaction device, and placing a sample introduction conduit (6) in a paramagnetic resonance cavity; vertically upwards placing a quartz test tube (7) and adding 10-50 mg of a sample to be tested; putting a quartz test tube (7) into the sample introduction guide pipe (6) from the lower part of the sample introduction guide pipe, moving the quartz test tube (7) through a sample introduction guide rod (9), and enabling the quartz test tube (7) to enter the spherical reactor (5), wherein a rubber sealing plug (8) is positioned between the spherical reactor (5) and the sample introduction guide pipe (6);
secondly, connecting a group of air inlet pipes (1) and air outlet pipes (3) with the latex tube respectively, introducing different reaction gases according to the reaction requirements of the sample, and opening an air inlet valve (2) and an air outlet valve (4), introducing the reaction gases with stable flow rate from the air inlet pipes (1), controlling the flow rate to be 5-100 m L/min, enabling the sample to be detected and the reaction gases to fully react in the spherical reactor (5), adjusting the position of a sample introduction guide rod (9) after the reaction is finished, enabling the sample to be positioned in the center of the paramagnetic resonant cavity, and then closing the air inlet valve (2) and the air outlet valve (4) to ensure that the gases are not exchanged with the outside;
the third step: carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the sample to be detected after reaction;
the fourth step: if a plurality of gas reactions or reaction results under the changed atmosphere are needed, the sample introduction guide rod (9) can be adjusted to enable the quartz test tube to enter the spherical reactor (5) again, and the second step and the third step are repeated.
8. A method for testing the in-situ electron paramagnetic resonance test reaction device of claim 7, wherein: in the second step, if a gas experiment is not carried out, the gas inlet valve (2) and the gas outlet valve (4) can be closed.
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