Non-contact controllable high-temperature heating reaction device and system for EPR detection

Abstract

The present invention provides a non-contact controllable high-temperature heating reaction device and system for EPR detection, which can effectively meet the heating and temperature control requirements in a small space of EPR, and effectively reduce the impact on EPR detection, and ensure the detection accuracy. The non-contact controllable high-temperature heating reaction device includes: a reaction tube, which is arranged in the detection cavity of an electron paramagnetic resonance device, and is provided with a sample loading area inside for carrying the sample to be detected, and the lower end axially penetrates the electron paramagnetic resonance device, and a temperature measuring window is provided at the bottom of the lower end; a heating module, which performs non-contact controllable high-temperature heating on the reaction tube, including: a spotlight cup, which is connected to the spotlight cup, penetrates the side wall of the electron paramagnetic resonance device and extends to the vicinity of the sample loading area, and guides the light irradiation emitted by the spotlight cup to the sample for irradiation heating; and a temperature sensor, which faces the temperature measuring window and monitors the temperature of the sample in the reaction tube in a non-contact manner.

Description

Technical Field

[0001] The invention belongs to the field of EPR test equipment, and in particular relates to a non-contact controllable high-temperature heating reaction device and system for EPR detection. Background Art

[0002] EPR (electron paramagnetic resonance) is a spectroscopic technique that can detect substances containing unpaired electrons. The lifetime of free electrons is usually very short, but they still play a vital role in many processes, such as photosynthesis, oxidation, catalysis, polymerization, etc. Therefore, EPR is a technology that spans multiple disciplines, including chemistry, physics, biology, materials science, medicine, etc. At present, there are relatively mature instruments for electron paramagnetic resonance spectroscopy detection.

[0003] In EPR detection, it is necessary to form a resonant cavity magnetic field area through the main magnetic field, and then form a resonant wave through the microwave system to detect the electron paramagnetic resonance absorption spectrum peak. Therefore, in order to ensure the precision and accuracy of the detection, the EPR instrument usually places the sample area with a small structure and a very compact space. On the other hand, the detection object of EPR is electrons or holes, that is, some free radical fragments, and these free radicals exist for a very short time and are very easy to annihilate. Therefore, there is still a big difference between putting the reaction intermediate state into EPR detection and the free radical reaction that occurs during the actual reaction process, which makes in-situ EPR detection of the reaction process very important. In order to carry out in-situ reactions, the need for heating and temperature control are the key to limiting the application of EPR in in-situ detection.

[0004] The traditional method of using resistance wire for heating, on the one hand, the internal space of EPR is small, it is difficult to put in a heater of suitable size, and the heating temperature is not high. On the other hand, due to the use of metal heating wire, there is a certain interference with the magnetic field and microwave in the EPR detection resonant cavity, affecting the detection accuracy. In addition, the introduction of current in the metal wire will also form an additional magnetic field, which is particularly fatal to EPR detection. Although the method of using hot air flow to carry heat into the reaction chamber can eliminate the problems of resistance wire heating, the heat flux density of the air flow carrying method is low, and the heat attenuation is serious. In order to make the sample in the resonant cavity reach a certain temperature, the temperature of the hot air flow blown in is extremely high, the power consumption is large, and it puts forward extremely high requirements on the thermal insulation performance of the reactor inserted in the EPR, and there is a large lag in the regulation of the sample temperature in the resonant cavity. Summary of the invention

[0005] The present invention is made to solve the above-mentioned problems, and its purpose is to provide a non-contact controllable high-temperature heating reaction device and system for EPR detection, which can effectively meet the heating and temperature control needs in the narrow space of EPR, and effectively reduce the impact on EPR detection and ensure detection accuracy.

[0006] In order to achieve the above object, the present invention adopts the following scheme:

[0007] <Device>

[0008] The invention provides a non-contact controllable high-temperature heating reaction device for EPR detection, which is characterized by comprising: a reaction tube, which is arranged in a detection cavity of an electron paramagnetic resonance (EPR) device, a sample loading area is arranged inside the reaction tube for carrying a sample to be detected, and the lower end thereof penetrates the electron paramagnetic resonance device along the axial direction, and a temperature measuring window is arranged at the bottom of the lower end; a heating module, which performs non-contact controllable high-temperature heating on the reaction tube, and comprises: a spotlight cup, which is connected to the spotlight cup, penetrates the side wall of the electron paramagnetic resonance device and extends to the vicinity of the sample loading area, and guides the light irradiation emitted by the spotlight cup to the sample for irradiation heating; and a temperature sensor, which faces the temperature measuring window and monitors the temperature of the sample in the reaction tube in a non-contact manner.

[0009] The beneficial effects of the above scheme are:

[0010] The heating module is inserted from the side of the EPR device and performs light irradiation heating on the sample area in the reaction tube. The temperature sensor is set at the bottom of the reaction tube to detect the sample temperature in the reaction tube. The heating module and the infrared temperature sensor both adopt non-contact methods. On the one hand, it meets the needs of heating and temperature control in the narrow space of EPR. On the other hand, it also reduces the number of components entering the resonant cavity (detection cavity), reduces the impact on EPR detection, and ensures detection accuracy.

[0011] Preferably, in the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention, it can also have the following characteristics: the reaction tube includes: a quartz outer tube; a sieve plate, placed in the quartz outer tube, located at the bottom of the sample loading area, for carrying the sample and allowing the reaction gas flow to flow in to contact the sample; a silicon nitride light-absorbing sleeve, embedded in the quartz outer tube, arranged around the sample loading area, absorbing the radiation from the heating module to heat the sample; an air inlet, arranged on the lower end side wall of the quartz outer tube, for introducing reaction gas; an exhaust port, arranged at the upper end of the quartz outer tube; and a temperature measuring window, arranged on the bottom surface of the quartz outer tube.

[0012] The beneficial effects of the above scheme are:

[0013] The silicon nitride light-absorbing sleeve can absorb the radiation from the spotlight cup to heat the sample. In this way, on the one hand, the characteristics of silicon nitride, such as good absorbance, high photothermal conversion efficiency, and high thermal conductivity, can be used to reduce the reduction in the control accuracy of the heating process caused by the difference in absorbance of different samples (even the absorbance of the same sample will change during the heating process). On the other hand, silicon nitride is relatively stable at high temperatures, which is conducive to more reliable and repeatable blank reference experiment calibration using non-contact radiation heating. The sieve plate can carry the sample and ensure the inflow of the reaction gas flow at the bottom. The reaction gas enters from the bottom and exits from the top, which can ensure its full contact with the sample. A temperature sensor is set outside the temperature measurement window. Since the reaction gas enters from the bottom and exits from the top, the gas composition and concentration at the bottom of the sieve plate can be kept constant, and there is no interference from the reaction products, which ensures the temperature detection accuracy and accuracy of the infrared temperature sensor.

[0014] Preferably, in the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention, it can also have the following characteristics: the guiding part includes: a light guide tube, which passes through the side wall of the electron paramagnetic resonance device, and the inner end extends to the vicinity of the sample loading area but does not enter the detection cavity, including: a quartz inner tube with a gold-coated inner wall, and a SiO2 aerogel sleeve connected to the outside of the quartz inner tube; and a light trap, which is funnel-shaped with a small front end and a large rear end, the inner wall of which is coated with gold, the front end is connected to the outer end of the light guide tube, and the rear end size matches the spotlight cup, and is opposite to and surrounds the light output area of ​​the spotlight cup.

[0015] The beneficial effects of the above scheme are:

[0016] Quartz is resistant to high temperatures and has a low coefficient of thermal expansion, which makes it easy to coat. The gold coating (gold coating) in the light guide and the light trap has a very good reflectivity for infrared and near-infrared light for heating, which can maximize the reflection and transmission of infrared and near-infrared light introduced into the light guide. SiO2 aerogel has good thermal insulation properties and a low coefficient of thermal expansion, which can ensure that the EPR device outside the light guide is not affected by the temperature of the light guide, ensuring detection accuracy. Furthermore, the light guide only extends to the vicinity of the sample loading area but does not enter the detection cavity, which can minimize the impact on the EPR magnetic field.

[0017] The working principle of the light guide is as follows: the focus of the spotlight cup is located inside the light guide, and incident light at different angles is dispersed again after passing through the focus. However, the gold coating on the inner wall of the light guide confines these light rays inside the light guide and transmits them forward through reflection, and then emits them from the light guide outlet. The light trap cooperates with the spotlight cup to confine the light rays that are not focused to the area surrounded by the light trap and the cup, and then enters the light guide after multiple reflections, thereby making maximum use of the light emitted by the cup. On the one hand, it is beneficial to increase energy utilization efficiency, and on the other hand, it can also maximize the irradiation energy density at the light guide outlet and increase the heating temperature.

[0018] Preferably, in the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention, it can also have the following characteristics: a positioning pin is provided on the outer wall of the light trap, and a positioning mechanism is provided on the side wall of the electron paramagnetic resonance device, which is matched with the positioning pin and connected to position the light guide tube to face the sample loading area.

[0019] Preferably, in the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention, it can also have the following characteristics: the guide part also includes: a lamp cup holder, which is arranged around the spotlight cup and is used to install and fix the spotlight cup; a fixing plate, which is provided with a connecting hole, which is used to fix the guide part on the front end of the lamp cup holder; and a heat dissipation fan, which is arranged in the lamp cup holder and is located behind the spotlight cup. The four sides of the lamp cup holder are provided with a plurality of narrow and long grooves for uniform heat dissipation. Under the rotation of the heat dissipation fan, the surrounding air is inhaled to dissipate the heat of the spotlight cup. The method of opening a plurality of narrow and long grooves on the four sides can ensure sufficient air circulation on the one hand, and prevent too much dust from being inhaled and adhering to the spotlight cup to affect the life of the lamp cup on the other hand.

[0020] Preferably, in the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention, it can also have the following feature: the temperature sensor is an infrared temperature sensor.

[0021] Preferably, the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention may also include: a controller, which is communicatively connected with the electron paramagnetic resonance device, the reaction tube, the heating module, and the temperature sensor, and stores a temperature control database of the sample loading area temperature and the heating rate under different spotlight cup powers. It can operate the spotlight cup at the corresponding power according to the operator's temperature control instructions and based on the data in the temperature control database, and feedback-adjust the power of the spotlight cup according to the real-time temperature monitored by the temperature sensor to ensure that the temperature change process of the reaction zone meets the experimental requirements, and record the electron paramagnetic resonance spectrum to achieve automatic and precise temperature control and ensure the temperature control effect.

[0022] Preferably, the non-contact controllable high-temperature heating reaction device for EPR detection involved in the present invention may also include: a DC power supply, connected to the heating module and communicated with the controller, to supply power to the spotlight cup according to control information of the controller.

[0023] <System>

[0024] The present invention also provides an EPR detection system, characterized in that it comprises: an electron paramagnetic resonance device; and the non-contact controllable high-temperature heating reaction device for EPR detection described in the above <Device>. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1Schematic diagram of the structure of the EPR detection system involved in the embodiment of the present invention;

[0026] Figure 2 is a schematic diagram of the structure of a reaction tube involved in an embodiment of the present invention;

[0027] Figure 3 is an exploded view of a heating module involved in an embodiment of the present invention;

[0028] Figure 4 It is a structural schematic diagram of a light guide tube and a light trap involved in an embodiment of the present invention;

[0029] Figure 5 Schematic diagram of the light path of the spotlight and the light guide tube involved in the embodiment of the present invention;. DETAILED DESCRIPTION

[0030] The non-contact controllable high-temperature heating reaction device and system for EPR detection according to the present invention will be described in detail below with reference to the accompanying drawings.

[0031] <Example>

[0032] like Figure 1 As shown, the EPR detection system 100 includes an electron paramagnetic resonance device 10 and a non-contact controllable high-temperature heating reaction device 20 .

[0033] The electron paramagnetic resonance (EPR) device 10 performs electron paramagnetic resonance detection on the sample placed in the detection chamber and obtains EPR data. In this embodiment, the electron paramagnetic resonance device 10 is an electron paramagnetic resonance spectroscopy instrument.

[0034] The non-contact controllable high-temperature heating reaction device 20 includes a reaction tube 21 , a heating module 22 , a temperature sensor 23 , a DC power supply 24 and a controller 25 .

[0035] like Figure 1 and 2As shown, the reaction tube 21 is sealed and arranged in the detection cavity of the electron paramagnetic resonance device 10, and the upper and lower ends are both sealed and penetrate the electron paramagnetic resonance device 10 in the axial direction. The middle part of the reaction tube 21 is provided with a sample loading area for carrying the sample S to be detected. The reaction tube 21 includes a quartz outer tube 21a, a sieve plate 21b, a silicon nitride light absorbing sleeve 21c, an air inlet 21d, an exhaust port 21e, and a temperature measuring window 21f. The sieve plate 21b is placed in the quartz outer tube 21a, located at the bottom of the sample loading area, for carrying the sample S, and allowing the reaction gas flow to flow into and contact the sample S evenly. The silicon nitride light absorbing sleeve 21c is embedded in the quartz outer tube 21a, arranged around the sample loading area, absorbing the radiation from the heating module, thereby uniformly and quickly heating the sample S. The air inlet 21d is arranged on the side wall of the lower end of the quartz outer tube 21a, and the reaction gas is introduced from bottom to top. The exhaust port 21e is arranged at the upper end of the quartz outer tube 21a. The temperature measuring window 21f is provided on the bottom surface of the quartz outer tube 21a for temperature detection.

[0036] like Figure 1 and 3 As shown, the heating module 22 is used to perform non-contact controllable high-temperature heating on the reaction tube 21, and includes a spotlight cup 22a, a light guide 22b, a light trap 22c, a lamp cup holder 22d, a fixing plate 22e, a cooling fan 22f and a connecting piece 22g.

[0037] The light guide 22b is sealed and penetrates the side wall of the electron paramagnetic resonance device 10, and the inner end of the light guide 22b extends to the vicinity of the sample loading area but does not enter the detection cavity. Figure 4 As shown, the light guide 22b includes a quartz inner tube 22b-2 with a gold coating 22b-1 on the inner wall, and a SiO2 aerogel sleeve 22b-3 sleeved on the outside of the quartz inner tube 22b-2.

[0038] The light trap 22c is in the shape of a funnel with a small front end and a large rear end, and the inner wall is plated with a gold coating 22b-1. The front end is sealed and connected to the outer end of the light guide 22b, and the rear end size matches the spotlight cup 22a, facing and surrounding the light output area of ​​the spotlight cup 22a. Two positioning pins 22c-1 are provided on the outer wall of the light trap 22c, and two positioning mechanisms (for example, bayonet) are provided on the side wall of the electron paramagnetic resonance device 10, which match and connect with the positioning pins 22c-1 to position the inner end (light output end) of the light guide 22b to face the sample loading area, so that the light irradiation emitted by the spotlight cup 22a is accurately focused and directed to the sample S for rapid irradiation heating.

[0039] The lamp cup holder 22d is arranged around the spotlight cup 22a and is used to install and fix the spotlight cup 22a. The four sides of the lamp cup holder 22d are all provided with a plurality of narrow and long grooves for uniform heat dissipation.

[0040] The fixing plate 22e matches the spotlight cup 22a, is fixedly connected to the periphery of the light trap 22c, and has connecting holes at four corners for fixing the light trap 22c to the front end of the lamp cup holder 22d.

[0041] The cooling fan 22f is disposed in the lamp cup holder 22d and is located behind the spotlight cup 22a.

[0042] The connecting member 22g is a plate-like structure, with a ventilation hole corresponding to the cooling fan 22f at the center and connecting holes around it for fixing the lamp cup holder 22d and further fixing the entire heating module 22.

[0043] like Figure 5 As shown, the focus of the spotlight cup 22a is located in the light guide 22b, and the incident light at different angles is dispersed again after passing through the focus. The gold coating on the inner wall of the light guide 22b limits these light rays in the light guide 22b and transmits them forward through reflection, and then emits them from the outlet of the light guide 22b; the light trap 22c cooperates with the spotlight cup 22a, and can limit the light rays that are not focused to the area surrounded by the light trap 22c and the spotlight cup 22a, and then enter the light guide 22b after multiple reflections, thereby making the most of the light emitted by the spotlight cup 22a. On the one hand, it is beneficial to increase the energy utilization efficiency, and on the other hand, it can also maximize the irradiation energy density at the outlet of the light guide 22b and increase the heating temperature.

[0044] The temperature sensor 23 is disposed toward the temperature measuring window 21f, and monitors the temperature of the sample S in the reaction tube 21 in a non-contact manner. In this embodiment, the temperature sensor 23 is an infrared temperature sensor.

[0045] The DC power supply 24 is connected to the heating module 22 and supplies power to the spotlight cup 22a according to control information.

[0046] The controller 25 is connected to the electron paramagnetic resonance device 10, the reaction tube 21, the heating module 22, the temperature sensor 23, and the DC power supply 24 in communication, and controls their operation. Furthermore, the controller 25 stores a temperature control database of the sample loading area temperature and the heating rate under different spotlight cup powers, and can operate the spotlight cup 22a at the corresponding power according to the operator's temperature control instruction and based on the data in the temperature control database, and feedback adjust the power of the spotlight cup 22a according to the real-time temperature monitored by the temperature sensor 23 to ensure that the temperature of the reaction area meets the experimental requirements, and obtain the data detected by the electron paramagnetic resonance device 10 to generate an electron paramagnetic resonance spectrum, and then display it.

[0047] The temperature control database can be established by an operator by calibrating the reaction zone temperature under different spotlight cup 22a powers under the reaction gas flow, obtaining sufficient data, inputting and storing it in the controller 25.

[0048] Based on the above structure, the specific working method of the EPR detection system 100 is:

[0049] Step 1. The operator inputs the experimental temperature change requirement through the controller 25, and the controller 25 presets the output power scheme of the spotlight cup 22a according to the data in the temperature control database;

[0050] Step 2. The controller 25 controls the power output of the spotlight cup 22a by adjusting the DC power supply 24 according to the preset output power scheme of the spotlight cup 22a. During this process, the controller 25 performs feedback adjustment according to the real-time temperature data monitored by the temperature sensor 23 to ensure that the temperature change process of the reaction zone meets the experimental requirements and obtain and record the EPR spectrum;

[0051] Step 3. Load sample S, repeat step 2, subtract the EPR spectrum of the unloaded sample S, and output and display the EPR spectrum lines of sample S during the heating process.

[0052] The above is merely an example of the technical solution of the present invention. The non-contact controllable high-temperature heating reaction device and system for EPR detection involved in the present invention are not limited to the structure described above, but are subject to the scope defined by the claims. Any modification, supplement or equivalent replacement made by a technician in the field of the present invention on this basis is within the scope of protection required by the claims of the present invention.

Claims

1. A non-contact controllable high-temperature heating reaction device for EPR detection, characterized in that: include: The reaction tube is arranged in the detection cavity of the electron paramagnetic resonance device, and has a sample loading area inside for carrying the sample to be detected, and the lower end thereof penetrates the electron paramagnetic resonance device in the axial direction, and a temperature measuring window is arranged at the bottom of the lower end; A heating module, which performs non-contact controllable high-temperature heating on the reaction tube, comprises: a spotlight cup, a guide portion connected to the spotlight cup, extending through the side wall of the electron paramagnetic resonance device to the vicinity of the sample loading area, and directing the light irradiation emitted by the spotlight cup to the sample for irradiation heating; and A temperature sensor, facing the temperature measuring window, monitors the temperature of the sample in the reaction tube in a non-contact manner; Wherein, the reaction tube comprises: Quartz outer tube; A sieve plate is placed in the quartz outer tube and at the bottom of the sample loading area, and is used to carry the sample and allow the reaction gas flow to flow into the sample; A silicon nitride light-absorbing sleeve, embedded in the quartz outer tube and arranged around the sample loading area, absorbs radiation from the heating module to heat the sample; An air inlet, arranged on the side wall of the lower end of the quartz outer tube, for introducing reaction gas; an exhaust port, disposed at the upper end of the quartz outer tube; and The temperature measuring window is arranged on the bottom surface of the quartz outer tube; The guide portion comprises: A light guide penetrating the side wall of the electron paramagnetic resonance device, with the inner end extending to the vicinity of the sample loading area but not entering the detection cavity, comprising: a quartz inner tube with a gold coating on the inner wall, and a SiO2 aerogel sleeve sleeved outside the quartz inner tube; and The light trap is in the shape of a funnel with a small front end and a large rear end, and the inner wall is plated with a gold coating. The front end is connected to the outer end of the light guide tube, and the rear end size matches the spotlight cup, facing and surrounding the light output area of ​​the spotlight cup.

2. The non-contact controllable high temperature heating reaction device for EPR detection according to claim 1, characterized in that: in, A positioning pin is arranged on the outer wall of the light trap, and a positioning mechanism matched with the positioning pin is arranged on the side wall of the electron paramagnetic resonance device so as to position the light guide tube to face the sample loading area.

3. The non-contact controllable high temperature heating reaction device for EPR detection according to claim 1, Features: in, The guide portion further comprises: A lamp cup seat, arranged around the spotlight cup, and used for installing and fixing the spotlight cup; A fixing plate, provided with a connecting hole, used for fixing the guide portion on the front end of the lamp cup holder; and The cooling fan is arranged in the lamp cup seat and is located behind the spotlight cup.

4. The non-contact controllable high temperature heating reaction device for EPR detection according to claim 3, characterized in that: in, The four sides of the lamp cup holder are each provided with a plurality of narrow and long grooves for uniform heat dissipation.

5. The non-contact controllable high temperature heating reaction device for EPR detection according to claim 1, characterized in that: in, The temperature sensor is an infrared temperature sensor.

6. The non-contact controllable high-temperature heating reaction device for EPR detection according to claim 1, characterized in that: Also includes: The controller is communicatively connected with the electron paramagnetic resonance device, the reaction tube, the heating module, and the temperature sensor, and stores a temperature control database of the sample loading area temperature and the heating rate under different spotlight cup powers. The controller can operate the spotlight cup under the corresponding power according to the temperature control instructions of the operator and based on the data in the temperature control database, and feedback-adjust the power of the spotlight cup according to the real-time temperature monitored by the temperature sensor to ensure that the temperature change process of the reaction zone meets the experimental requirements, and record the electron paramagnetic resonance spectrum.

7. The non-contact controllable high temperature heating reaction device for EPR detection according to claim 6, characterized in that: Also includes: A direct current power supply is connected to the heating module and is in communication with the controller, and supplies power to the spotlight cup according to control information from the controller.

8. An EPR detection system, characterized in that: include: Electron paramagnetic resonance device; and A non-contact controllable high-temperature heating reaction device for EPR detection as described in any one of claims 1 to 7.

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