A combined calorimetric and infrared device and method for simultaneous determination of the strength and state of solid-gas (liquid) interactions

Abstract

This invention discloses a calorimetric and infrared (IR) coupled device and method capable of simultaneously detecting the strength and state of solid-gas (liquid) interactions. The device, combined with a calorimeter having a measuring channel and an infrared measurement module, can simultaneously measure the strength and state of solid-gas (liquid) interactions. This invention also discloses a method for studying and detecting the strength and state of solid-gas (liquid) interactions. The amount of gas or liquid involved in the interaction is obtained by subtracting the amount of gas or liquid after the interaction from the initial mass of the gas or liquid, and the amount of substance is quantitatively obtained through a mass spectrometer connected to the device. The calorimetric and infrared coupled device and method disclosed in this invention can simultaneously obtain the strength and state of solid-gas (liquid) interactions in a single experiment.

Description

Technical Field

[0001] This invention belongs to the field of solid-gas and solid-liquid interaction research and evaluation technology, specifically relating to a calorimetric and infrared spectroscopy device and method capable of simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions. This device and method can simultaneously detect the heat change caused by the interaction between a solid and a gas or liquid, as well as the corresponding state change (i.e., the adsorbed state of the gas or liquid). A direct link can be established between the intensity and state of the interaction, leading to a better understanding of the nature of the interaction. This device can be widely applied in catalysis, adsorption, process safety, and other fields. Background Technology

[0002] Interactions between substances (such as solid-gas or solid-liquid interactions) are widespread in various research fields, including catalysis, adsorption, process safety, and materials preparation. Measuring and studying the strength of these interactions is of great research value in advancing these fields. For example, a catalytic reaction cycle involves reactant adsorption, followed by the adsorbed reactants reacting to form products, and finally, the products desorbing, thus completing the catalytic cycle. The adsorption of gaseous (liquid) reactants on the surface of a solid catalyst is the starting point of the catalytic reaction and determines whether the reaction can proceed smoothly. If the reactant adsorption is too strong, it may prevent the adsorption of other reactants, thus inhibiting the reaction. If the reactant adsorption is too weak, it may not be activated on the catalyst and thus fail to react. Therefore, the strength of the chemical bonds formed between reactants and catalysts is of great guiding significance for understanding the catalytic performance of catalysts. Catalytic adsorption is a typical process of interaction between reactants and catalysts, which can form chemical bonds and manifest as heat. Therefore, measuring this heat change allows us to understand the strength of the interaction between catalysts and reactants.

[0003] Measuring the strength of interactions between substances requires highly sensitive calorimetric instruments. Conventional thermal analysis methods, such as thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), rely on a single thermocouple to detect temperature changes between the sample and reference cells. Due to heat losses from conduction, convection, and radiation, their detection efficiency is only 20-30%. In contrast, heat flow calorimeters based on the Tian-Calvet principle, using hundreds or even thousands of thermocouples to detect heat, can achieve a detection efficiency of over 95%, making them an effective means of detecting the strength of interactions between substances. However, conventional heat flow calorimeters only provide information on the intensity of the interaction (heat), but the nature of this interaction remains unclear. To better understand interactions between substances, other characterization methods should be used to reveal their essence. Infrared spectroscopy is an effective means of detecting the molecular structure of substances, providing information about the molecular structure during interactions. For example, when ethylene is adsorbed on a Pt single-crystal model system, infrared detection reveals three interaction forms: ethylene, double σ-bond ethylene, and π-bond ethylene. Calorimetry, however, shows that these correspond to different interaction strengths. Therefore, if we can study and measure the intensity and state of interactions simultaneously, we can clearly understand the nature of interactions between matter. Although it is currently possible to detect these interactions through separate tests, the different testing conditions (such as temperature, testing area, and sample morphology) of the two techniques prevent the results from being directly correlated.

[0004] Based on this, the present invention proposes a calorimetric and infrared spectroscopy device and method that can simultaneously detect the intensity and state of solid-gas or solid-liquid interactions, thereby obtaining information on the intensity and state of interactions between substances on the same sample and under the same conditions. Summary of the Invention

[0005] The purpose of this invention is to provide a calorimetric and infrared combined device capable of simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions.

[0006] Another object of the present invention is to provide a method for studying the strength and state of interactions between substances using the above-described combined device.

[0007] To achieve the above objectives, the specific technical solution of the present invention is as follows:

[0008] A calorimetric and infrared combined device capable of simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions includes: a calorimeter having a measuring channel tube; an infrared light source and an infrared detector respectively provided at both ends of the calorimeter extending outwards; a sealing gasket (3), a body (1), and a gold-plated infrared reflector (7) symmetrically arranged from the inside to the outside of the calorimeter; an infrared internal reflection crystal (4) movable inside the measuring channel tube of the calorimeter; the calorimeter, sealing gasket (3), body (1), infrared internal reflection crystal (4), and gold-plated infrared reflector (7) fixed by a clamp (2) set on the outside; a stainless steel tube-Ⅰ (8) with an outwardly extending opening is provided at the weld between the body (1) and the sealing gasket (3) on the infrared detector side; a stainless steel tube-Ⅱ (8') with an outwardly extending opening is provided at the weld between the body (1) and the sealing gasket (3) on the infrared light source side. The stainless steel tube-Ⅰ (8) and the stainless steel tube-Ⅱ (8') have different outward extending directions.

[0009] Furthermore, in the above technical solution, O-rings (5) are fitted between the outer sides of the infrared internal reflection crystal (4) and the body (1), and the gold-plated infrared reflector (7) is located between the infrared light source and the O-rings (5) and between the infrared detector and the O-rings (5), respectively. The device is provided with a rotating cap (6) that pushes the gold-plated infrared reflector (7) to press the O-rings (5) tightly. The through openings of the sealing gasket (3), the body (1) and the gold-plated infrared reflector (7) are the same as the openings of the calorimeter measuring channel tube. A solid sample film (9) is fixed on the infrared internal reflection crystal (4). The solid sample film (9) is fixed on the infrared internal reflection crystal (4) by deposition.

[0010] Furthermore, in the above technical solution, the stainless steel tube-II (8') is connected to a mass spectrometer; the stainless steel tube-I (8) can be used to introduce gas or liquid molecules, and the stainless steel tube-II (8') connected to the mass spectrometer is used to quantify the gas and liquid molecules after interaction.

[0011] Furthermore, in the above technical solution, the calorimeter is a Sensys calorimeter from Seteram or any other calorimeter with a measuring channel tube design in its measuring module; the infrared internal reflection crystal (4) is cylindrical with 30° to 60° conical surfaces on both sides, and is made of one of ZnSe, Si and Ge; the gold-plated infrared reflector (7) is hemispherical with a hole punched at the apex of the sphere, and the conical surface of the cylindrical infrared internal reflection crystal extends into the hole punched at the apex of the sphere.

[0012] This invention also provides a method for studying and evaluating the intensity and state of solid-gas or solid-liquid interactions using a combined calorimetric and infrared spectroscopy device.

[0013] 1) Research on the strength and state of solid-gas interactions, specifically including:

[0014] A solid sample film (9) was immobilized on a cylindrical infrared internal reflection crystal (4). The calorimeter was then programmed to reach the required temperature, and a treatment atmosphere was introduced through stainless steel tube-I (8) to treat the solid sample film (9). After treatment, the calorimeter was lowered to the experimental temperature under an inert atmosphere. First, the gas to be studied was switched to the initial mass of the mass spectrometer. Then, the gas was introduced onto the solid sample through stainless steel tube-I (8) to induce a solid-gas interaction. The mass of the remaining gas after the interaction was quantitatively obtained by the mass spectrometer connected to stainless steel tube-II (8'). The interaction intensity was measured by the calorimeter, while the interaction state was obtained by collecting infrared light through a reflector (7). The infrared internal reflection crystal (4) reflected the infrared light through the solid sample film (9), and the result was finally measured by an infrared detector.

[0015] 2) Research on the strength and state of solid-liquid interactions, specifically including:

[0016] A solid sample film (9) was immobilized on a cylindrical infrared internal reflection crystal (4). The calorimeter was then programmed to reach the required temperature, and a treatment atmosphere was introduced through stainless steel tube-I (8) to treat the solid sample film (9). After treatment, the calorimeter was lowered to the experimental temperature under an inert atmosphere. The liquid sample was introduced by passing inert gas into a bubbler containing the liquid to be studied. Under constant temperature and flow rate, the amount of liquid molecules carried out by the inert gas per unit time could be calculated based on the liquid vapor pressure and the gas flow rate. The inert gas carried the liquid to be studied through stainless steel tube-I (8) to the solid sample, causing a solid-liquid interaction. The amount of liquid remaining after the interaction was quantitatively obtained by mass spectrometry connected to stainless steel tube-II (8'). The amount of liquid interacting with the solid could be obtained by quantitatively determining the decrease in liquid mass before and after the interaction using mass spectrometry. The strength and state of the solid-liquid interaction could be obtained by combining calorimetry and infrared spectroscopy.

[0017] Furthermore, in the above technical solution, the preparation of the solid sample film (9) is as follows: the solid sample is first ground to obtain a powder with a mesh size of 200 to 800 mesh; then it is dispersed in a solvent to obtain a stable suspension, the suspension is sprayed onto the middle region of a cylindrical infrared internal reflection crystal (4), and baked by an infrared lamp to form a solid sample film (9).

[0018] Furthermore, in the above technical solution, the grinding is done using a ball mill, and the ball milling time is 3 to 5 hours; the dispersion is done using ultrasonic dispersion, and the ultrasonic dispersion solvent includes one of water and ethanol, and the ultrasonic dispersion time is 0.5 to 1 hour; the suspension is sprayed using a spray gun.

[0019] Furthermore, in the above technical solution, the method measures the intensity and state of the interaction between a gas or liquid and a solid, wherein the gas to be studied is one of CO, H2, O2, and NH3.

[0020] Furthermore, in the above technical solution, the introduced processing atmosphere is one of H2, O2, He or Ar; the inert atmosphere is He or Ar.

[0021] Furthermore, in the above technical solution, the amount of gas or liquid that interacts is obtained by subtracting the amount of gas or liquid after the interaction from the initial amount of gas or liquid. The amount of substance is quantitatively obtained by mass spectrometry connected to stainless steel tube-II (8').

[0022] The present invention has the following advantages:

[0023] 1. When combined with a calorimeter with a measuring channel tube (such as the Sensys model from Setaram) and an infrared measurement module, simultaneous calorimetry and infrared detection can be achieved.

[0024] 2. Be able to understand the nature of inter-matter interactions by combining the intensity of the interaction between substances (heat) and the state of the interaction between substances (the adsorption form of gas / or liquid on solid).

[0025] 3. This apparatus and method can not only study the nature of the interaction between reactants and solid catalysts during the adsorption process at the initiation step of catalytic reactions, but can also be widely applied in many other fields involving interactions between substances. Attached Figure Description

[0026] Figure 1 A schematic diagram of the device for simultaneously detecting the strength and state of interactions between substances, provided by the present invention.

[0027] Wherein: 1-body; 2-clamp; 3-sealing gasket; 4-infrared internal reflection crystal; 5-O ring; 6-rotary pressure cap; 7-gold-plated infrared reflector; 8-stainless steel tube-I; 8'-stainless steel tube-II; 9-solid sample film

[0028] Figure 2 Figure (a) shows the intensity measurement results of the interaction between CO and Pd / FeOx catalyst simultaneously detected in Example 3, and Figure (b) shows the infrared spectrum of the interaction state between CO and Pd / FeOx catalyst simultaneously detected in Example 3. Detailed Implementation

[0029] Example 1

[0030] A calorimetric and infrared combined device capable of simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions, the device comprising a calorimeter with a measuring channel tube; an infrared light source and an infrared detector are respectively provided at both ends of the calorimeter extending outwards; a sealing gasket 3, a body 1, and a gold-plated infrared reflector 7 are symmetrically arranged sequentially from the inside out on both sides of the calorimeter (only the device on the side near the infrared light source is labeled in the figure, the other side is symmetrically labeled but not specifically drawn); an infrared internal reflection crystal 4 is movably disposed inside the measuring channel tube of the calorimeter; the calorimeter, sealing gasket 3, body 1, infrared internal reflection crystal 4, and gold-plated infrared reflector 7 are fixed by clamps 2 set on the outside; a stainless steel tube-Ⅰ8 with an outwardly extending opening is provided at the weld between the body 1 and the sealing gasket 3 on the infrared detector side; a stainless steel tube-Ⅱ8' with an outwardly extending opening is provided at the weld between the body 1 and the sealing gasket 3 on the infrared light source side.

[0031] The infrared internal reflective crystal 4 has O-rings 5 ​​fitted around its outer sides and the body 1. The gold-plated infrared reflector 7 is located between the infrared light source and the O-rings 5 ​​and between the infrared detector and the O-rings 5, respectively. The device is equipped with a rotating cap 6 that pushes the gold-plated infrared reflector 7 to press the O-rings 5 ​​tightly. The through openings of the sealing gasket 3, the body 1, and the gold-plated infrared reflector 7 are the same as the openings of the calorimeter measuring channel tube. A solid sample film 9 is fixed on the infrared internal reflective crystal 4. The solid sample film 9 is fixed on the infrared internal reflective crystal 4 by deposition.

[0032] The stainless steel tube-Ⅱ8' is connected to the mass spectrometer; the stainless steel tube-Ⅰ8 can introduce gas or liquid molecules, and the stainless steel tube-Ⅱ8' connected to the mass spectrometer can quantify the gas and liquid molecules after interaction.

[0033] The calorimeter is a Sensys calorimeter from Seteram or any other calorimeter with a measuring channel tube design; the infrared internal reflection crystal 4 is cylindrical with 30° to 60° conical surfaces on both sides, and is made of one of ZnSe, Si, and Ge; the gold-plated infrared reflector 7 is hemispherical with a hole drilled at the apex, and the conical surface of the cylindrical infrared internal reflection crystal extends into the hole drilled at the apex of the sphere.

[0034] A method for studying and evaluating the intensity and state of solid-gas or solid-liquid interactions using a combined calorimetric and infrared spectroscopy device.

[0035] (1) Research on the strength and state of solid-gas interactions, specifically including:

[0036] A solid sample film 9 is immobilized on a cylindrical infrared internal reflection crystal 4. The calorimeter is then programmed to reach the desired temperature, and a treatment atmosphere is introduced through stainless steel tube-I8 to treat the solid sample film 9. After treatment, the calorimeter is cooled to the experimental temperature under an inert atmosphere. First, the gas to be studied is switched to the initial mass level in a mass spectrometer. Then, the gas is introduced onto the solid sample through stainless steel tube-I8 to induce a solid-gas interaction. The mass level of the remaining gas after the interaction is quantitatively obtained by the mass spectrometer connected to stainless steel tube-II8'. The interaction strength is measured by the calorimeter, while the interaction state is determined by collecting infrared light through a gold-plated infrared reflector 7. The infrared light reflected by the infrared internal reflection crystal 4 passes through the solid sample film 9 and is ultimately measured by an infrared detector.

[0037] (2) Research on the strength and state of solid-liquid interactions, specifically including:

[0038] A solid sample film 9 is immobilized on a cylindrical infrared internal reflection crystal 4. The calorimeter is then programmed to reach the desired temperature, and a treatment atmosphere is introduced through stainless steel tube-I8 to treat the solid sample film 9. After treatment, the calorimeter is cooled to the experimental temperature under an inert atmosphere. For the liquid sample, inert gas is passed through a bubbler containing the liquid to be studied. At a constant temperature and flow rate, the amount of liquid molecules carried out by the inert gas per unit time can be calculated based on the liquid vapor pressure and the gas flow rate. The inert gas carries the liquid to be tested through stainless steel tube-I8 to the solid sample, causing a solid-liquid interaction. The amount of liquid remaining after the interaction is quantitatively obtained by mass spectrometry connected to stainless steel tube-II8'. The amount of liquid that interacted with the solid can be determined by the decrease in liquid mass before and after the interaction. The strength and state of the solid-liquid interaction can be obtained by combining calorimetry and infrared spectroscopy.

[0039] Preparation of the solid sample film 9: The solid sample is first ground to obtain a powder with a mesh size of 200-800 mesh; then it is dispersed in a solvent to obtain a stable suspension, and the suspension is sprayed onto the middle region of the cylindrical infrared internal reflection crystal 4 and baked by an infrared lamp to form the solid sample film 9.

[0040] The grinding is performed using a ball mill for 3-5 hours; the dispersion is performed using ultrasonic dispersion, with the ultrasonic dispersion solvent including water or ethanol, and the ultrasonic dispersion time is 0.5-1 hour; the suspension is sprayed using a spray gun.

[0041] The method measures the strength and state of the interaction between a gas or liquid and a solid; the gas under study includes one of CO, H2, O2, NH3, etc. The introduced treatment atmosphere is one of H2, O2, He, or Ar; the inert atmosphere is He or Ar.

[0042] The amount of gas or liquid involved in the interaction is obtained by subtracting the amount of gas or liquid after the interaction from the initial mass of the gas or liquid. The amount of substance is quantitatively obtained by mass spectrometry connected to a stainless steel tube-Ⅱ8'.

[0043] Example 2

[0044] The following is a detailed introduction to this device, using a schematic diagram of a calorimetric and infrared spectroscopy device capable of simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions.

[0045] First, the device needs to be fixed to a calorimeter with a measuring channel tube. The device has two bodies 1 (only the side closest to the infrared light source is labeled in the diagram; the other side is symmetrically labeled but not shown). Each body has an opening identical to the calorimeter's measuring channel. The bodies 1 are fixed to both sides of the calorimeter using clamps 2, with a sealing gasket 3 placed in the middle to ensure tight contact between the bodies and the calorimeter, and that the channels are aligned. A cylindrical infrared internal reflection crystal 4 is placed inside the calorimeter's measuring channel tube. O-rings 5 ​​are fitted around the crystal on both sides, and rotating the pressure cap 6 pushes the gold-plated infrared reflector 7 to press the O-rings 5 ​​tightly, thus fixing the infrared internal reflection crystal 4 into the calorimeter's channel. Stainless steel tubes-Ⅰ8 and-Ⅱ8' are welded to the symmetrical sides of the bodies. Gas or liquid molecules can be introduced through stainless steel tube-Ⅰ8, and mass spectrometry is connected through stainless steel tube-Ⅱ8' to quantify the interacting gas and liquid molecules. The solid sample film 9 is deposited onto the infrared internal reflection crystal.

[0046] The infrared internal reflection crystal 4 of the device is cylindrical with 30° to 60° conical surfaces on both sides, and is made of materials such as ZnSe, Si, and Ge. The gold-plated infrared reflector 7 of the device is hemispherical with a hole punched at the apex, into which the conical surface of the cylindrical infrared internal reflection crystal extends to ensure that the reflector reflects infrared light onto the conical surface of the crystal.

[0047] First, the solid sample to be studied is ball-milled for 3-5 hours, and then ultrasonically dispersed in solvents such as water and ethanol for 0.5-1 hours to obtain a stable suspension. Then, the suspension is placed in a spray gun and sprayed onto the middle region of a cylindrical infrared internal reflection crystal 4. The suspension is then baked by an infrared lamp to form a fixed sample film 9.

[0048] Subsequently, the infrared internal reflection crystal 4, which supports the solid sample film 9, is placed into the measuring channel tube of the calorimeter. O-rings 5 ​​are fitted onto the crystal on both sides, and the pressure cap 6 is rotated to push the gold-plated infrared reflector 7 to press the O-rings 5 ​​tightly, thus fixing the infrared internal reflection crystal 4 into the calorimeter channel. Then, a treatment atmosphere (H2, O2, He, Ar, etc.) is introduced through the stainless steel pipe-Ⅰ8, and the calorimeter is controlled to perform programmed temperature rise to pre-treat the solid sample. After treatment, the calorimeter is cooled to the required experimental temperature under an inert atmosphere such as He. After sample treatment, the sample is stabilized at the temperature to be measured for 2-3 hours to allow the calorimeter signal to stabilize.

[0049] To study solid-gas interactions, the gas under investigation (e.g., CO, H2, O2, NH3) is first quantified. The flow rate of the gas is set, and the standard gas is first analyzed by mass spectrometry to obtain the mass spectrometry quantitative correction coefficient. By controlling the gas inlet time through valve switching, pulsed injection can be achieved, and the initial amount of gas can be quantified. The standard gas and He purge gas are connected to the stainless steel pipe-Ⅰ8 of the apparatus via a four-way valve. During measurement, the four-way valve is switched to introduce 5% CO / He standard gas. Gas molecules that do not interact enter the mass spectrometer through the stainless steel pipe-Ⅱ8' for quantification. The initial gas volume minus the amount of uninteracted gas equals the amount of interacting gas. The heat detected by the calorimeter divided by the amount of interacting gas is the differential heat of adsorption (unit: kJ / mol). The interaction state (adsorption state of gas molecules) is obtained by collecting infrared light through a gold-plated infrared reflector 7, reflecting infrared light through an infrared internal reflective crystal 4, passing it through the solid sample film 9, and finally measured by an infrared detector.

[0050] To study the strength and state of solid-liquid interactions, the liquid sample is introduced by passing an inert gas through a bubbler. At a constant temperature and flow rate, the amount of liquid molecules carried out by the inert gas per unit time can be calculated based on the liquid's vapor pressure and the gas flow rate. The inert gas carries the liquid under study through a stainless steel tube (Ⅰ8) onto the solid sample to induce solid-liquid interaction. The amount of liquid interacting with the solid can be determined by the decrease in liquid mass before and after the interaction, based on the quantitative analysis using mass spectrometry.

[0051] As can be seen from this embodiment, the device has the advantages of simple structure, convenient operation, and easy use and maintenance.

[0052] Example 3

[0053] The intensity and state of the interaction between CO and Pd / FeOx catalyst were measured using the calorimetric and infrared spectroscopy device provided by this invention.

[0054] First, the Pd / FeOx catalyst solid powder was ball-milled for 3 hours to obtain an ultrafine powder with a mesh size of 200-800 mesh. Then, 100 mg of catalyst powder was added to 50 mL of ultrapure water at a solid mass to solvent volume ratio of 2 mg / mL, and ultrasonically dispersed for 1 hour to obtain a clear suspension. The clear suspension was placed in a spray gun and sprayed onto the middle part of a cylindrical infrared internal reflection crystal 4. Under infrared lamp irradiation, as the liquid water evaporated, the solid sample was deposited onto the crystal rod. After repeated exposure, a solid sample film 9 was formed on the surface of the infrared internal reflection crystal 4.

[0055] Subsequently, the infrared internal reflection crystal 4, which supports the solid sample film 9, is placed into the measuring channel tube of the calorimeter. O-rings 5 ​​are fitted onto the crystal on both sides, and the pressure cap 6 is rotated to push the gold-plated infrared reflector 7 to press the O-rings 5 ​​tightly, thus fixing the infrared internal reflection crystal 4 into the calorimeter channel. Then, 30 mL / min of high-purity hydrogen is introduced through the stainless steel tube-Ⅰ8, and the calorimeter is programmed to rise to 300℃ to reduce the sample for 1 hour. Afterward, the temperature is switched to high-purity He for purging for half an hour to remove hydrogen adsorbed on the catalyst surface. Finally, the calorimeter is cooled to 30℃ under He atmosphere and stabilized at this temperature for 2-3 hours to allow the calorimeter signal to stabilize.

[0056] The flow rate of the 5% CO / He standard gas to be studied was set to 30 mL / min. First, the standard gas was analyzed by mass spectrometry to obtain its mass spectrometry correction coefficient. The initial amount of gas was quantified using pulse injection. The 5% CO / He standard gas was then introduced through the stainless steel tube-Ⅰ8 via a four-way valve. Gas molecules that did not interact with the standard gas entered the mass spectrometer through the stainless steel tube-Ⅱ8' for quantification. The initial gas volume minus the amount of uninteracted gas yielded the amount of interacting gas. The heat detected by the calorimeter divided by the amount of interacting gas yielded the differential heat of adsorption (unit: kJ / mol). The interaction state (adsorption state of gas molecules) was collected by the gold-plated infrared reflector 7, and the infrared light reflected by the infrared internal reflector crystal 4 passed through the solid sample film 9 and was finally measured by the infrared detector.

[0057] To better describe the interaction process between substances, the experiment involved multiple sample injections. For example... Figure 2 As shown, initially, CO mainly exists in linear adsorption, releasing 85 kJ / mol of heat. With the continuous introduction of CO, bridging adsorption is clearly observed to gradually increase, and the corresponding heat gradually increases. This is mainly because the heat of bridging adsorption is higher than that of linear adsorption (according to...). Figure 2(b) Under evacuation conditions, the linear adsorption peak decreases more significantly, indicating that the heat of linear adsorption is weaker than that of bridged adsorption. Further introduction of CO causes its heat of adsorption to decrease continuously, mainly due to adsorption at weaker linear sites. This unique characteristic of adsorption at weaker linear sites ensures that the catalyst will not inhibit oxygen activation due to strong CO adsorption, thus exhibiting good activity in the CO oxidation reaction.

Claims

1. A combined calorimetric and infrared device capable of simultaneously detecting the strength and state of solid-gas or solid-liquid interaction, characterized in that, include: The device includes a calorimeter with a measuring channel tube; an infrared light source and an infrared detector are respectively provided at both ends of the calorimeter extending outward; a sealing gasket, a body, and a gold-plated infrared reflector are symmetrically arranged through both sides of the calorimeter from the inside to the outside; an infrared internal reflection crystal is movably installed inside the measuring channel tube of the calorimeter; the calorimeter, sealing gasket, body, infrared internal reflection crystal, and gold-plated infrared reflector are fixed by clamps set on the outside; a stainless steel tube-Ⅰ with an outwardly extending opening is provided at the weld between the body and the sealing gasket on the infrared detector side; a stainless steel tube-Ⅱ with an outwardly extending opening is provided at the weld between the body and the sealing gasket on the infrared light source side.

2. The simultaneous detection of solid-gas or solid-liquid interaction strength and state calorimetric and infrared combined device according to claim 1, characterized in that, The infrared internal reflection crystal has O-rings on both sides of its outer periphery and between it and the main body. The gold-plated infrared reflector is located between the infrared light source and the O-rings and between the infrared detector and the O-rings, respectively. The device is equipped with a rotating pressure cap that pushes the gold-plated infrared reflector to press the O-rings tightly. A solid sample film is fixed on the infrared internal reflection crystal. The solid sample film is fixed on the infrared internal reflection crystal by deposition.

3. The simultaneous calorimetric and infrared dual-bathing apparatus for detecting strength and state of solid-gas or solid-liquid interaction according to claim 1, wherein The stainless steel tube-II is connected to the mass spectrometer; the stainless steel tube-I can introduce gas or liquid molecules, and the stainless steel tube-II is connected to the mass spectrometer to quantify the interacting gas and liquid molecules.

4. The calorimetric and infrared spectroscopy device for simultaneously detecting the intensity and state of solid-gas or solid-liquid interactions according to claim 1, characterized in that, The infrared internal reflection crystal is cylindrical, with 30mm diameter fins on both sides. The cone-shaped surface has a ~60° angle and is made of one of ZnSe, Si, and Ge. The gold-plated infrared reflector is hemispherical with a hole drilled at the apex. The cylindrical infrared internal reflection crystal cone extends into the hole at the apex of the sphere.

5. A method for studying and evaluating the intensity and state of solid-gas or solid-liquid interactions using a combined calorimetric and infrared spectroscopy device, characterized in that... 1) Research on the strength and state of solid-gas interactions, specifically including: A solid sample film was immobilized on a cylindrical infrared internal reflection crystal. The calorimeter was then programmed to reach the desired temperature, and a treatment atmosphere was introduced through stainless steel tube I to treat the solid sample film. After treatment, the calorimeter was cooled to the experimental temperature under an inert atmosphere. First, the gas to be studied was switched to a mass spectrometer to quantify the initial amount. Then, the gas was introduced onto the solid sample through stainless steel tube I to induce a solid-gas interaction. The amount of the remaining gas after the interaction was quantified by the mass spectrometer connected to stainless steel tube II. The interaction intensity was measured by the calorimeter, while the interaction state was determined by collecting infrared light through a gold-plated infrared reflector. The infrared light reflected by the infrared internal reflection crystal passed through the solid sample film and was finally measured by an infrared detector. 2) Research on the strength and state of solid-liquid interactions, specifically including: A solid sample film is immobilized on a cylindrical infrared internal reflection crystal. The calorimeter is then programmed to reach the desired temperature, and a treatment atmosphere is introduced through stainless steel tube-I to treat the solid sample film. After treatment, the calorimeter is cooled to the experimental temperature under an inert atmosphere. For liquid sample introduction, inert gas is passed into a bubbler containing the liquid to be studied. At a constant temperature and flow rate, the amount of liquid molecules carried out by the inert gas per unit time can be calculated based on the liquid vapor pressure and gas flow rate. The inert gas carries the liquid to be tested through stainless steel tube-I to the solid sample, causing a solid-liquid interaction. The amount of liquid remaining after the interaction is quantitatively obtained by mass spectrometry connected to stainless steel tube-II. The amount of liquid interacting with the solid can be determined by the decrease in liquid mass before and after the interaction, while the strength and state of the solid-liquid interaction can be obtained by combining calorimetry and infrared spectroscopy. The calorimetric and infrared combined device is the device described in any one of claims 1 to 4.

6. The method of claim 5, wherein, Preparation of the solid sample film: The solid sample is first ground to obtain a powder with a mesh size of 200~800 mesh; then it is dispersed in a solvent to obtain a stable suspension, and the suspension is sprayed onto the middle region of a cylindrical infrared internal reflection crystal and baked with an infrared lamp to form a solid sample film.

7. The method according to claim 6, characterized in that, The grinding is performed using a ball mill for 3-5 hours; the dispersion is performed using ultrasonic dispersion, with the ultrasonic dispersion solvent including water or ethanol, and the ultrasonic dispersion time is 0.5-1 hour; the suspension is sprayed using a spray gun.

8. The method of claim 5, wherein, The method measures the intensity and state of the interaction between a gas or liquid and a solid, wherein the gas under study is one of CO, H2, O2, and NH3.

9. The method of claim 5, wherein, The introduced treatment atmosphere is one of H2, O2, He or Ar; the inert atmosphere is He or Ar.

10. The method of claim 5, wherein, The amount of gas or liquid involved in the interaction is obtained by subtracting the amount of gas or liquid after the interaction from the initial mass of the gas or liquid. The amount of substance is quantitatively obtained by mass spectrometry connected to a stainless steel tube-II.

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