技术领域technical field
本发明涉及一种机理研究的方法，特别是涉及一种气相光催化机理研究的装置和方法。The invention relates to a method for mechanism research, in particular to a device and method for gas phase photocatalytic mechanism research.
背景技术Background technique
近年来，二氧化碳的催化转化、甲烷氧化、一氧化碳加氢、甲醇氧化等研究引起了人们的广泛关注。在众多转化方法中，光催化还原能够利用自然界的太阳光实时直接转化，生成高附加值的化学品，且操作过程简单、无二次污染、稳定性好，因此具有较好的研究意义和发展前景。然而，目前对于上述反应的机理和过程研究还不深入，也没有达成统一明确的认识，且光催化过程较复杂，给机理研究增加了困难。In recent years, studies on the catalytic conversion of carbon dioxide, methane oxidation, carbon monoxide hydrogenation, and methanol oxidation have attracted widespread attention. Among many conversion methods, photocatalytic reduction can use natural sunlight to directly convert in real time to generate high value-added chemicals, and the operation process is simple, no secondary pollution, and good stability, so it has good research significance and development. prospect. However, the research on the mechanism and process of the above reactions is still not in-depth, and a unified and clear understanding has not been reached, and the photocatalytic process is more complicated, which adds difficulties to the mechanism research.
红外光谱技术是光催化研究中最常用和最有效的手段之一，它是分子吸收光谱中的一种，可以根据分子的特征震动和转动所导致的红外光吸收而进行定性或定量分析。当有红外光照射时，分子中某个基团的振动频率或转动频率和红外光的频率一样时，分子中的化学键或官能团会发生振动吸收，不同的化学键或官能团吸收频率是不同的，因此会处于红外光谱的不同位置，从光谱结果可获得分子中含有的化学键或官能团信息。由于红外光谱能够对催化剂自身以及催化剂表面吸附物种进行探测，常被用于多相催化研究中来分析催化剂的表面组成、活性位点等表面信息。Infrared spectroscopy is one of the most commonly used and effective means in photocatalysis research. It is a kind of molecular absorption spectrum, which can be used for qualitative or quantitative analysis according to the infrared light absorption caused by the characteristic vibration and rotation of molecules. When irradiated by infrared light, when the vibration frequency or rotation frequency of a certain group in the molecule is the same as the frequency of infrared light, the chemical bond or functional group in the molecule will undergo vibrational absorption. Different chemical bonds or functional groups have different absorption frequencies, so It will be in different positions of the infrared spectrum, and the chemical bond or functional group information contained in the molecule can be obtained from the spectral results. Because infrared spectroscopy can detect the catalyst itself and the species adsorbed on the surface of the catalyst, it is often used in the research of heterogeneous catalysis to analyze the surface information of the catalyst such as surface composition and active sites.
发明内容Contents of the invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种气相光催化机理研究的装置和方法，用于解决现有技术中气相光催化机理研究不够透彻及研究方法不完善的问题。In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a device and method for studying the mechanism of gas-phase photocatalysis, which is used to solve the problems in the prior art that the research on the mechanism of gas-phase photocatalysis is not thorough enough and the research method is not perfect.
为实现上述目的及其他相关目的，本发明是通过以下技术方案获得的。In order to achieve the above purpose and other related purposes, the present invention is achieved through the following technical solutions.
本发明公开了一种气相光催化机理研究的装置，所述装置包括红外光谱仪、进气通路、出气通路和光照灯；所述红外近红外光谱仪包括用于承载催化剂和/或反应气体的样品池，所述进气通路的一端与反应气体气路连通，所述进气通路的另一端与所述样品池气路连通；所述出气通路的一端与所述样品池气路连通；所述样品池上设有用于使得光照灯的光线通过的透明玻璃窗口。The invention discloses a device for studying the mechanism of gas phase photocatalysis. The device includes an infrared spectrometer, an air inlet passage, an air outlet passage and a lighting lamp; the infrared near infrared spectrometer includes a sample pool for carrying catalyst and/or reaction gas , one end of the air inlet passage communicates with the reaction gas passage, the other end of the inlet passage communicates with the sample cell air passage; one end of the gas outlet passage communicates with the sample chamber air passage; the sample The pool is provided with a transparent glass window for the light of the illumination lamp to pass through.
优选地，所述装置还包括惰性气体通路，所述惰性气体通路与所述出气通路的气体连通。Preferably, the device further includes an inert gas passage, and the inert gas passage is in gas communication with the gas outlet passage.
优选地，所述惰性气体通路上设有开关阀。Preferably, an on-off valve is provided on the inert gas passage.
优选地，所述惰性气体通路上设有流量计。Preferably, a flow meter is provided on the inert gas passage.
优选地，所述装置还包括水浴部件，所述样品池设于所述水浴部件提供的水浴环境中。Preferably, the device further includes a water bath component, and the sample pool is provided in a water bath environment provided by the water bath component.
优选地，所述装置还包括加热部件，所述加热部件用于加热所述样品池。Preferably, the device further includes a heating component for heating the sample cell.
优选地，所述装置还包括尾气吸收部件，所述出气通路的另一端与尾气吸收部件气体连通。所述尾气吸收部件用于吸收反应的尾气。Preferably, the device further includes an exhaust gas absorbing component, and the other end of the outlet passage is gas-communicated with the exhaust gas absorbing component. The tail gas absorbing part is used to absorb reaction tail gas.
优选地，所述进气通路上设有开关阀。Preferably, an on-off valve is provided on the intake passage.
优选地，所述进气通路上还设有流量计。Preferably, a flow meter is also provided on the intake passage.
优选地，所述透明玻璃窗口上的窗片材质为氯化钠、溴化钾、氟化钡或硒化锌中的一种。Preferably, the material of the window sheet on the transparent glass window is one of sodium chloride, potassium bromide, barium fluoride or zinc selenide.
本发明还公开了一种气相光催化机理研究的方法，所述方法是采用如上述所述的装置，在光照灯的光照射和催化剂的催化条件下，通过红外光谱仪实时监测扫描反应池中反应气体在催化剂表面反应产生的反应产物的谱图。The invention also discloses a method for studying the mechanism of gas-phase photocatalysis. The method is to use the above-mentioned device to monitor the reaction in the scanning reaction pool in real time through an infrared spectrometer under the conditions of light irradiation of the illumination lamp and the catalysis of the catalyst. Spectrum of reaction products produced by gases reacting on the surface of a catalyst.
优选地，所述红外光谱仪为漫反射红外光谱仪。Preferably, the infrared spectrometer is a diffuse reflectance infrared spectrometer.
优选地，所述方法包括如下特征中的一种或多种：Preferably, the method includes one or more of the following features:
所述的催化剂为二氧化钛与分子筛的混合物；Described catalyst is the mixture of titanium dioxide and molecular sieve;
所述的二氧化钛与所述分子筛的质量比为0.1～1。The mass ratio of the titanium dioxide to the molecular sieve is 0.1-1.
优选地，所述分子筛为选自ETS-10、ZSM-5和MCM-68中的一种或多种。Preferably, the molecular sieve is one or more selected from ETS-10, ZSM-5 and MCM-68.
优选地，所述的光照灯为氙灯。Preferably, the illumination lamp is a xenon lamp.
优选地，所述的反应气体为负载有水蒸气的一氧化碳、负载有水蒸气的甲烷、惰性气体负载的甲醇和负载有水蒸气的二氧化碳中的一种。Preferably, the reaction gas is one of carbon monoxide loaded with water vapor, methane loaded with water vapor, methanol loaded with inert gas and carbon dioxide loaded with water vapor.
更优选地，所述负载有水蒸气的一氧化碳是采用一氧化碳气体进入水后逸出形成。More preferably, the carbon monoxide loaded with water vapor is formed by the escape of carbon monoxide gas after entering the water.
更优选地，所述负载有水蒸气的甲烷是采用甲烷气体进入水后逸出形成。More preferably, the methane loaded with water vapor is formed by methane gas entering water and then escaping.
更优选地，所述惰性气体负载的甲醇是采用惰性气体进入甲醇后逸出形成。More preferably, the inert gas-supported methanol is formed by using an inert gas to enter the methanol and then escape.
更优选地，负载有水蒸气的二氧化碳是采用二氧化碳气体进入水后逸出形成。More preferably, the carbon dioxide loaded with water vapor is formed using carbon dioxide gas entering the water and then escaping.
优选地，所述的方法包括如下特征中的一种或多种：Preferably, the method includes one or more of the following features:
反应的温度为25～80℃；The temperature of reaction is 25～80 ℃;
反应气体的气流流速为1～30ml/min；The gas flow rate of the reaction gas is 1-30ml/min;
光照灯的光照时间为5～20min。The illumination time of the illumination lamp is 5-20 minutes.
优选地，所述方法包括如下特征中的一种或多种：Preferably, the method includes one or more of the following features:
所述方法还包括在反应前先采用惰性气体进入进气通道对气路进行除杂的步骤；The method also includes the step of using an inert gas to enter the intake channel to remove impurities from the gas path before the reaction;
对气路进行除杂时，还包括加热所述样品池至100℃～300℃；还包括除杂完成后降温的步骤；降温采用液氮辅助降温；When removing impurities from the gas path, it also includes heating the sample pool to 100°C to 300°C; it also includes a step of cooling after the removal of impurities; the cooling is assisted by liquid nitrogen;
所述方法还包括除杂后通入惰性气体采集背景红外光谱的步骤；The method also includes the step of introducing an inert gas to collect a background infrared spectrum after removing impurities;
所述方法还包括扣除背景红外光谱图获得通入惰性气体时的原位红外谱图的步骤；The method also includes the step of subtracting the background infrared spectrum to obtain the in-situ infrared spectrum when the inert gas is introduced;
所述方法还包括通入反应气体，收集其原位红外光谱图的步骤；The method also includes the step of introducing reaction gas and collecting its in-situ infrared spectrogram;
所述方法还包括关掉反应气体，用通入惰性气体，收集原位红外谱图的步骤；The method also includes the steps of turning off the reaction gas and feeding in an inert gas to collect in-situ infrared spectra;
所述方法还包括关掉惰性气体和反应气体，光照并收集光照反应后原位红外谱图的步骤。The method also includes the steps of turning off the inert gas and the reaction gas, illuminating and collecting the in-situ infrared spectrogram after the illuminating reaction.
优选地，所述方法还包括在反应前采用水浴部件将样品池置于水浴环境中用于检测样品池的气密性。Preferably, the method further includes using a water bath component to place the sample pool in a water bath environment for testing the airtightness of the sample pool before the reaction.
优选地，所述惰性气体为氦气、氮气和氩气中的一种或多种。Preferably, the inert gas is one or more of helium, nitrogen and argon.
本发明技术方案主要有以下技术效果：The technical solution of the present invention mainly has the following technical effects:
本发明提供的一种原位红外技术用于气相光催化机理研究的方法，适用于几乎所有的粉末样品，操作过程简单，对样品的损坏率小，且样品可回收利用，极大降低了污染。该方法应用于二氧化碳还原、甲烷氧化、一氧化碳加氢、甲醇氧化等气相光催化反应中，能够对反应条件下的吸附物种和中间体进行原位动态跟踪，直观看出光照后中间物种的变化情况，通过谱图结果中峰的归属，能够给机理研究提供依据。此外，该方法也可用于其他物质的光催化反应，对于解决现有机理研究困难问题，以及未来的发展方向具有指导意义。The method provided by the present invention for the study of gas phase photocatalytic mechanism by in-situ infrared technology is suitable for almost all powder samples, the operation process is simple, the damage rate to the sample is small, and the sample can be recycled, which greatly reduces the pollution . This method is applied to gas-phase photocatalytic reactions such as carbon dioxide reduction, methane oxidation, carbon monoxide hydrogenation, and methanol oxidation. It can dynamically track the adsorbed species and intermediates under the reaction conditions in situ, and intuitively see the changes of intermediate species after illumination. , through the assignment of peaks in the spectrum results, it can provide a basis for mechanism research. In addition, this method can also be used for the photocatalytic reaction of other substances, which has guiding significance for solving the difficult problems of existing mechanism research and the future development direction.
附图说明Description of drawings
图1显示为本发明中的气相光催化机理研究的装置的结构示意图。FIG. 1 shows a schematic structural diagram of a device for gas-phase photocatalytic mechanism research in the present invention.
图1中元件标号说明Description of component numbers in Figure 1
1红外光谱仪1 infrared spectrometer
2进气通路2 intake passages
3出气通路3 outlet channels
4光照灯4 lights
5惰性气体通路5 inert gas passage
6尾气吸收部件6 Exhaust gas absorption parts
图2显示为本申请实施例3中实验过程中获得的原位红外谱图。Figure 2 shows the in-situ infrared spectrum obtained during the experiment in Example 3 of the present application.
图3显示为本申请实施例7中实验过程中获得的原位红外谱图。Figure 3 shows the in-situ infrared spectrum obtained during the experiment in Example 7 of the present application.
具体实施方式Detailed ways
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The implementation of the present invention will be illustrated by specific specific examples below, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.
在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围。下列实施例中未注明具体条件的试验方法，通常按照常规条件，或者按照各制造商所建议的条件。Before further describing the specific embodiments of the present invention, it should be understood that the protection scope of the present invention is not limited to the following specific specific embodiments; it should also be understood that the terms used in the examples of the present invention are to describe specific specific embodiments, It is not intended to limit the protection scope of the present invention. The test methods for which specific conditions are not indicated in the following examples are usually in accordance with conventional conditions, or in accordance with the conditions suggested by each manufacturer.
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。When the examples give numerical ranges, it should be understood that, unless otherwise stated in the present invention, the two endpoints of each numerical range and any value between the two endpoints can be selected. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to those skilled in the art's grasp of the prior art and the description of the present invention, the methods, equipment, and materials described in the embodiments of the present invention can also be used Any methods, apparatus and materials of the prior art similar or equivalent to the practice of the present invention.
实施例1Example 1
本申请中具体公开了气相光催化机理研究的装置，具体如图1所示，所述装置包括红外光谱仪1、进气通路2、出气通路3和光照灯4；所述红外近红外光谱仪1包括用于承载催化剂和/或反应气体的样品池，所述进气通路2的一端与原料反应气气路连通，所述进气通路2的另一端与所述样品池气路连通；所述出气通路3的一端与所述样品池气路连通；所述样品池上设有用于使得光照灯4的光线通过的透明玻璃窗口。The application specifically discloses a device for gas phase photocatalytic mechanism research, specifically as shown in Figure 1, the device includes an infrared spectrometer 1, an air intake passage 2, an air outlet passage 3 and an illumination lamp 4; the infrared near-infrared spectrometer 1 includes A sample cell for carrying catalyst and/or reaction gas, one end of the inlet passage 2 communicates with the gas path of the raw material reaction gas, and the other end of the inlet passage 2 communicates with the gas path of the sample cell; the gas outlet One end of the channel 3 communicates with the air path of the sample cell; the sample cell is provided with a transparent glass window for allowing the light of the illuminating lamp 4 to pass through.
如图1所示，在一个具体的实施例中，所述装置还包括惰性气体通路5，所述惰性气体通路5与所述出气通路的气体连通。As shown in FIG. 1 , in a specific embodiment, the device further includes an inert gas passage 5 , and the inert gas passage 5 communicates with the gas of the gas outlet passage.
在一个具体的实施例中，所述惰性气体通路5上设有开关阀。In a specific embodiment, an on-off valve is provided on the inert gas passage 5 .
在一个具体的实施例中，所述惰性气体通路5上设有流量计。In a specific embodiment, a flow meter is provided on the inert gas passage 5 .
在一个具体的实施例中，所述装置还包括水浴部件，所述样品池设于所述水浴部件提供的水浴环境中。In a specific embodiment, the device further includes a water bath component, and the sample pool is arranged in a water bath environment provided by the water bath component.
在一个具体的实施例中，所述装置还包括加热部件，所述加热部件用于加热所述样品池。In a specific embodiment, the device further includes a heating component for heating the sample cell.
如图1所示，在一个具体的实施例中，所述装置还包括尾气吸收部件6所述出气通路3的另一端与尾气吸收部件6体连通。As shown in FIG. 1 , in a specific embodiment, the device further includes an exhaust gas absorbing component 6 , and the other end of the outlet passage 3 communicates with the exhaust gas absorbing component 6 .
如图1所示，在一个具体的实施例中，所述进气通路2设有开关阀。As shown in FIG. 1 , in a specific embodiment, the intake passage 2 is provided with an on-off valve.
如图1所示，在一个具体的实施例中，所述进气通路2设有流量计。As shown in FIG. 1 , in a specific embodiment, the air intake passage 2 is provided with a flow meter.
在一个更具体的实施例中，如图1所示，所述进气通路2上设有供所述进气通路2中的气体进入并逸出的溶液容器。如所述惰性气体负载的甲醇是采用惰性气体进入甲醇后逸出形成；负载有水蒸气的二氧化碳是采用二氧化碳气体进入水后逸出形成等；用于使得光催化反应能够顺利进行。In a more specific embodiment, as shown in FIG. 1 , the air intake passage 2 is provided with a solution container for the gas in the air intake passage 2 to enter and escape. For example, the methanol supported by the inert gas is formed by the inert gas entering the methanol and escaping; the carbon dioxide loaded with water vapor is formed by escaping after the carbon dioxide gas enters the water; it is used to make the photocatalytic reaction go smoothly.
实施例2Example 2
将制备好的二氧化钛与分子筛的复合比为0.1的催化剂放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时；以作为本实施例中的催化剂粉末。所述分子筛为ETS-10。The prepared catalyst with a composite ratio of titanium dioxide and molecular sieve of 0.1 was put into a mortar, ground evenly, and then dried in an oven at 50°C for 2 hours; it was used as the catalyst powder in this example. The molecular sieve is ETS-10.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和反应气气路；取下红外光谱仪的样品池，将干燥后的催化剂粉末填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and reaction gas path; remove the sample cell of the infrared spectrometer, fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴环境中用于检测样品池及气体通路的气密性，水浴部件可以为循环水仪。Then the sample cell is placed in a water bath environment for testing the airtightness of the sample cell and the gas passage, and the water bath part can be a circulating water instrument.
待装置不漏水后，在通氦气条件下，按照5℃/min程序升温至100℃，在该温度下保温0.5小时，再降温至80℃，降温时采用液氮对样品池进行降温处理。此步骤为前处理步骤，用于去除气路中的杂质气体，加温有利于气路中杂质气体的去除。After the device is leak-proof, under the condition of helium gas, the temperature is raised to 100°C according to the 5°C/min program, kept at this temperature for 0.5 hours, and then cooled to 80°C, and liquid nitrogen is used to cool the sample cell during cooling. This step is a pretreatment step for removing impurity gases in the gas path, and heating is beneficial to the removal of impurity gases in the gas path.
在1ml/min的流速控制下，通入He，采集背景红外光谱谱图；在扣除背景红外光谱谱图后，获得通He氛围下原位红外光谱谱图；关闭He，再通入水蒸气饱和的CO2，收集其原位红外光谱谱图；然后关水蒸气饱和的CO2，改为He吹扫5min，收集原位红外谱图；再关闭He和水蒸气饱和的CO2，开始光照，光照5min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，进而探究相应的光催化机理。Under the control of the flow rate of 1ml/min, He was introduced to collect the background infrared spectrum; after subtracting the background infrared spectrum, the in-situ infrared spectrum was obtained under the He atmosphere; the He was closed, and then the water vapor saturated CO2 , collect its in-situ infrared spectrum; then turn off the water vapor-saturated CO2 , change to He purging for 5 minutes, and collect the in-situ infrared spectrum; then turn off He and water vapor-saturated CO2 , start to illuminate, light After 5 minutes, the light source was turned off, and the in-situ infrared spectrum results after the photoreaction were collected. The obtained spectrum results were divided into peaks, and the peak changes before and after the light reaction were observed, so as to explore the corresponding photocatalytic mechanism.
本实施例中所述水蒸气饱和的CO2即为负载有水蒸气的二氧化碳，其是采用二氧化碳气体进入水后逸出形成的。The water vapor-saturated CO2 described in this embodiment is carbon dioxide loaded with water vapor, which is formed by the escape of carbon dioxide gas after entering water.
实施例3Example 3
将制备好的二氧化钛与分子筛的复合比为1的催化剂放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时，以此作为本实施例中的催化剂粉末。所述分子筛为ETS-10。The prepared catalyst with a composite ratio of titanium dioxide and molecular sieve of 1 was put into a mortar, ground evenly, and then dried in an oven at 50° C. for 2 hours, which was used as the catalyst powder in this example. The molecular sieve is ETS-10.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和二氧化碳气路；取下红外样品池，将干燥后的催化剂粉末填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and carbon dioxide gas lines; remove the infrared sample cell, fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴环境中用于检测样品池及气体通路的气密性，水浴部件可以为循环水仪，所述循环水仪提供水浴环境，并且水浴为由循环水提供。循环水的供给用于给所述样品池提供恒定的温度。Then the sample cell is placed in a water bath environment for testing the airtightness of the sample cell and the gas passage, and the water bath part can be a circulating water instrument, which provides a water bath environment, and the water bath is provided by circulating water. A supply of circulating water was used to provide a constant temperature to the sample cell.
待装置不漏水后，在通氦气条件下，按照20℃/min程序升温至300℃，在该温度下保温3小时，再降温至25℃，降温时采用液氮对样品池进行降温处理。此步骤采用惰性气体先去除气路中的杂质气体，加温有利于气路中杂质及气体的去除。加温升温控制可以由气相光催化机理研究的装置中的加热部件来控制。After the device is leak-free, the temperature is raised to 300°C according to the program of 20°C/min under the condition of helium gas, kept at this temperature for 3 hours, and then lowered to 25°C, and liquid nitrogen is used to cool the sample cell during cooling. In this step, the inert gas is used to remove the impurity gas in the gas path first, and heating is beneficial to the removal of impurities and gas in the gas path. The heating and heating control can be controlled by the heating components in the device for gas-phase photocatalytic mechanism research.
在30ml/min的流速控制下，通入He，采集背景红外光谱谱图；在扣除背景红外光谱谱图后，获得通He氛围下原位红外谱图；关闭He，再通入水蒸气饱和的CO2，收集其原位红外谱图；然后关水蒸气饱和的CO2，改为He吹扫5min，收集原位红外谱图；再关闭He和水蒸气饱和的CO2，开始光照，光照20min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，进而探究相应的光催化机理。Under the control of the flow rate of 30ml/min, He was introduced to collect the background infrared spectrum; after subtracting the background infrared spectrum, the in-situ infrared spectrum was obtained under the He atmosphere; the He was closed, and then the water vapor saturated CO2 , collect its in-situ infrared spectrum; then turn off the water vapor-saturated CO2 , change to He purging for 5 minutes, and collect the in-situ infrared spectrum; then turn off He and water vapor-saturated CO2 , start to illuminate, and after 20 minutes of illumination Turn off the light source, and collect the results of the in-situ infrared spectrum after the photoreaction. The obtained spectrum results were divided into peaks, and the peak changes before and after the light reaction were observed, so as to explore the corresponding photocatalytic mechanism.
本实施例中所述水蒸气饱和的CO2即为负载有水蒸气的二氧化碳，其是采用二氧化碳气体进入水后逸出形成的。The water vapor-saturated CO2 described in this embodiment is carbon dioxide loaded with water vapor, which is formed by the escape of carbon dioxide gas after entering water.
本实施例中采用溴化钾粉末代替催化剂填充入所述反应池中，其他不变用于作为空白对照试验，以说明本申请中红外谱图的变化反应出的产物的变化是由于催化剂的添加形成的。In this embodiment, potassium bromide powder is used instead of catalyst to fill in the reaction cell, and other changes are used as a blank control test to illustrate that the change in the product reflected by the change in the infrared spectrogram in this application is due to the addition of the catalyst Forming.
具体原位红外谱图如图2所示，其中，1阶段为扣除背景后，通He条件下原位红外谱图；2阶段为通水蒸气饱和的二氧化碳条件下原位红外谱图；3阶段为He吹扫条件下原位红外谱图；4阶段为光照反应后原位红外谱图。The specific in-situ infrared spectrum is shown in Figure 2, wherein, the first stage is the in-situ infrared spectrum under the condition of He after deducting the background; the second stage is the in-situ infrared spectrum under the condition of passing water vapor saturated carbon dioxide; the third stage In situ infrared spectrum under He purging condition; stage 4 is in situ infrared spectrum after light reaction.
由图2可以看出：图中存在二氧化碳的吸附峰，和O-H、C-H、C＝O的伸缩振动峰，其中C＝O为生成乙醇的重要中间体CHO的特征峰，与我们的光催化反应相对应，为反应机理探究提供了依据。It can be seen from Figure 2 that there are adsorption peaks of carbon dioxide in the figure, and stretching vibration peaks of O-H, C-H, and C=O, among which C=O is the characteristic peak of CHO, an important intermediate for generating ethanol, which is compatible with our photocatalytic reaction Correspondingly, it provides a basis for exploring the reaction mechanism.
实施例4Example 4
将制备好的二氧化钛与分子筛的复合比为0.5的催化剂放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时；以作为本实施例中的催化剂粉末。所述分子筛为ZSM-5。The prepared catalyst with a composite ratio of titanium dioxide and molecular sieve of 0.5 was put into a mortar, ground evenly, and then dried in an oven at 50°C for 2 hours; it was used as the catalyst powder in this example. The molecular sieve is ZSM-5.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和一氧化碳气路；取下红外样品池，将干燥后的催化剂粉末小心填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and carbon monoxide gas lines; remove the infrared sample cell, carefully fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴部件的水浴环境中以检验样品池以及气体通路的气密性。Then place the sample cell in the water bath environment of the water bath part to test the airtightness of the sample cell and the gas passage.
待装置不漏水后，在通氦气条件下，按照10℃/min程序升温至200℃，在该温度下保温2小时，再降温至60℃。降温时采用液氮对样品池进行降温处理。此步骤采用惰性气体去除气路中的杂质气体，加温有利于气路中杂质及气体的完全去除。加温升温控制可以由气相光催化机理研究的装置中的加热部件来控制。After the device is watertight, under the condition of helium gas, the temperature is raised to 200°C according to the program of 10°C/min, kept at this temperature for 2 hours, and then cooled to 60°C. Liquid nitrogen was used to cool down the sample cell during cooling. In this step, inert gas is used to remove impurity gases in the gas path, and heating is conducive to the complete removal of impurities and gases in the gas path. The heating and heating control can be controlled by the heating components in the device for gas-phase photocatalytic mechanism research.
在5ml/min的流速控制下，通入He，采集背景红外光谱谱图；在扣除背景谱图后，获得通He氛围下原位红外谱图；关闭He，再通入水蒸气饱和的CO，收集其原位红外谱图；然后关水蒸气饱和的CO，改为He吹扫5min，收集原位红外谱图；再关闭He和水蒸气饱和的CO，开始光照，光照10min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，进而探究相应的光催化一氧化碳加氢机理。Under the control of the flow rate of 5ml/min, He was introduced to collect the background infrared spectrum; Its in-situ infrared spectrum; then turn off the water vapor-saturated CO, change to He purging for 5 minutes, and collect the in-situ infrared spectrum; then turn off the He and water vapor-saturated CO, start the light, turn off the light source after 10 minutes of light, and collect the light In situ infrared spectrum results after the reaction. The obtained spectral results were assigned to peaks, and the peak changes before and after the light reaction were observed, so as to explore the corresponding photocatalytic carbon monoxide hydrogenation mechanism.
本申请中的水蒸气饱和的CO是采用CO气体通入水后逸出形成的。The water vapor-saturated CO in this application is formed by passing CO gas into water and then escaping.
实施例5Example 5
将制备好的二氧化钛与分子筛的复合比为0.3的催化剂放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时，以作为本实施例中的催化剂粉末。所述分子筛为MCM-68。The prepared catalyst with a composite ratio of titanium dioxide and molecular sieve of 0.3 was put into a mortar, ground evenly, and then dried in an oven at 50° C. for 2 hours to serve as the catalyst powder in this example. The molecular sieve is MCM-68.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和甲烷气路；取下红外样品池，将干燥后的催化剂粉末小心填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and methane gas lines; remove the infrared sample cell, carefully fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴部件的水浴环境中以检查样品池及气体通路的气密性。Then place the sample cell in the water bath environment of the water bath part to check the airtightness of the sample cell and gas passage.
待装置不漏水即气密性良好后，在通氦气条件下，按照5℃/min程序升温至300℃，在该温度下保温2小时，再降温至50℃，降温时采用液氮对样品池进行降温处理。此步骤采用惰性气体先去除气路中的杂质气体，加温有利于气路中杂质及气体的去除。加温升温及其控制可以由装置中的加热部件处理。After the device does not leak water, that is, the airtightness is good, under the condition of helium gas, the temperature is raised to 300°C according to the 5°C/min program, kept at this temperature for 2 hours, and then cooled to 50°C, and the sample is cooled with liquid nitrogen. The pool is cooled. In this step, the inert gas is used to remove the impurity gas in the gas path first, and heating is beneficial to the removal of impurities and gas in the gas path. Heating The temperature rise and its control can be handled by heating components in the device.
在5ml/min的流速控制下，通入He，采集背景红外谱图；在扣除背景红外谱图后，获得通He氛围下原位红外谱图；关闭He，再通入水蒸气饱和的甲烷，收集其原位红外谱图；然后关水蒸气饱和的甲烷，改为He吹扫5min，收集原位红外谱图；再关闭He和水蒸气饱和的甲烷，开始光照，光照5min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，进而探究相应的光催化甲烷氧化机理。Under the control of the flow rate of 5ml/min, He was fed to collect the background infrared spectrum; Its in-situ infrared spectrum; then turn off the water vapor-saturated methane, change to He purging for 5 minutes, and collect the in-situ infrared spectrum; then turn off He and water vapor-saturated methane, start the light, turn off the light source after 5 minutes of light, and collect the light In situ infrared spectrum results after the reaction. The obtained spectral results were assigned to the peaks, and the peak changes before and after the light reaction were observed to explore the corresponding photocatalytic methane oxidation mechanism.
本实施例中，所述水蒸气饱和的甲烷是采用甲烷气体进入水中后逸出形成的。In this embodiment, the water vapor-saturated methane is formed by escaping after methane gas enters the water.
实施例6Example 6
将制备好的二氧化钛与分子筛的复合比为0.7的催化剂放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时，以作为本实施例中的催化剂粉末。所述分子筛为ZSM-5。The prepared catalyst with a composite ratio of titanium dioxide and molecular sieve of 0.7 was put into a mortar, ground evenly, and then dried in an oven at 50° C. for 2 hours to serve as the catalyst powder in this example. The molecular sieve is ZSM-5.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和氮气气路；取下红外样品池，将干燥后的催化剂粉末小心填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and nitrogen gas lines; remove the infrared sample cell, carefully fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴环境中用于检测样品池及气体通络的气密性。Then the sample cell is placed in a water bath environment to test the airtightness of the sample cell and the gas channel.
待装置不漏水后，进行样品前处理，即在通氦气条件下，按照5℃/min程序升温至200℃，在该温度下保温2小时，再降温至50℃，前处理完成。After the device is leak-free, the sample pretreatment is carried out, that is, under the condition of helium, the temperature is raised to 200°C according to the 5°C/min program, kept at this temperature for 2 hours, and then cooled to 50°C, and the pretreatment is completed.
在10ml/min的流速控制下，通入He，收集背景红外光谱谱图；在扣除背景谱图后，获得通He氛围下原位红外谱图；关闭He，再通入甲醇、水蒸气饱和的氮气，收集其原位红外谱图；然后关甲醇、水蒸气饱和的氮气，改为He吹扫5min，收集原位红外谱图；再关闭He和甲醇、水蒸气饱和的氮气，开始光照，光照10min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，进而探究相应的光催化甲醇氧化机理。Under the control of the flow rate of 10ml/min, He was introduced to collect the background infrared spectrum; after subtracting the background spectrum, the in-situ infrared spectrum was obtained under the He atmosphere; the He was closed, and then methanol, water vapor saturated Nitrogen, collect its in-situ infrared spectrum; then turn off methanol, water vapor-saturated nitrogen, change to He purge for 5min, collect in-situ infrared spectrum; then turn off He, methanol, water vapor-saturated nitrogen, start to illuminate, light After 10 minutes, the light source was turned off, and the in-situ infrared spectrum results after the photoreaction were collected. The spectrum results were divided into peaks, and the peak changes before and after the light reaction were observed, so as to explore the corresponding photocatalytic methanol oxidation mechanism.
本申请中所述甲醇、水蒸气饱和的氮气是由氮气进入甲醇水溶液中逸出后形成的。The nitrogen gas saturated with methanol and water vapor mentioned in this application is formed after the nitrogen gas enters the aqueous methanol solution and escapes.
实施例7Example 7
将制备好的单一二氧化钛放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时，以作为本实施例中的催化剂。分子筛为选自ETS-10。Put the prepared single titanium dioxide into a mortar, grind it evenly, and put it into an oven at 50° C. for 2 hours to be used as the catalyst in this example. The molecular sieve is selected from ETS-10.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和二氧化碳气路；取下红外样品池，将干燥后的催化剂粉末小心填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and carbon dioxide gas lines; remove the infrared sample cell, carefully fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴环境中用于检测样品池及气体通路的气密性。Then the sample cell is placed in a water bath environment to test the airtightness of the sample cell and the gas passage.
待装置不漏水后，在通氦气条件下，按照5℃/min程序升温至200℃，在该温度下保温2小时，再降温至50℃，降温时采用液氮对样品池进行降温处理。此步骤为前处理步骤，用于去除气路中的杂质气体，加温有利于气路中杂质及气体的完全去除。After the device is leak-free, the temperature is raised to 200°C according to the program of 5°C/min under the condition of helium gas, kept at this temperature for 2 hours, and then cooled to 50°C, and liquid nitrogen is used to cool the sample cell during cooling. This step is a pretreatment step, used to remove impurity gases in the gas path, and heating is conducive to the complete removal of impurities and gases in the gas path.
在10ml/min的流速控制下，通入He，收集背景红外光谱谱图；在扣除背景红外光谱谱图后，收集通He氛围下原位红外谱图；关闭He，再通入水蒸气饱和的CO2，收集其原位红外谱图；然后关水蒸气饱和的CO2，改为He吹扫10min，收集原位红外谱图；再关闭He和水蒸气饱和的CO2，开始光照，光照10min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，作为复合体系催化剂的对比。Under the control of a flow rate of 10ml/min, feed He to collect the background infrared spectrum; after subtracting the background infrared spectrum, collect the in-situ infrared spectrum under the atmosphere of He; close the He, and then feed the water vapor-saturated CO2 , collect its in-situ infrared spectrum; then turn off the water vapor-saturated CO2 , change to He purging for 10 minutes, and collect the in-situ infrared spectrum; then turn off He and water vapor-saturated CO2 , start to illuminate, and after 10 minutes of light Turn off the light source, and collect the results of the in-situ infrared spectrum after the photoreaction. The results of the spectra were divided into peaks and assigned, and the peak changes before and after the light reaction were observed, as a comparison of the catalysts of the composite system.
具体原位红外谱图如图3所示，其中，1阶段为扣除背景后，通He条件下原位红外谱图；2阶段为通水蒸气饱和的二氧化碳条件下原位红外谱图；3阶段为He吹扫条件下原位红外谱图；4阶段为光照反应后原位红外谱图。The specific in-situ infrared spectrum is shown in Figure 3, wherein, the first stage is the in-situ infrared spectrum under the condition of He after deducting the background; the second stage is the in-situ infrared spectrum under the condition of passing water vapor saturated carbon dioxide; the third stage In situ infrared spectrum under He purging condition; stage 4 is in situ infrared spectrum after light reaction.
图2和图3对比：可以明显看出二氧化钛和分子筛复合催化剂相对于单一二氧化钛，对二氧化碳和水的吸附性较弱，峰型较缓，峰强度较弱；且单一二氧化钛的原位红外图中不存在生成乙醇C＝O的特征峰，这与光催化反应的结果相符合。因此可以说明我们制备的复合催化剂体系具有较强的光催化活性，且原位红外结果为我们的机理探究提供了依据。Comparison of Figure 2 and Figure 3: It can be clearly seen that the composite catalyst of titanium dioxide and molecular sieve has weaker adsorption to carbon dioxide and water, slower peak shape and weaker peak intensity than single titanium dioxide; and the in-situ infrared image of single titanium dioxide There is no characteristic peak of ethanol C=O, which is consistent with the result of photocatalytic reaction. Therefore, it can be shown that the composite catalyst system we prepared has strong photocatalytic activity, and the in situ infrared results provide a basis for our mechanism exploration.
实施例8Example 8
将制备好的单一分子筛放入研钵中，研磨均匀，后放入50℃烘箱中干燥2小时，以作为本实施例中的催化剂。所述分子筛为选自ETS-10。The prepared single molecular sieve was put into a mortar, ground evenly, and then dried in an oven at 50° C. for 2 hours to be used as the catalyst in this example. The molecular sieve is selected from ETS-10.
本实施例中采用的红外光谱仪为漫反射红外光谱仪。The infrared spectrometer used in this embodiment is a diffuse reflectance infrared spectrometer.
连接好需要的高纯氦气和二氧化碳气路；取下红外样品池，将干燥后的催化剂粉末小心填入样品池中，压平表面，清洁透明玻璃窗口。Connect the required high-purity helium and carbon dioxide gas lines; remove the infrared sample cell, carefully fill the dried catalyst powder into the sample cell, flatten the surface, and clean the transparent glass window.
然后将样品池置于水浴环境中用于检测样品池及气体通路的气密性。Then the sample cell is placed in a water bath environment to test the airtightness of the sample cell and the gas passage.
待装置不漏水后，在通氦气条件下，按照5℃/min程序升温至200℃，在该温度下保温2小时，再降温至50℃，降温时采用液氮对样品池进行降温处理。此步骤为前处理步骤，用于去除气路中的杂质气体，加温有利于气路中杂质及杂质气体的完全去除。After the device is leak-free, the temperature is raised to 200°C according to the program of 5°C/min under the condition of helium gas, kept at this temperature for 2 hours, and then cooled to 50°C, and liquid nitrogen is used to cool the sample cell during cooling. This step is a pretreatment step, used to remove impurity gases in the gas path, and heating is conducive to the complete removal of impurities and impurity gases in the gas path.
在10ml/min的流速控制下，通入He，收集背景红外光谱谱图；在扣除背景红外光谱谱图后，收集通He氛围下原位红外光谱谱图；关闭He，再通入水蒸气饱和的CO2，收集其原位红外谱图；然后关水蒸气饱和的CO2，改为He吹扫10min，收集原位红外谱图；再关闭He和水蒸气饱和的CO2，开始光照，光照10min后关闭光源，收集光反应后原位红外谱图结果。将所得谱图结果分峰归属，观察光照反应前后峰变化，作为复合体系催化剂的对比。Under the control of the flow rate of 10ml/min, He was introduced to collect the background infrared spectrum; after subtracting the background infrared spectrum, the in-situ infrared spectrum was collected under the He atmosphere; CO2 , collect its in-situ infrared spectrum; then turn off the water vapor-saturated CO2 , change to He purging for 10 minutes, and collect the in-situ infrared spectrum; then turn off He and water vapor-saturated CO2 , start to illuminate, and light for 10 minutes Finally, the light source was turned off, and the in-situ infrared spectrum results after the photoreaction were collected. The obtained spectrum results were divided into peaks and assigned, and the peak changes before and after the light reaction were observed, as a comparison of the composite system catalysts.
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.
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| CN201810117635.8ACN108344708A (en) | 2018-02-06 | 2018-02-06 | A kind of device and method of gas-phase photocatalysis mechanism study |
| Application Number | Priority Date | Filing Date | Title |
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| CN201810117635.8ACN108344708A (en) | 2018-02-06 | 2018-02-06 | A kind of device and method of gas-phase photocatalysis mechanism study |
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| CN201810117635.8APendingCN108344708A (en) | 2018-02-06 | 2018-02-06 | A kind of device and method of gas-phase photocatalysis mechanism study |
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