CN106290161B - Sample cell for dynamic absorption spectrum collection - Google Patents
Sample cell for dynamic absorption spectrum collection Download PDFInfo
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- CN106290161B CN106290161B CN201610824572.0A CN201610824572A CN106290161B CN 106290161 B CN106290161 B CN 106290161B CN 201610824572 A CN201610824572 A CN 201610824572A CN 106290161 B CN106290161 B CN 106290161B
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- 238000000862 absorption spectrum Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 230000003287 optical effect Effects 0.000 claims abstract description 17
- 125000006850 spacer group Chemical group 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 230000002093 peripheral effect Effects 0.000 claims abstract description 4
- 230000001737 promoting effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 41
- 238000001228 spectrum Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000007246 mechanism Effects 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000011949 solid catalyst Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000004378 air conditioning Methods 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 238000004847 absorption spectroscopy Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 10
- 239000000523 sample Substances 0.000 description 201
- 239000010453 quartz Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 238000001816 cooling Methods 0.000 description 16
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- 238000003825 pressing Methods 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- 230000004913 activation Effects 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/0332—Cuvette constructions with temperature control
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N2021/0339—Holders for solids, powders
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Optical Measuring Cells (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to a sample cell for dynamic absorption spectrum collection, which comprises: a spacer structure having a set thickness and having a sample hole; the pair of light-transmitting sheets are respectively overlapped on two sides of the gasket structure, and the inner surfaces of the pair of light-transmitting sheets and the sample hole define a film-shaped sample space; the temperature control device is arranged at the outer side of the light-transmitting sheet and close to the peripheral position of the sample space so as to control the temperature of the sample in the sample space; and the clamping devices are arranged on the outer sides of the paired light transmitting sheets so as to enable the gasket structure to be tightly attached to the light transmitting sheets. The gasket structure comprises a single gasket or a plurality of gaskets which are detachably and tightly overlapped to form a series of sample spaces with set optical paths, and the contact surface of the gasket and the sample in the sample space has catalytic activity for promoting the reaction of the sample in the sample space. The sample cell has the advantages of compact structure, high heat transfer efficiency and flexible use.
Description
Technical Field
The invention relates to an optical device applied to the field of analytical chemistry, in particular to a sample cell for continuously collecting dynamic absorption spectrum in a sample reaction process.
Background
By utilizing the sample absorption spectrum signal, the chemical composition and chemical junction information of the sample can be obtained rapidly and nondestructively. The reaction process of the sample is combined with the absorption spectrum measurement, so that the on-line continuous monitoring of the chemical reaction is realized, and the dynamic absorption spectrum of the sample in the chemical reaction environment can be obtained, thereby realizing accurate depiction of the whole reaction process, and being applicable to the fields of reaction kinetics and thermodynamic research, substance qualitative and concentration analysis, catalyst activity evaluation and the like. Therefore, the development reaction-detection integrated spectrum sample cell structure has important academic research and engineering application value.
Currently, there are several common spectrum sample cell structures that can achieve the above functions to some extent: one is a constant temperature sample cell, i.e. a constant temperature jacket is added on a conventional cuvette bracket so as to maintain the sample in the cuvette at a required reaction temperature, thereby starting a specific reaction and collecting the reaction dynamic spectrum of the sample. The main defect of the sample cell structure is that the heat transfer area is small, so the heat transfer rate and the temperature uniformity are low; and no mass transfer strengthening mechanism is provided, so that the uniformity of chemical composition is poor. And secondly, a flowing sample cell, namely, continuously inputting a sample in the external reactor into a cuvette through a pipeline and a pump and keeping flowing, so as to collect dynamic spectrum. The main problems of the sample cell are that the structure is complex, the high-viscosity fluid is difficult to process, and certain hysteresis exists in the spectrum signal acquisition in the reaction process. And thirdly, an optical fiber probe can be directly inserted into a reactor body to collect dynamic spectrum on line. But is costly and difficult to achieve optical path adjustment and difficult to clean if probe contamination occurs. In addition to the above-mentioned drawbacks, these dynamic spectrum acquisition schemes all require a larger sample volume, resulting in lower temperature control sensitivity and accuracy. More importantly, the optical path length of the structures is generally not smaller than 1mm, so that the samples with high absorbance cannot be directly measured, and the samples are required to be diluted by a solvent. This brings three limitations: (1) The effect of the solvent on the reaction and the interference with the spectroscopic measurements must be considered; (2) The preparation process of the sample solution and the errors introduced by the preparation process must be considered in quantitative determination; (3) For high temperature reactions, the high pressure hazards of solvent evaporation or its vapor generation are also considered.
In summary, the existing dynamic spectrum acquisition devices have certain limitations.
Disclosure of Invention
Aiming at the limitations of the existing dynamic absorption spectrum acquisition device, the invention provides a novel dynamic absorption spectrum acquisition sample cell which has compact structure, high efficiency of heat transfer, flexible use and capability of executing various homogeneous and heterogeneous reactions. The method can be directly applied to the current mainstream desk-top ultraviolet, visible light and infrared spectrometers, and can also be used for small portable absorption spectrum instruments, so that the application range of spectrum analysis is further widened.
The sample cell for dynamic absorption spectrum acquisition of the invention comprises: a spacer structure having a set thickness and having a sample hole; the pair of light-transmitting sheets are respectively overlapped on two sides of the gasket structure, and the inner surfaces of the pair of light-transmitting sheets and the sample hole define a film-shaped sample space; the temperature control device is arranged at the outer side of the light-transmitting sheet and close to the peripheral position of the sample space so as to control the temperature of the sample in the sample space; and the clamping devices are arranged on the outer sides of the paired light transmitting sheets so as to enable the gasket structure to be tightly attached to the light transmitting sheets. The gasket structure comprises a single gasket or a plurality of gaskets which are detachably and tightly overlapped to form a series of sample spaces with set optical paths, and the contact surface of the gasket and the sample in the sample space has catalytic activity for promoting the reaction of the sample in the sample space.
In a preferred embodiment of the present invention, each of the spacers is a metal plate having a predetermined thickness composed of platinum, rhodium, palladium, nickel, copper, iron, aluminum or an alloy thereof capable of functioning as a catalyst of the reaction system in the sample space, or a ceramic plate having a surface on which a solid catalyst capable of functioning as a catalyst of the reaction system in the sample space is supported.
In a preferred embodiment of the invention, each spacer has a thickness of 0.01-0.5mm; and/or the diameter of the sample hole is 6-20mm.
In a preferred embodiment of the invention, an overflow trough communicated with the sample hole is arranged on the surface of a gasket attached to the light transmitting sheet.
In a preferred embodiment of the invention, the spacer is further provided with positioning holes at the periphery of the sample hole to facilitate alignment with each other in the case of a plurality of spacers.
In a preferred embodiment of the present invention, the clamping device comprises: the clamping plates are used for being respectively overlapped on the outer sides of the paired light transmitting sheets; and the fastening mechanism is used for clamping the pair of clamping plates so as to keep the position of the light transmitting sheet and the gasket between the clamping plates fixed and tightly attached.
In a preferred embodiment of the present invention, the temperature control device includes: the heating plate and/or the refrigerating plate are/is arranged on the inner or outer side surface of one clamping plate, and the temperature sensor is arranged on the inner or inner side surface of the other clamping plate, and the temperature sensor can be connected with the relay and can control the opening and closing of the heating/refrigerating plate.
In a preferred embodiment of the present invention, the fastening mechanism is selected from the group consisting of screw fastening, elastic fastening, and magnetic fastening; the area of the gasket is not smaller than 3 times of the area of the sample hole, the surface area of the pair of light-transmitting sheets, which are in fit contact with the gasket, is not smaller than 3 times of the area of the sample hole, and the surface area of the pair of clamping plates, which are in fit contact with the light-transmitting sheets, is not smaller than 3 times of the area of the sample hole.
In a preferred embodiment of the present invention, the gasket structure comprises a plurality of gaskets which are detachably overlapped, and the sizes of the sample holes of the adjacent gaskets are different, so as to obtain a sample space with increased and adjustable liquid-solid contact interface area.
In a preferred embodiment of the invention, the gasket structure comprises a plurality of gaskets which are detachably and tightly overlapped up and down, and at least one gasket close to the upper side is provided with a diversion trench communicated with the sample hole so as to obtain a sample space with a stable gas-liquid contact interface, thereby being suitable for dynamic spectrum collection of gas-liquid reaction.
The invention has the advantages that: (1) The distance between the quartz plates is adjusted by using a spacer with a preset thickness, so that the accurate control of the optical path of the film-shaped sample cell can be realized; (2) Because the sample is in the film space, the optical path is easy to set to be one hundredth or even one thousandth of a traditional device, and for the sample with high absorbance, the sample can be directly observed without dilution by solvent; (3) The film-shaped sample cell has small volume but large heat exchange area, so the temperature control is more sensitive and accurate; (4) The film-shaped sample cell can provide a larger solid-liquid or gas-liquid contact interface for a small-volume sample, and can still obtain higher mass transfer efficiency and reaction uniformity for a heterogeneous reaction system; (5) The gasket has catalytic activity with the sample contacting surface to promote sample reaction without the need to add a solid catalyst in the sample space.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a sample cell of the present invention;
FIG. 2 is a schematic diagram of a second embodiment of the sample cell of the present invention when it is used in a solid-liquid reaction system; a kind of electronic device with high-pressure air-conditioning system
FIG. 3 is a schematic diagram of a third embodiment of the sample cell of the present invention when it is used in a gas-liquid reaction system.
Detailed Description
The nature of dynamic absorption spectrum is that the absorption spectrum signals of substances are related to time, so that the dimension and precision of sample characterization and depiction can be increased, and the method has important application value in the aspects of chemical reaction dynamics and thermodynamic research, substance qualitative and quantitative and catalyst activity evaluation.
The invention relates to a sample cell for dynamic absorption spectrum acquisition, which comprises the following components: the middle part of the precision gasket is provided with a sample hole for loading a sample, and the contact surface of the precision gasket and the sample can also have catalytic activity for promoting the sample to participate in chemical reaction; the paired light-transmitting sheets, such as quartz sheets, are respectively positioned at two sides of the precision gasket and serve as two light-transmitting surfaces of the sample cell, and the inner surfaces of the paired light-transmitting sheets and the sample holes define a film-shaped sample space. The temperature control device is arranged at the outer side of the light transmitting sheet and close to the peripheral position of the sample space so as to control the temperature of the sample in the sample space. The clamping device is arranged on the outer sides of the paired light transmitting sheets so that the gaskets are tightly attached to the light transmitting sheets.
The optical path of the sample cell can be accurately adjusted and serialized by adopting a mode of overlapping single-layer or multi-layer precise gaskets, so that the sample cell has wide universality and flexibility for various samples with different absorbance properties. Therefore, another feature of the present invention is that the precision spacer can be used in a single layer or in a multi-layer stack, thereby adjusting the spacing of the quartz plates to form a series of sample cells having a set optical path.
Preferably, the thickness of each spacer may be selected to be 0.01-0.5mm.
Preferably, the sample well according to the present invention is a circular well having a diameter of 6-20mm.
The material of the precision shim should generally have the following characteristics: (1) precision machining is easy to realize; (2) has a high hardness in the use temperature range; (3) has better heat conducting property. For example, a metal sheet or a ceramic sheet may be used.
When a metal sheet is used as the precision gasket, a metal such as platinum, rhodium, palladium, nickel, copper, iron, aluminum, or an alloy thereof may be used. When the ceramic plate is used as a precision gasket, a layer of catalyst can be covered on the surface of the ceramic plate.
The other preferable characteristic of the precision gasket is that the periphery of the sample hole in the middle part is also provided with at least 2 positioning hole structures, which play a role in assembly and positioning. For example, the positioning holes are 2-6mm circular holes, the number of the positioning holes is 4, and the 4 positioning holes are uniformly distributed around the sample hole, so that the sealing surface is uniformly stressed, and the sample leakage is avoided.
In addition, some samples can generate excessive pressure on the light transmitting sheet due to thermal expansion under high temperature conditions, so that the sealing surface between the light transmitting sheet and the precision gasket is invalid, the samples leak and run off, and finally the stability of the dynamic spectrum acquisition process is damaged. For this purpose, one of the features of the present invention is that an overflow channel may be provided on the surface of the precision gasket in communication with the sample well. For example, a rectangular overflow trough with the width of 1-2mm is arranged, when the sample is heated and swells, the sample overflows from the overflow trough, and the residual sample can still fill the sample cell and keep the reaction process and the spectrum acquisition process stable.
The temperature control device can comprise a heating/refrigerating sheet and a temperature sensor, and is used for heating/cooling and measuring the temperature of a sample in the sample cell, and the temperature sensor can be connected with a temperature relay and used for controlling the opening and closing of the heating body.
The clamping device may comprise: the clamping plates are used for keeping the positions of the quartz plates and the precision gaskets between the clamping plates fixed and tightly attached; and fastening means for fixing the positions of the pair of clamping plates and maintaining the clamping force.
In order to control the temperature of the sample in the sample cell uniformly and sensitively, a sufficient contact heat conduction area must be ensured to achieve a good heat transfer effect. To this end, one of the features of the present invention is that the area of the precision spacer is not less than 3 times the area of the sample hole thereon; the pair of quartz plates are respectively positioned at two sides of the precise gasket and are attached to the precise gasket, and the surface area which can be attached to and contacted with the precise gasket is not less than 3 times of the area of the sample hole; the paired clamping plates are respectively positioned on the outer sides of the quartz plates and are attached to the quartz plates, and the surface area of the paired clamping plates, which is attached to and contacted with the quartz plates, is not smaller than 3 times of the area of the sample hole.
The heating/cooling fin is in contact with one of the pair of clamping plates and serves as a heating/cooling source, for example, the heating fin and/or the cooling fin may be disposed inside or outside a clamping plate. The temperature sensor may be provided inside or on the inner side surface of the same or another clamping plate. The temperature sensor can be connected with the relay and control the opening and closing of the heating/cooling sheet.
Preferably, the temperature sensor is contacted with the clamping plate at the other side and senses temperature. The heating/cooling source and the temperature sensor are arranged on the different side of the sample cell instead of the same side, and the reason is that when the heating/cooling source and the temperature sensor are arranged on the same side, the heat conduction path of the heating/cooling source and the temperature sensor is shorter, and the measured temperature is closer to the temperature of the heating/cooling source; when the two are on different sides, the heat conduction path between the temperature sensor and the sample cell is shorter, and the measured temperature is closer to the temperature of the sample cell. The clamping plates are usually made of a material having good heat conducting properties and sufficient strength. For example, stainless steel, aluminum, copper or alloys may be used.
In general, the heating plate is used to provide the heat required by the sample cell because the chemical reaction needs to be started (over activation energy) or has an observable reaction rate at over a certain temperature. However, when the sample cell is used for infrared dynamic absorption spectrum collection, the sample in the sample cell may exceed a set temperature due to the continuous heating effect of infrared radiation; in addition, when the chemical reaction is exothermic, it may cause the sample in the sample cell to exceed a set temperature, and thus it is necessary to remove excessive heat using a cooling fin. Therefore, the direct current semiconductor heating/cooling sheet is selected as a heat source or a cold source of the sample cell, and the sample cell can be heated or cooled by switching the positive electrode and the negative electrode of the direct current power supply.
And a heat insulation layer can be arranged on the outer side of the clamping plate and used for reducing heat loss of the sample cell and avoiding other parts of the spectrometer from being affected by high temperature.
Because the sample cell is formed by combining the components, various samples including high-viscosity liquid are easy to load in a decomposition state, and the contact surfaces of the components are required to be tightly attached based on a certain clamping force in the combination state, so that the leakage of the samples is prevented, and the heat transfer effect is ensured. To this end, the sample cell of the present invention also has fastening means in the form of, but not limited to, screw fastening, elastic fastening and magnetic fastening.
The screw fastening and the elastic fastening are mechanical fastening modes, and the magnetic fastening means that permanent magnets or electromagnets are respectively fixed on the clamping plates at two sides, and the fastening is realized by utilizing the attraction effect of a strong magnetic field when the clamping plates are mutually close. The magnetic fastening is the preferred fastening mode, so that the disassembling-assembling operation of the sample cell is simpler, and the clamping force is more balanced and stable.
In addition, when precision shims with sample holes of different diameters are used in superposition, a sample cell with an annular solid-liquid contact interface can be formed. The annular contact interface may be formed by exposed upper and/or lower surfaces on the gasket of the smaller diameter sample well at the periphery of the sample well, for example, fig. 2 (b) shows a small diameter sample well gasket 70 sandwiched between two precision gaskets, which provides two annular solid-liquid contact interfaces defined by the exposed upper and lower surfaces. The interface area can also be precisely controlled by selecting the difference in diameter and/or increasing or decreasing the number of superimposed layers of shims (preferably, alternating superimposed of precision shims with sample holes of different diameters). When the precise gasket is made of a material with catalytic activity, the catalytic interface area and the volume of the sample body are adjustable, so that the precise gasket has outstanding practical value for the dynamic research of solid-liquid catalytic reaction.
The invention can provide a structural scheme for liquid-solid reaction dynamic spectrum measurement, namely a sample cell formed by alternately superposing more than two precise gaskets with different sample hole diameters, and the sample cell has an annular solid-liquid contact interface with controllable area.
On the other hand, when the reaction system is a gas-liquid system, a structure of overlapping a precise gasket with a diversion trench and a precise gasket without a diversion trench can be adopted. When the liquid sample is loaded, if the liquid sample level exceeds the thickness of the lower layer non-diversion trench precision gasket, the liquid sample overflows through the diversion trench on the upper layer precision gasket, so that the set liquid sample thickness can be obtained. When the sample cell is closed and fastened and kept in a horizontal state, a certain volume of gas phase is kept in the sample hole of the upper-layer precise gasket with the diversion trench, and an interface with stable and controllable area is formed between the upper-layer gas phase and the lower-layer liquid phase (the size of the interface can be realized by selecting the diameter of the sample hole). Starting the reaction process under this condition will allow continuous acquisition of the dynamic spectrum of the gas-liquid reaction.
The invention also provides a structural scheme for dynamic spectrum measurement of gas-liquid reaction, namely a sample cell which is formed by overlapping at least one piece of precise gaskets with diversion grooves and at least one piece of precise gaskets without diversion grooves and is horizontally placed, and the sample cell has a gas-liquid contact interface with controllable area.
For a better understanding of the principles and advantages of the present invention, reference is made to the following detailed description of the preferred embodiments of the invention, taken in conjunction with the accompanying drawings.
Referring to FIG. 1, which is a schematic diagram of one embodiment of the sample cell of the present invention, FIG. 1 (a) is a top plan view of a gasket in the sample cell and FIG. 1 (b) is a side cross-sectional view of the sample cell. In the sample cell of this embodiment, a set of precision shims 4 are stacked together to form a sample well having a controlled thickness (optical path length). A quartz plate 3 is closely attached to two sides of the precision gasket respectively, so that a film space capable of loading liquid samples is formed by the quartz plate and sample holes on the precision gasket. A clamping plate 1 is respectively attached to the two outer sides of the two quartz plates. The heating/refrigerating sheet 6 is arranged on the clamping plate on one side and is used as a heat source/cold source, and the temperature sensing probe 2 is arranged on the clamping plate on the other side and is used for measuring the temperature and is connected with the temperature relay to control the on-off of the heating/refrigerating sheet so as to form a constant temperature environment. In order to keep the precision gasket, the quartz plate and the clamping plate tightly attached, magnetic fastening mechanisms 5 are arranged at two ends of the clamping plate. As can be seen from the top view of the precision gasket 4, i.e., fig. 1 (a), the precision gasket 4 is provided with at least 2 positioning holes 7 for positioning the precision gasket; in addition, there is a circular sample well 8. If the device is used for dynamic spectrum signal acquisition of higher temperature (more than 80 ℃) reaction, a layer of heat insulation material can be adhered to the outer side of the clamping plate 1.
The invention is not limited to the specific number and materials in this embodiment, but 3 shims are shown, each having a predetermined thickness (e.g., 0.05 mm). The sample holes of each spacer were aligned with each other and had a diameter of 10mm. According to the reaction requirement of the sample, a metal sheet or a ceramic sheet can be selected. For the metal sheet, platinum, rhodium, palladium, nickel, copper, iron, aluminum or alloys thereof may be selected. The surface of the ceramic sheet is covered with a solid catalyst layer. The solid catalyst can be used as a catalyst for the reaction system in the sample space, such as a solid acid catalyst or a solid base catalyst.
The method of using the sample cell of the present embodiment will be described below.
The dynamic absorption spectrum signal of the liquid sample is collected by the following steps: (1) Mixing the liquid sample with the reactants and, if desired, the homogeneous catalyst; (2) Stacking a side clamping plate, a quartz plate and a precision gasket with a set thickness (optical path) horizontally from bottom to top, and dripping and filling the mixture into a sample hole of the precision gasket; (3) Stacking another quartz plate and the clamping plate at the other side on the sample hole filled with the mixture, and pressing the components by using a magnetic fastening mechanism to integrate the components; (4) Placing the combined sample cell between a light source transmitting end and a light source receiving end of the spectrometer, and ensuring that a quartz plate window is vertically opposite to a light path; (5) And starting a heating/cooling sheet on the dynamic spectrum sample cell to a set temperature and keeping the temperature constant, and continuously collecting a series of dynamic spectrum signals of a sample by utilizing a spectrometer.
The following introduces the advantages of using the device to collect dynamic spectrum signals of a sample: (1) The optical path of the sample cell can be accurately regulated and controlled by utilizing the precise gasket or the superposition combination thereof, and a sample with high absorbance can be directly observed without solvent dilution; (2) The sample has a film-shaped sample space, and the sample has small volume and large heat transfer area, so that uniform and sensitive temperature control is easy to realize; (3) The whole device is easy to disassemble or combine, is convenient for loading high-viscosity samples, and is easy to clean thoroughly so as to avoid pollution among the samples; (4) The structure is simple and compact, the device can be universally used for various spectrometers, and the response-measurement integrated acquisition signal has no hysteresis. This embodiment is suitable for use in liquid homogeneous reaction systems, i.e. the reactants and catalyst (if desired) are miscible in one phase.
FIG. 2 is a schematic diagram of a second embodiment of the sample cell of the present invention when used in a solid-liquid reaction system, wherein FIG. 2 (a) is a top plan view of a gasket in the sample cell and FIG. 2 (b) is a side sectional view of the sample cell. In the sample cell, a set of catalytically active precision shims 40 and 70 having different sample well diameters are stacked together to form a sample well having a controlled thickness (optical path length). And because of the different diameters of the precision shim sample bore, and the substantially coaxial arrangement, has an annular solid-liquid contact interface defined by the exposed upper and lower surfaces of the shim. A quartz plate 30 is closely attached to both sides of the precision pad, so that a thin film space for loading a liquid sample is formed with the sample hole on the precision pad. A clamping plate 10 is attached to each of the two outer sides of the two quartz plates. A heating/cooling plate 60 is installed on one side of the clamping plate and is used as a heat source/cold source, and a temperature sensing probe 20 is installed on the other side of the clamping plate and is used for measuring temperature and connecting with a temperature relay to control the opening and closing of a heating body so as to form a constant temperature environment. In order to keep the precision pad, quartz plate and clamping plate tightly attached, elastic fastening mechanisms 50 are also arranged at two ends of the clamping plate. As can be seen from the top view of fig. 2 (a) of the precision shim, the precision shim is provided with at least 2 positioning holes 80 for positioning the precision shim; in addition, there is a circular sample well 90. If the device is used for dynamic spectrum signal acquisition of higher temperature (more than 80 ℃) reaction, a layer of heat insulation material can be adhered to the outer side of the clamping plate 10.
Wherein the precision gasket is a metal material with a catalytic effect or a ceramic plate with a surface loaded with a catalyst.
The method of using the sample chamber of the present embodiment is described below.
The dynamic absorption spectrum signal of the liquid sample is collected by the following steps: (1) mixing the liquid sample with the reactant uniformly; (2) Horizontally stacking a side clamping plate, a quartz plate and a precision gasket with a set thickness (optical path) and an annular solid catalytic interface from bottom to top, and dripping and filling the mixture into a sample hole of the precision gasket; (3) Stacking another quartz plate and the clamping plate at the other side on the sample hole filled with the mixture, and pressing the components by using an elastic fastening mechanism to integrate the components; (4) Placing the combined sample cell between a light source transmitting end and a light source receiving end of the spectrometer, and ensuring that a quartz plate window is vertically opposite to a light path; (5) And starting a heating/cooling sheet on the dynamic spectrum sample cell to a set temperature and keeping the temperature constant, and continuously collecting a series of dynamic spectrum signals of a sample by utilizing a spectrometer.
The following introduces the advantages of using the device to collect dynamic spectrum signals of a sample: (1) The solid catalytic interface area can be accurately regulated and controlled by selecting the diameter difference or increasing or decreasing the number of layers of gasket superposition (precise gaskets with sample holes with different diameters need to be alternately superposed); (2) The device has a film-shaped sample space, has a large contact surface between the sample and the solid catalyst, and is favorable for obtaining a uniform reaction effect. This embodiment is suitable for use in a solid-liquid heterogeneous reaction system.
Fig. 3 is a schematic view of a third embodiment of the sample cell of the present invention when used in a gas-liquid reaction system, wherein fig. 3 (a) is a top plan view of a gasket in the sample cell and fig. 3 (b) is a side sectional view of the sample cell. The sample cell of this embodiment is constructed as follows:
stacking a set of precision shim 700 with channels 900 and precision shim 400 without channels; a piece of quartz plate 300 is closely attached to both sides of the precision pad, respectively, so that a thin film space for loading liquid sample is formed with the sample holes on the precision pad. A clamping plate 100 is attached to each of the two outer sides of the two quartz plates. A heating/cooling sheet 600 is installed on one side of the clamping plate as a heat source/cold source, and a temperature sensing probe 200 is installed on the other side of the clamping plate for measuring temperature and controlling the opening and closing of the heating body by being connected with a temperature relay so as to form a constant temperature environment. In order to maintain the tight adhesion of the precision gasket, the quartz plate, and the clamping plate, screw fastening mechanisms 500 are provided at both ends of the clamping plate. As can be seen from fig. 3 (a) which is a top view of the precision shim, the precision shim is provided with at least 2 positioning holes 800 for positioning the precision shim; in addition, there is a circular sample hole and a flow guide groove 900 communicating with the sample hole. If the device is used for dynamic spectrum signal acquisition of higher temperature (more than 80 ℃) reaction, a layer of heat insulation material can be adhered to the outer side of the clamping plate 1.
The method of using the sample chamber of the present embodiment is described below.
The dynamic absorption spectrum signal of the liquid sample is collected by the following steps: (1) Stacking a side clamping plate, a quartz plate and a precise gasket combination from bottom to top horizontally (wherein the precise gasket without a diversion trench is arranged below the precise gasket with the diversion trench), (2) dripping liquid sample into a sample hole of the precise gasket, and overflowing from the diversion trench on the upper layer when the liquid sample level exceeds the sample hole without the diversion trench; (3) Stacking another quartz plate and the clamping plate at the other side on the sample hole filled with the mixture, and pressing the components by using a screw fastening mechanism to integrate the components; (4) Placing the combined sample cell horizontally, placing the light source emitting end and the light source receiving end of the spectrometer on the upper side and the lower side of the sample cell respectively, and ensuring that the quartz sheet window is vertically opposite to the light path; (5) And starting a heating/cooling sheet on the dynamic spectrum sample cell to a set temperature and keeping the temperature constant, and continuously collecting a series of dynamic spectrum signals of a sample by utilizing a spectrometer.
The following introduces the advantages of using the device to collect dynamic spectrum signals of a sample: (1) Dynamic spectrum acquisition of a gas-liquid heterogeneous reaction process can be implemented; (2) The device has a film-shaped sample space, and the contact surface of the sample and the gas phase is large, so that the uniform reaction effect is favorable. This embodiment is suitable for use in a gas-liquid heterogeneous reaction system, but requires that the light source emitting and receiving ends of the spectrometer be capable of being vertically arranged.
In summary, the sample cell for dynamic absorption spectrum collection provided by the invention has the following advantages: (1) The distance between the light transmitting sheets is determined or adjusted by using a spacer with a preset thickness, so that the accurate control of the optical path of the film-shaped sample cell can be realized; (2) Because the sample is in the film space, the optical path can realize only one hundredth or even one thousandth of the traditional device, and for the sample with high absorbance, the sample can be directly observed without dilution by solvent; (3) The film-shaped sample cell has small volume but large heat exchange area, so the temperature control is more sensitive and accurate; (4) The film-shaped sample cell can provide a larger solid-liquid or gas-liquid contact interface for a small-volume sample, and can still obtain higher mass transfer efficiency and reaction uniformity for a heterogeneous reaction system; (5) Easy to disassemble and combine, and is convenient for the measurement and cleaning of high-viscosity samples. (6) The structure is simple and compact, can be widely used for various existing spectrum devices, and can realize reaction-measurement integration.
Claims (8)
1. A sample cell for dynamic absorption spectroscopy acquisition, comprising:
a spacer structure having a set thickness and having a sample hole;
the pair of light-transmitting sheets are respectively overlapped on two sides of the gasket structure, and the inner surfaces of the pair of light-transmitting sheets and the sample hole define a film-shaped sample space;
the temperature control device is arranged at the outer side of the light-transmitting sheet and close to the peripheral position of the sample space so as to control the temperature of the sample in the sample space; a kind of electronic device with high-pressure air-conditioning system
The clamping devices are arranged at the outer sides of the paired light transmitting sheets so as to enable the gasket structure to be tightly attached to the light transmitting sheets,
the gasket structure comprises a plurality of gaskets which are detachably and tightly overlapped to form a series of sample spaces with set optical paths, and the contact surface of the gasket and a sample in the sample spaces has catalytic activity for promoting the reaction of the sample in the sample spaces; the sizes of the sample holes of the adjacent gaskets are different, so that a sample space with increased and adjustable liquid-solid contact interface area is obtained; when gaskets with sample holes with different diameters are overlapped, a sample cell with an annular solid-liquid interface is formed, and the annular contact surface is formed by the upper surface and/or the lower surface exposed at the periphery of the sample hole on the gasket with the smaller diameter sample hole, so that the area of the solid catalytic interface is accurately regulated and controlled by selecting the diameter difference and increasing and decreasing the overlapped layers of the gaskets;
the temperature control device comprises a heating sheet and/or a refrigerating sheet arranged on the inner or outer side surface of one clamping plate and a temperature sensor arranged on the inner or inner side surface of the other clamping plate, wherein the temperature sensor can be connected with the relay and used for controlling the opening and closing of the heating/refrigerating sheet.
2. The cuvette according to claim 1, wherein each of the gaskets is a metal plate having a predetermined thickness composed of platinum, rhodium, palladium, nickel, copper, iron, aluminum or an alloy thereof, which can be used as a catalyst of the reaction system in the sample space, or a ceramic plate having a surface on which a solid catalyst which can be used as a catalyst of the reaction system in the sample space is supported.
3. The sample cell of claim 1, wherein each spacer has a thickness of 0.01-0.5mm; and/or the diameter of the sample hole is 6-20mm.
4. The cuvette according to claim 1, wherein an overflow channel is provided on a surface of a gasket attached to the light transmitting sheet in communication with the sample aperture for allowing the sample to overflow out of the sample space when inflated.
5. The cuvette according to any one of claims 1-4, wherein the gasket is further provided with positioning holes at the periphery of the sample well to facilitate alignment with each other in case of a plurality of gaskets.
6. The cuvette according to any one of claims 1-4, wherein the clamping means comprises: the clamping plates are used for being respectively overlapped on the outer sides of the paired light transmitting sheets; and the fastening mechanism is used for clamping the pair of clamping plates so as to keep the position of the light transmitting sheet and the gasket between the clamping plates fixed and tightly attached.
7. The sample cell of claim 6, wherein the fastening mechanism is selected from the group consisting of screw fastening, elastic fastening, and magnetic fastening; and is also provided with
The area of the gasket is not smaller than 3 times of the area of a sample hole on the gasket, the surface area of the pair of light-transmitting sheets, which is in fit contact with the gasket, is not smaller than 3 times of the area of the sample hole, and the surface area of the pair of clamping plates, which is in fit contact with the light-transmitting sheets, is not smaller than 3 times of the area of the sample hole.
8. The cuvette according to any one of claims 1 to 4, wherein the gasket structure comprises a plurality of gaskets detachably stacked one on top of the other, and at least one of the gaskets near the upper side has a flow guide groove communicating with the sample hole, so as to obtain a sample space with a stable gas-liquid contact interface, thereby being suitable for dynamic spectrum collection of gas-liquid reaction.
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| CN109959610A (en) * | 2017-12-26 | 2019-07-02 | 中国科学院化学研究所 | A kind of microfluidic liquid sample pool tested and analyzed for dynamic spectrum and its purposes |
| CN110579432B (en) * | 2019-09-24 | 2023-01-10 | 南京工业大学 | Dual-purpose sealing assembly and operation method |
| CN111239079B (en) * | 2020-03-09 | 2022-11-11 | 上海交通大学 | Time-varying turbid field simulation device with fixed optical depth |
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