CN100567952C - The metal porphyrin langmuir blodgett film optical fiber gas sensor - Google Patents
The metal porphyrin langmuir blodgett film optical fiber gas sensor Download PDFInfo
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- CN100567952C CN100567952C CNB2007100785596A CN200710078559A CN100567952C CN 100567952 C CN100567952 C CN 100567952C CN B2007100785596 A CNB2007100785596 A CN B2007100785596A CN 200710078559 A CN200710078559 A CN 200710078559A CN 100567952 C CN100567952 C CN 100567952C
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Abstract
A kind of metal porphyrin langmuir blodgett film optical fiber gas sensor relates to the sensor that detects harmful gas device in the industrial production environment.Sensor of the present invention mainly comprises both arms optical fiber, reaction chamber and metalloporphyrin LB membrane array plate etc.Because sensor of the present invention has characteristics such as detectability is low, highly sensitive, reusable, and the detected gas scope is wide,, be specially adapted to NO in the commercial production so the present invention can be widely used in the various volatility toxic gases that detect in the human being's production living environment
2, SO
2, NO, CO, H
2S reaches the detection of noxious gas emission qualifications such as phosgene and the detection of leakage.
Description
Technical field
The invention belongs to the technical field that detects harmful gas in the atmospheric environment, particularly detect the sensor of harmful gas in the industrial production environment.
Background technology
Along with the high speed development of industrial technology, commercial production has been brought a large amount of pollutants to human habitat, wherein based on volatile organic matter (VOCs) gas, as: nitrogen dioxide (NO
2), nitrogen monoxide (NO), ammonia (NH
3), sulfuretted hydrogen (H
2S), phosgene or the like.These volatile organic gas have had a strong impact on human daily life environment, and the physical and mental health that is constantly jeopardizing people.Wherein nitrogen dioxide has corrosivity and physiological stimulation effect, and it is impaired to cause lung to grow, and causes lung's structural change, it is one of principal element that forms photo-chemical smog, also be one of source of acid rain, to human body, environment and crops etc. all can cause quite serious harm; And sulfuretted hydrogen has very big damaging effect to human central nervous, can cause illnesss such as pulmonary edema, bronchitis, pneumonia; Particularly point out in addition, phosgene is a kind of special commercial production raw material, and it has great toxicity, and very micro-phosgene just is enough to make an adult to get killed.Phosgene derives from the commercial production treatment of waste gas not exclusively and the leakage of industrial installation or the like mostly.Therefore detect these toxic gases (phosgene etc.), and take corresponding control measures, to the living environment that purifies people and prevent that aspect such as environment major accident generation is all significant.
Optochemical sensor is a kind of novel microscratch measurement amount technology that development in recent years is got up, and now is used widely.The Fibre Optical Sensor of existing detected gas is " light filtering ammonia sensitive optical fibre sensor " patent of CN1057904A as publication number, and disclosed Fibre Optical Sensor is by sheath, incident optical, outgoing optical fiber, incident lens, exit lens, tin ash sensitive membrane and uv filter are formed.This Fibre Optical Sensor adopts the mode of transmission, by detection light source by with ammonia gas react after sensitive membrane, the variation that its optical characteristics produces realizes the detection to the object ammonia.Existing fiber gas sensor generally is to adopt transmission-type or reflective two kinds of optic path mechanism to make.This type optical fiber gas sensor, its maximum characteristics are to adopt the optic path form of singly going into singly to go out, the sensor that the optical texture that indivedual employings singly go into to have more is wherein arranged, but certain single information that remains target substance that the multi beam outgoing optical fiber that it adopts is detected is a certain certain sensitive characteristic that incoming signal or outgoing signal all only can be represented a kind of material.Such fiber gas sensor can only be realized a kind of material or have the identification of a class material of identical characteristics, and its selectivity recognition capability is relatively poor, and sensitivity is also not high enough.For the sensor of using metalloporphyrin as sensitive materials; " researchs of four pairs of bromophenyl platinum porphyrins Polyvinylchloride sensitive membrane dissolved oxygen sensors " as Sichuan University; its sensitive membrane is directly done the preparation of film instrument by rotation; such sensor sensing film; usually can be not exclusively because of reaction, problem such as accuracy of detection and selectivity and influence the promotion and application of this type of sensor.
Summary of the invention
The objective of the invention is deficiency, a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor is provided at the existing fiber gas sensor.This sensor has that gas sensitization is good, and volume is little, and the selectivity recognition capability is strong, resolving power height, advantage such as reusable.
Principle of the present invention: for sensitive materials, porphyrin is the general name that the porphines outer shroud has substituent homolog and derivant, promptly forms the metalloporphyrin complex after 2 protons of nitrogen on the porphyrin are replaced by metallic ion.Metalloporphyrin has langmuir blodgett film (being called for short the LB film) film forming characteristics, can make the LB film by film balance or film transfer method.The LB membrane technology is one of several advanced technologies of preparation ultrathin membrane on molecular level, it is a kind of unimolecular film deposition technique that can accurately control film thickness and molecules align, it can control the structure of material and physics, chemical property on molecular level, realize the permutation and combination on the molecular level, thereby set up supramolecular structure and ultra micro compound substance, and observe chemical reaction and the physical phenomenon that to carry out generally speaking, and even some other specific function and biologically active or the like.In experiment, responsive thing LB film and detected object gas generation chemical action, because the LB film is a unimolecular film, its great advantage is to make sensitive materials with object gas generation complete reaction.From mechanism of action, studies show that the porphyrin and the derivative L B film of cyclic conjugated structure, has semiconductor property, metalloporphyrin with object gas in conjunction with after, the electronics give and accept relation takes place in the molecule, thereby make the extinction characteristic of sensitive materials metalloporphyrin LB film, photoelectricity physical propertys such as reflective characteristic change.Therefore, when light source reaches metalloporphyrin LB film by incident optical, the photoelectric properties that light signal will take place under the effect of the reacted LB film with object gas in various degree change, make and the light generation change in various degree that spreads out of from outgoing optical fiber comprise the change of character such as wavelength, color.Therefore, the light signal that spreads out of by outgoing optical fiber has just been represented unique optical signature information of this tested gas, can detect the existence of corresponding gas molecule in view of the above.For example, existing research has found that copper porphyrin is to NO
2Has very high susceptibility.And the sensitive element that the LB film of copper, cobalt, nickel, manganoporphyrin and some other metalloporphyrins is made successfully is applied in NO
2, H
2S, CO and Cl
2In the detection Deng gas.
In addition, with respect to other sensitive membrane, the LB film has following outstanding feature:
(1) the LB film is ultra-thin in order, can design laminate structure on molecular scale, so can accurately control thickness;
(2) molecule is the sequential 2 D arrangement in the rete, and when being used for detection of gas, the ultra-thin property of film can cause the maximum of sensitive layer electricity and optical parametric to change;
(3) the orderly arrangement of molecule and good repeatability in the rete can make the response time shorten, and can form required generation little energy and do not destroy macromolecular structure at normal temperatures and pressures.
The object of the present invention is achieved like this: a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor mainly comprises optical fiber, reaction chamber, metalloporphyrin LB membrane array plate etc.Wherein optical fiber is both arms optical fiber, and metalloporphyrin LB membrane array plate is made up of metalloporphyrin LB membrane array, substrate and minute surface.Both arms optical fiber is the 2-6 group, the group number of both arms optical fiber is corresponding consistent with metalloporphyrin LB membrane array number, each group both arms optical fiber is by an incident optical, outgoing optical fiber and fibre-optical probe constitute, and reserve very short optical fiber head part at the other end of fibre-optical probe, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the optical path direction that the outgoing optical fiber head is reserved part all will point to the central point of the metalloporphyrin LB film of this group both arms optical fiber correspondence, so that can accurately be received by the outgoing optical fiber head after the light process substrate direct reflection of incident optical head incident.The other end of 2-6 root incident optical is connected with light-source system, and the other end of 2-6 root outgoing optical fiber is connected with the fiber facet array detector, so 2-6 group both arms optical fiber can be finished importing into and efferentation of light signal simultaneously.2-6 group both arms optical fiber parallel equidistant is installed in a side of reaction chamber, and 2-6 fibre-optical probe and reaction chamber fixed seal connection are used for the input of light source light signal and with the output of the light signal after the effect of metalloporphyrin LB membrane array.The present invention adopts multichannel both arms optical fiber can realize can realizing the identification to multiple gases simultaneously to metalloporphyrin LB membrane array transmission of Information and identification, and its selectivity recognition capability is strong, and the sensitivity of detected gas is higher.Reaction chamber is a glass chamber, the one side is fixedly connected with 2-6 group both arms optical fiber, in the opposite side of reaction chamber, be placed with metalloporphyrin LB membrane array plate, the leakage of changing reacted metalloporphyrin LB membrane array plate for convenience and preventing poison gas, be provided with a sealing dodge gate in this side of reaction chamber, by this replaceable metalloporphyrin LB membrane array plate, reach the duplicate detection purpose, solved existing gas sensor fixing use sensitive materials and can only detect a kind of target substance and because of the irreversible sensor that causes of sensitive materials reaction can not reusable problem.Lower end at reaction chamber is provided with air intake near both arms optical fiber one side, reacts with metalloporphyrin LB film sensitization array so that gas to be measured enters in the reaction chamber.Side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber is provided with the gas outlet, so that under the effect of peristaltic pump, makes gas to be measured flow in reaction chamber, and fully reacts with metalloporphyrin LB membrane array, to improve accuracy of detection.Placed metal porphyrin LB membrane array plate in reaction chamber, in order to gas reaction to be measured.This array board is deposited on the substrate by the 2-6 kind metalloporphyrin LB film in nickel-porphyrin, cobalt porphyrin, zinc protoporphyrin, iron porphyrin, copper porphyrin, manganoporphyrin, plumbous porphyrin, the platinum porphyrins etc. and makes.Wherein metalloporphyrin LB film is made by film transfer method or film balance method.The characteristics that different object gas had sensitive property according to different metalloporphyrins, according to the object gas that will detect, determine concrete metalloporphyrin LB membrane array number,, improve the range of application and the dirigibility of sensor greatly in order to finish detection to object gas.Substrate is a transparency glass plate, and the substrate two sides is identical, is used for plated metal porphyrin LB membrane array corresponding to the one side of both arms optical fiber, and the substrate another side is a mirror surface.By silver mirror reaction, utilize electrochemical plating on substrate, to make this smooth uniform mirror surface.Transmit the light of coming in when incident optical, through with gas reaction after metalloporphyrin LB film after, corresponding change will take place in its character, when the light after changing reaches minute surface, the outgoing optical fiber head place of the light signal reflected back optical fiber probe after this minute surface just changes this exports for outgoing optical fiber.
After the present invention adopts technique scheme, mainly contain following characteristics:
The present invention is by making up convertibility LB film sensitization array, and in conjunction with the uses of organizing both arms fibre-optic transmission system (FOTS)s and multidimensional sensitive membrane array more, both utilized the advantage of many groups both arms fibre system transmitting optical signal, made full use of the superiority of metalloporphyrin LB film again with gas reaction, and the sensitization array advantages such as selectivity recognition capability high to target substance of multiple sensitive membrane composition, guaranteed the comparability of signals before and after the reaction from many aspects:
1, sensitive membrane is the LB film, the advantage that the LB film is had has determined the high susceptibility and the selectivity of sensor, be LB film advantage with respect to other technologies in molecular recognition, comprise that the LB film reacts completely with target substance, the film forming good uniformity, thickness can accurately be controlled, and can carry out selective modification to improve sensitive materials selectivity or the like to it by hydridization, therefore with respect in the past fiber gas sensor, its detectability can improve an order of magnitude.
2, sensor of the present invention adopts many group both arms optical fiber to finish the transmission of optical path signal, and both arms optical fiber is finished the input and the output of signal simultaneously.Adopt many group both arms optical fiber, can disposable realization to the reading of array information, utilized optical fiber transmission signal quick simultaneously, accurately, real-time advantage.
3, the structure of convertibility sensitization array is the breakthrough of this fiber gas sensor, and it has guaranteed the advantage of sensor on range of application from three aspects.
(1), by making up sensitization array, the same sensitization array of having realized utilizing different responsive things compositions has solved a kind of sensitive element of traditional fiber sensor and can only detect shortcoming a kind of or a class material the possibility that one or more target substances detect.
(2), sensor sensing array reaction of the present invention back is replaceable, has overcome sensitive materials with the irreversible shortcoming of object gas reaction, and the sensitive membrane preparation easily, so the sensor reusability is good.
(3), in addition, the different target thing is had sensitivity characteristic, reasonably select responsive thing to form new array, can realize detection again new target substance according to different sensitive materials.Like this, fundamentally solved the problem of sensor application scope.
Therefore, the metal porphyrin langmuir blodgett film optical fiber gas sensor of both arms optical fiber transmission signal is organized in the utilization that the present invention makes up more, its maximum characteristics are to detect in real time, the susceptibility height, highly sensitive, selectivity is good, detectability is low, and the sensitive membrane array has light transmission, can change arbitrarily, reusable, sensing range is wide, and it is single to have overcome existing fiber sensor selectivity, and reusability is poor, sensing range is narrow and react numerous shortcomings such as incomplete, has good environmental protection and practical value.
Sensor of the present invention is applicable to the detection to various volatility toxic gases, comprise the detection of various toxic gases in the detection of waste gas in the human habitat and the commercial production, especially phosgene in the commercial production is discharged the detection of qualification, i.e. the detection that phosgene content and phosgene leak in the industrial production environment.
Description of drawings
Fig. 1 is the structural drawing of embodiment 1;
Fig. 2 is the schematic diagram that utilizes detected gas of the present invention.
Among the figure: 1 incident optical, 2 outgoing optical fiber, 3 fibre-optical probes, 4 reaction chambers, 5 gas outlets, 6 metalloporphyrin LB membrane arrays, 7 substrates, 8 minute surfaces, 9 air intakes, 10 gases to be measured, 11 fiber facet array detectors, 12 light sources, 13 condensers, 14 fiber linear arrays probe, 15 peristaltic pumps.
Embodiment
Further specify the present invention below in conjunction with embodiment.
As shown in Figure 1, a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor mainly comprises 4 groups of both arms optical fiber, 4,4 groups of metalloporphyrin LB of reaction chamber membrane array plate.Metalloporphyrin LB membrane array plate is made up of metalloporphyrin LB membrane array 6 and substrate 7 and minute surface 8.Optical fiber is general optical fiber, incident optical 1 is identical with the aperture of outgoing optical fiber 2, every group of both arms optical fiber is by an incident optical 1, an outgoing optical fiber 2 and a fibre-optical probe 3 constitute, the other end of fibre-optical probe 3 is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the optical path direction that the outgoing optical fiber head is reserved part all will point to the central point of the metalloporphyrin LB film of this group both arms optical fiber correspondence, so that can accurately be received by the outgoing optical fiber head after light process substrate minute surface 8 reflections of incident optical head incident.The other end of 4 incident opticals 1 is connected with light-source system, and the other end of 4 outgoing optical fiber 2 is connected with fiber facet array detector 11, and therefore 4 groups of both arms optical fiber can be finished importing into and efferentation of light signal simultaneously.4 groups of both arms optical fiber parallel equidistant are installed in a side of reaction chamber 4, and 4 fibre-optical probes 3 are connected surely with reaction chamber 4 fluid sealant cementations, are used for the input of light source light signal and with the output of the light signal after metalloporphyrin LB membrane array 6 effect.Reaction chamber 4 is a glass chamber, and its thickness is 5 millimeters.Have 4 circular holes that size is identical at reaction chamber 4 near both arms optical fiber one side, 4 holes are equally distributed on a side of reaction chamber 4, so that be connected with four fibre-optical probes 3.In the opposite side of reaction chamber 4, be placed with 4 groups of metalloporphyrin LB membrane array plates, the reacted metalloporphyrin LB of replacing for convenience membrane array plate and prevent the leakage of poison gas, be provided with a sealing dodge gate in reaction chamber 4 these sides, by this replaceable metalloporphyrin LB membrane array plate, reach the duplicate detection purpose.Lower end at reaction chamber 4 is provided with air intake 9 near both arms optical fiber one side, react with metalloporphyrin LB membrane array 6 so that gas 10 to be measured sent in the reaction chamber 4, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber 4 is provided with gas outlet 5, so that under the effect of peristaltic pump 15, make gas 10 to be measured in reaction chamber 4, flow, and fully react with metalloporphyrin LB membrane array 6, improve accuracy of detection.Placed metal porphyrin LB membrane array plate in reaction chamber 4 is deposited on the substrate 7 by cobalt porphyrin, zinc protoporphyrin, iron porphyrin and four kinds of metalloporphyrin LB of platinum porphyrins film and makes sensitization array, in order to detecting sulfur dioxide gas, thereby improves accuracy of detection.Wherein metalloporphyrin LB film is made by the film transfer method.Substrate 7 is a transparency glass plate, and substrate 7 two sides are identical, is used to deposit four kinds of metalloporphyrin LB membrane arrays 6 corresponding to the one side of both arms optical fiber, and substrate 7 another sides are mirror surface 8.By silver mirror reaction, utilize electrochemical plating on substrate 7, to make smooth uniform mirror surface 8.
A kind of metal porphyrin langmuir blodgett film optical fiber gas sensor mainly comprises 2 groups of both arms optical fiber, 4,2 groups of metalloporphyrin LB of reaction chamber membrane array plate.Metalloporphyrin LB membrane array plate is made up of metalloporphyrin LB membrane array 6 and substrate 7 and minute surface 8.Optical fiber is general optical fiber, incident optical 1 is identical with the aperture of outgoing optical fiber 2, every group of both arms optical fiber is by an incident optical 1, an outgoing optical fiber 2 and a fibre-optical probe 3 constitute, the other end of fibre-optical probe 3 is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the optical path direction that the outgoing optical fiber head is reserved part all will point to the central point of the metalloporphyrin LB film of this group both arms optical fiber correspondence, so that can accurately be received by the outgoing optical fiber head after light process substrate minute surface 8 reflections of incident optical head incident.The other end of 2 incident opticals 1 is connected with light-source system, and the other end of 2 outgoing optical fiber 2 is connected with fiber facet array detector 11, and therefore 2 groups of both arms optical fiber can be finished importing into and efferentation of light signal simultaneously.2 groups of both arms optical fiber parallel equidistant are installed in a side of reaction chamber 4, and 2 fibre-optical probes 3 are connected surely with reaction chamber 4 fluid sealant cementations, are used for the input of light source light signal and with the output of the light signal after metalloporphyrin LB membrane array 6 effect.Reaction chamber 4 is a glass chamber, and its thickness is 5 millimeters.Have 2 circular holes that size is identical at reaction chamber 4 near both arms optical fiber one side, 2 holes are equally distributed on a side of reaction chamber 4, so that be connected with two fibre-optical probes 3.In the opposite side of reaction chamber 4, be placed with 2 groups of metalloporphyrin LB membrane array plates, the reacted metalloporphyrin LB of replacing for convenience membrane array plate and prevent the leakage of poison gas, be provided with a sealing dodge gate in reaction chamber 4 these sides, by this replaceable metalloporphyrin LB membrane array plate, reach the duplicate detection purpose.Lower end at reaction chamber 4 is provided with air intake 9 near both arms optical fiber one side, react with metalloporphyrin LB membrane array 6 so that gas 10 to be measured sent in the reaction chamber 4, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber 4 is provided with gas outlet 5, so that under the effect of peristaltic pump 15, make gas 10 to be measured in reaction chamber 4, flow, and fully react with metalloporphyrin LB membrane array 6, improve accuracy of detection.Placed metal porphyrin LB membrane array plate in reaction chamber 4 is deposited on the substrate 7 by zinc protoporphyrin and two kinds of metalloporphyrin LB of plumbous porphyrin film and makes sensitization array, in order to detecting phosgene, thereby improves accuracy of detection.Wherein metalloporphyrin LB film is made by the film transfer method.Substrate 7 is a transparency glass plate, and substrate 7 two sides are identical, is used to deposit two kinds of metalloporphyrin LB membrane arrays 6 corresponding to the one side of both arms optical fiber, and substrate 7 another sides are mirror surface 8.By silver mirror reaction, utilize electrochemical plating on substrate 7, to make smooth uniform mirror surface 8.
A kind of metal porphyrin langmuir blodgett film optical fiber gas sensor mainly comprises 6 groups of both arms optical fiber, 4,6 groups of metalloporphyrin LB of reaction chamber membrane array plate.Metalloporphyrin LB membrane array plate is made up of metalloporphyrin LB membrane array 6 and substrate 7 and minute surface 8.Optical fiber is general optical fiber, incident optical 1 is identical with the aperture of outgoing optical fiber 2, every group of both arms optical fiber is by an incident optical 1, an outgoing optical fiber 2 and a fibre-optical probe 3 constitute, the other end of fibre-optical probe 3 is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the optical path direction that the outgoing optical fiber head is reserved part all will point to the central point of the metalloporphyrin LB film of this group both arms optical fiber correspondence, so that can accurately be received by the outgoing optical fiber head after light process substrate minute surface 8 reflections of incident optical head incident.The other end of 6 incident opticals 1 is connected with light-source system, and the other end of 6 outgoing optical fiber 2 is connected with fiber facet array detector 11, and therefore 6 groups of both arms optical fiber can be finished importing into and efferentation of light signal simultaneously.6 groups of both arms optical fiber parallel equidistant are installed in a side of reaction chamber 4, and 6 fibre-optical probes 3 are connected surely with reaction chamber 4 fluid sealant cementations, are used for the input of light source light signal and with the output of the light signal after metalloporphyrin LB membrane array 6 effect.Reaction chamber 4 is a glass chamber, and its thickness is 5 millimeters.Have 6 circular holes that size is identical at reaction chamber 4 near both arms optical fiber one side, 6 holes are equally distributed on a side of reaction chamber 4, so that be connected with six fibre-optical probes 3.In the opposite side of reaction chamber 4, be placed with 6 groups of metalloporphyrin LB membrane array plates, the reacted metalloporphyrin LB of replacing for convenience membrane array plate and prevent the leakage of poison gas, be provided with a sealing dodge gate in reaction chamber 4 these sides, by this replaceable metalloporphyrin LB membrane array plate, reach the duplicate detection purpose.Lower end at reaction chamber 4 is provided with air intake 9 near both arms optical fiber one side, react with metalloporphyrin LB membrane array 6 so that gas 10 to be measured sent in the reaction chamber 4, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber 4 is provided with gas outlet 5, so that under the effect of peristaltic pump 15, make gas 10 to be measured in reaction chamber 4, flow, and fully react with metalloporphyrin LB membrane array 6, improve accuracy of detection.Placed metal porphyrin LB membrane array plate in reaction chamber 4, be deposited on the substrate 7 by nickel-porphyrin, copper porphyrin, manganoporphyrin, cobalt porphyrin, zinc protoporphyrin and six kinds of metalloporphyrin LB of iron porphyrin film and make sensitization array, in order to the detection nitrogen dioxide gas, thereby improve accuracy of detection.Wherein metalloporphyrin LB film is made by the film balance method.Substrate 7 is a transparency glass plate, and substrate 7 two sides are identical, is used to deposit six kinds of metalloporphyrin LB membrane arrays 6 corresponding to the one side of both arms optical fiber, and substrate 7 another sides are mirror surface 8.By silver mirror reaction, utilize electrochemical plating on substrate 7, to make smooth uniform mirror surface 8.
Adopt the concrete course of work of detected gas of the present invention
As shown in Figure 2, embodiment 1 utilizes the device of sensor gas to be made up of light source 12, fiber linear array probe 14, fiber gas sensor, peristaltic pump 15, gas to be measured 10 and fiber facet array detector 11.When peristaltic pump 15 work, gas 10 to be measured is pumped in the reaction chamber 4, and reacts with metalloporphyrin LB membrane array 6, and metalloporphyrin LB film optical property changes.After reacting completely, light-source system is started working, and light source 12 is converged by condenser 13, obtains directional light.This directional light incides on the fiber linear array probe, fiber linear array probe is converted to the directional light of incident in the incident optical 1 that lightwave signal imports every group of both arms optical fiber respectively into, and reach the incident optical head place of fibre-optical probe, form the incident light part of sensor thus.When incident light 1 is mapped on the metalloporphyrin LB membrane array 6, can be with the reacted metalloporphyrin LB of object gas film to some fixed wave length light signal generating absorption in the light signal.After this section wavelength energy was absorbed, the incident light after the change reflected via the minute surface 8 of substrate opposite side again, and enters the outgoing optical fiber head place of both arms fibre-optical probe.After emergent light is successfully received, reach fiber facet array detector 11, and receive, be converted into colouring information by the fiber facet array detector by outgoing optical fiber 2.This colouring information also is RGB (RGB) tristimulus signals, constitutes 3 * 4 information array (3 kinds of color detection signals, 4 kinds of metalloporphyrins) thus, finally obtains 12 response signals thus.By software these 12 signals are handled at last, pattern-recognition, and to the end recognition result.
Claims (4)
1. metal porphyrin langmuir blodgett film optical fiber gas sensor, mainly comprise optical fiber, reaction chamber (4), it is characterized in that metalloporphyrin LB membrane array plate in addition, optical fiber is both arms optical fiber, metalloporphyrin LB membrane array plate is made up of metalloporphyrin LB membrane array (6) and substrate (7) and minute surface (8), both arms optical fiber is the 2-6 group, the group number of both arms optical fiber is corresponding consistent with metalloporphyrin LB membrane array number, each group both arms optical fiber is by an incident optical (1), outgoing optical fiber (2) and fibre-optical probe (3) constitute, and reserve very short optical fiber head part at the other end of fibre-optical probe (3), its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in opposite directions in the fibre-optical probe (3), and incident, the outgoing optical fiber head is reserved the central point that optical path direction partly all will point to the metalloporphyrin LB film of this group both arms optical fiber correspondence, the other end of 2-6 root incident optical (1) is connected with light-source system, the other end of 2-6 root outgoing optical fiber (2) is connected with fiber facet array detector (11), 2-6 road both arms optical fiber parallel equidistant is installed in a side of reaction chamber (4), 2-6 fibre-optical probe (3) and reaction chamber (4) fixed seal connection, reaction chamber (4) is a glass chamber, the one side is fixedly connected with 2-6 group both arms optical fiber, in the opposite side of reaction chamber (4), be placed with metalloporphyrin LB membrane array plate, be provided with the dodge gate of a sealing in this side of reaction chamber (4), lower end at reaction chamber (4) is provided with air intake (9) near both arms optical fiber one side, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber (4) is provided with gas outlet (5), placed metal porphyrin LB membrane array plate in reaction chamber (4), by nickel-porphyrin, the cobalt porphyrin, zinc protoporphyrin, iron porphyrin, copper porphyrin, manganoporphyrin, plumbous porphyrin, 2-6 kind metalloporphyrin LB film in the platinum porphyrins is deposited on the substrate (7) to be made, wherein metalloporphyrin LB film is made by film transfer method or film balance method, the characteristics that different object gas had sensitive property according to different metalloporphyrins, the requirement of the object gas that detects according to need, determine concrete metalloporphyrin LB membrane array number, substrate (7) is a transparency glass plate, substrate (7) two sides is identical, one side corresponding to both arms optical fiber is used for plated metal porphyrin LB membrane array (6), substrate (7) another side is mirror surface (8), by silver mirror reaction, utilize electrochemical plating on substrate (7), to make smooth uniform mirror surface (8).
2. according to the described metal porphyrin langmuir blodgett film optical fiber gas sensor of claim 1, it is characterized in that a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor, mainly comprise 4 groups of both arms optical fiber, reaction chamber (4), 4 groups of metalloporphyrin LB film sensitization array plates, metalloporphyrin LB film sensitization array plate is made up of metalloporphyrin LB membrane array (6) and substrate (7) and minute surface (8), optical fiber is general optical fiber, incident optical (1) is identical with the aperture of outgoing optical fiber (2), every group of both arms optical fiber is by an incident optical (1), an outgoing optical fiber (2) and a fibre-optical probe (3) constitute, the other end of fibre-optical probe is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the outgoing optical fiber head is reserved the central point that optical path direction partly all will point to the metalloporphyrin LB film of this group both arms optical fiber correspondence, the other end of 4 incident opticals (1) is connected with light-source system, the other end of 4 outgoing optical fiber (2) is connected with fiber facet array detector (11), 4 road both arms optical fiber parallel equidistant are installed in a side of reaction chamber (4), 4 fibre-optical probes (3) are connected surely with reaction chamber (4) fluid sealant cementation, reaction chamber (4) is a glass chamber, its thickness is 5 millimeters, have 4 circular holes that size is identical at reaction chamber (4) near both arms optical fiber one side, 4 holes are equally distributed on a side of reaction chamber (4), so that be connected with four fibre-optical probes (3), in the opposite side of reaction chamber (4), be placed with 4 groups of metalloporphyrin LB membrane array plates, be provided with the dodge gate of a sealing in this side of reaction chamber (4), lower end at reaction chamber (4) is provided with air intake (9) near both arms optical fiber one side, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber (4) is provided with gas outlet (5), placed metal porphyrin LB membrane array plate in reaction chamber (4), by the cobalt porphyrin, zinc protoporphyrin, iron porphyrin and four kinds of metalloporphyrin LB of platinum porphyrins film are deposited on the sensitization array of making on the substrate (7), in order to detect sulfur dioxide gas, wherein metalloporphyrin LB film is made by the film transfer method, substrate (7) is a transparency glass plate, substrate (7) two sides is identical, one side corresponding to both arms optical fiber is used to deposit four kinds of metalloporphyrin LB membrane arrays (6), substrate (7) another side is mirror surface (8), by silver mirror reaction, utilize electrochemical plating on substrate (7), to make smooth uniform mirror surface (8).
3. according to the described metal porphyrin langmuir blodgett film optical fiber gas sensor of claim 1, it is characterized in that a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor, mainly comprise 2 groups of both arms optical fiber, reaction chamber (4), 2 groups of metalloporphyrin LB film sensitization array plates, metalloporphyrin LB film sensitization array plate is made up of metalloporphyrin LB membrane array (6) and substrate (7) and minute surface (8), optical fiber is general optical fiber, incident optical (1) is identical with the aperture of outgoing optical fiber (2), every group of both arms optical fiber is by an incident optical (1), an outgoing optical fiber (2) and a fibre-optical probe (3) constitute, the other end of fibre-optical probe is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the outgoing optical fiber head is reserved the central point that optical path direction partly all will point to the metalloporphyrin LB film of this group both arms optical fiber correspondence, the other end of 2 incident opticals (1) is connected with light-source system, the other end of 2 outgoing optical fiber (2) is connected with fiber facet array detector (11), 2 road both arms optical fiber parallel equidistant are installed in a side of reaction chamber (4), 2 fibre-optical probes (3) are connected surely with reaction chamber (4) fluid sealant cementation, reaction chamber (4) is a glass chamber, its thickness is 5 millimeters, have 2 circular holes that size is identical at reaction chamber (4) near both arms optical fiber one side, 2 holes are equally distributed on a side of reaction chamber (4), so that be connected with two fibre-optical probes (3), in the opposite side of reaction chamber (4), be placed with 2 groups of metalloporphyrin LB membrane array plates, be provided with the dodge gate of a sealing in this side of reaction chamber (4), lower end at reaction chamber (4) is provided with air intake (9) near both arms optical fiber one side, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber (4) is provided with gas outlet (5), placed metal porphyrin LB membrane array plate in reaction chamber (4), be deposited on the sensitization array of making on the substrate (7) by zinc protoporphyrin and two kinds of metalloporphyrin LB of plumbous porphyrin film, in order to detect phosgene, wherein metalloporphyrin LB film is made by the film transfer method, substrate (7) is a transparency glass plate, substrate (7) two sides is identical, one side corresponding to both arms optical fiber is used to deposit two kinds of metalloporphyrin LB membrane arrays (6), substrate (7) another side is mirror surface (8), by silver mirror reaction, utilize electrochemical plating on substrate (7), to make smooth uniform mirror surface (8).
4. according to the described metal porphyrin langmuir blodgett film optical fiber gas sensor of claim 1, it is characterized in that a kind of metal porphyrin langmuir blodgett film optical fiber gas sensor, mainly comprise 6 groups of both arms optical fiber, reaction chamber (4), 6 groups of metalloporphyrin LB film sensitization array plates, metalloporphyrin LB film sensitization array plate is made up of metalloporphyrin LB membrane array (6) and substrate (7) and minute surface (8), optical fiber is general optical fiber, incident optical (1) is identical with the aperture of outgoing optical fiber (2), every group of both arms optical fiber is by an incident optical 1, an outgoing optical fiber (2) and a fibre-optical probe (3) constitute, the other end of fibre-optical probe (3) is reserved very short optical fiber head part, its incident, the outgoing optical fiber head is with equal angular, be symmetrically fixed in the fibre-optical probe in opposite directions, and incident, the outgoing optical fiber head is reserved the central point that optical path direction partly all will point to the metalloporphyrin LB film of this group both arms optical fiber correspondence, the other end of 6 incident opticals (1) is connected with light-source system, the other end of 6 outgoing optical fiber (2) is connected with fiber facet array detector (11), 6 road both arms optical fiber parallel equidistant are installed in a side of reaction chamber (4), 6 fibre-optical probes (3) are connected surely with reaction chamber (4) fluid sealant cementation, reaction chamber (4) is a glass chamber, its thickness is 5 millimeters, have 6 circular holes that size is identical at reaction chamber (4) near both arms optical fiber one side, 6 holes are equally distributed on a side of reaction chamber (4), so that be connected with six fibre-optical probes (3), in the opposite side of reaction chamber (4), be placed with 6 groups of metalloporphyrin LB membrane array plates, be provided with the dodge gate of a sealing in this side of reaction chamber (4), lower end at reaction chamber (4) is provided with air intake (9) near both arms optical fiber one side, side at the close metalloporphyrin LB membrane array plate in the upper end of reaction chamber (4) is provided with gas outlet (5), placed metal porphyrin LB membrane array plate in reaction chamber (4), by nickel-porphyrin, copper porphyrin, manganoporphyrin, the cobalt porphyrin, zinc protoporphyrin and six kinds of metalloporphyrin LB of iron porphyrin film are deposited on the sensitization array of making on the substrate (7), in order to detect nitrogen dioxide gas, wherein metalloporphyrin LB film is made by the film balance method, substrate (7) is a transparency glass plate, substrate (7) two sides is identical, one side corresponding to both arms optical fiber is used to deposit six kinds of metalloporphyrin LB membrane arrays (6), substrate (7) another side is mirror surface (8), by silver mirror reaction, utilize electrochemical plating on substrate (7), to make smooth uniform mirror surface (8).
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| JP6797688B2 (en) * | 2014-03-02 | 2020-12-09 | マサチューセッツ インスティテュート オブ テクノロジー | Gas sensor based on metal-carbon complex |
| CN104897733B (en) * | 2015-04-27 | 2017-12-15 | 济南大学 | A kind of nitrogen dioxide gas sensor based on p-aminophenyl substitution porphyrin aggregate material |
| CN105223237B (en) * | 2015-09-10 | 2017-12-26 | 济南大学 | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO2Gas sensor |
| CN112924424B (en) * | 2021-01-21 | 2023-04-14 | 重庆大学 | Preparation method of fluorescent thin block and TATP optical fiber fluorescent probe for trace explosives |
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