CN108007988B - Nanocomposite and its electrochemical sensor for specific recognition cadmium ion - Google Patents
Nanocomposite and its electrochemical sensor for specific recognition cadmium ion Download PDFInfo
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Abstract
The invention discloses the nanocomposites and electrochemical sensor for specific recognition cadmium ion, by graphene oxide, gold nanoparticle, tetraphenylporphyrin, which combines, plays synergistic effect, prepare graphene oxide/gold nano grain/tetraphenylporphyrin compound, and it is combined with electrochemical measuring technique, a kind of novel highly selective and high-precision electrochemical sensor for measuring the heavy metal especially heavy metal Cd in aqueous solution, detection sensitivity is high, high specificity, and quick and precisely, and it is easy to operate, price is lower, it avoids using large-scale instrument, and live Emergent detection can be carried out.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to for specific recognition cadmium ion nanocomposite,
Electrochemical sensor.
Background technique
Heavy metal in the ecosystem indefinitely exists due to its not biodegradable, their existence rings to the mankind
Border and health constitute great threat, and heavy metal pollution was emphasis pollutant by united nations environment plan column in 1974.Cadmium (Cd)
As most heavy one of heavy metal is endangered in heavy metal pollution, in plating, nickel-cadmium cell, alloy, pigment, fluorescent powder, pesticide etc.
Multiple industries are widely applied, and excessive cadmium causes serious water pollution, soil pollution and food pollution.The World Health Organization proposes
The intake of Cd (II) ion drinking water standard of 3ng/mL, excessive cadmium ion can produce the human organs such as liver, lung, kidney and prostate
Raw damage, and main accumulation is in kidney, in the intracorporal long half time of people up to 10~35 years.At present the cadmium developed from
Sub- detection technique, such as fluorescent spectrometry, atomic absorption spectrophotometry, atomic emission spectrometry, colorimetric method, electrochemical analysis
Some inevitable disadvantages, such as detection device valuableness are faced, operating cost is high, and operator's specialization requires height, point
The analysis time is long, and sensitivity is low, is not easy to rapid field application etc.；However monitoring fast and convenient in terms of cadmium pollution emergency processing
It is very necessary for protection human health and environment, therefore, be badly in need of it is a kind of quickly, it is simple, can field application high sensitivity point
Analysis method carrys out Monitoring of Cadmium ion concentration.
Different from conventional method, electrochemical detection method has an analysis, and speed is fast, easy to operate, high sensitivity, at low cost
The advantages that.Gold nanoparticle is because having biggish specific surface area, and good biocompatibility and excellent electric conductivity are in electrochemistry
It is used widely in detection, the electricity between biomolecule and the redox center of electrode surface can be enhanced in gold nanoparticle
Son transfer is also used as the reaction rate that catalyst improves electrochemistry；Graphene be one kind by carbon atom with sp2 hybridized orbit
The flat film that hexangle type is in honeycomb lattice is formed, there is brilliant calorifics, machinery and chemical property, graphene has pole
Big specific surface area, can be with the abundant combination such as metal, polymer and metallorganic, to prepare, electric conductivity is excellent, ties
The stable nanocomposite of structure, and lower production costs are very suitable to exploitation high-performance composite materials；Porphyrin is as a kind of tool
There is the electron mediator of good electrocatalysis characteristic, because its special chemical structure and performance have specificly-response to metal ion；
Graphene oxide, gold nanoparticle, tetraphenylporphyrin are combined there is presently no relevant report and prepare graphene oxide/gold nano
Particle/tetraphenylporphyrin composite material, combines with electrochemical measuring technique, develops novel highly selective and high-precision electrification
Sensor is learned to be used to measure the cadmium ion in aqueous solution.
Summary of the invention
For the drawbacks described above for overcoming the prior art, the purpose of the present invention is to provide receiving for specific recognition cadmium ion
Nano composite material；The object of the invention is also to provide the preparation methods of above-mentioned nanocomposite.
The object of the invention is also to provide the electrochemical sensors prepared by above-mentioned nanocomposite；Mesh of the invention
Also reside in the preparation method of above-mentioned electrochemical sensor be provided
On the one hand, present inventor combines graphene oxide, gold nanoparticle, tetraphenylporphyrin, plays collaboration
Effect, prepares graphene oxide/gold nano grain/tetraphenylporphyrin composite material, combines with electrochemical measuring technique, invents
A kind of novel highly selective and high-precision electrochemical sensor is used to measure the heavy metal cadmium ion in aqueous solution.
On the other hand, by using tetraphenylporphyrin, alternatively property biomolecule combination cadmium ion, graphene oxide promote
Into the complexation reaction of cadmium ion and derivatives of porphyrin, the electric conductivity of electrode surface is improved.Further, gold nanoparticle passes through gold
Tetraphenylporphyrin with sulfydryl is connected further to graphene oxide/gold nano grain composite material surface by mercapto key, is improved
Highly sensitive, the quick detection to heavy metal cadmium ion is realized in the sensitivity of Electrochemical Detection.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
For the nanocomposite of specific recognition cadmium ion, including graphene oxide/gold nano grain/tetraphenyl porphin
Quinoline compound.
The preparation method of the above-mentioned nanocomposite for specific recognition cadmium ion, includes the following steps:
(1) it prepares graphene oxide/gold nano grain compound: being first distributed to a certain amount of graphene oxide ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxide of 10ml molten
Liquid mixes in round-bottomed flask with the chlorauric acid solution that 0.04ml concentration is 0.25M/L, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid removes supernatant, obtaining concentration is by above-mentioned black dispersion liquid after being centrifuged 30min under revolving speed is 13000rpm
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) it prepares graphene oxide/gold nano grain/tetraphenylporphyrin compound: taking graphite oxide in 4ml step (1)
5- [4- (4- sulfydryl butoxy)-phenyl] -10,15,20- triphen that alkene/gold nano grain compound and 25uL concentration are 1mM/L
The mixing of base porphyrin, stirs for 24 hours at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating to obtain the final product.
The method for preparing electrochemical sensor by above-mentioned nanocomposite, includes the following steps:
(1) it prepares graphene oxide/gold nano grain compound: being first distributed to a certain amount of graphene oxide ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxide of 10ml molten
Liquid mixes in round-bottomed flask with the chlorauric acid solution that 0.04ml concentration is 0.25M/L, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid removes supernatant, obtaining concentration is by above-mentioned black dispersion liquid after being centrifuged 30min under revolving speed is 13000rpm
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) it prepares graphene oxide/gold nano grain/tetraphenylporphyrin compound: taking graphite oxide in 4ml step (1)
5- [4- (4- sulfydryl butoxy)-phenyl] -10,15,20- triphen that alkene/gold nano grain compound and 25uL concentration are 1mM/L
The mixing of base porphyrin, stirs for 24 hours at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating；
(3) glass-carbon electrode of preparation modification: being respectively 1.0um with partial size using sand paper and the alumina powder of 0.05um is to glass
After carbon electrode is polished, it is inserted into acetone, each ultrasound 3min in ultrapure water respectively, then uses ultrapure water, nitrogen is dried；It will
Graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex that 5uL step (2) obtains is added drop-wise to treated
Glassy carbon electrode surface continues to be added dropwise 5uL mass fraction as the chitosan solution of 0.05wt%, then must aoxidize stone after drying after drying
Black alkene/gold nano grain/tetraphenylporphyrin nano-complex modification glass-carbon electrode；
(4) it prepares electrochemical sensor: the modified electrode prepared in step (3) being inserted into 40ul cadmium-ion solution and is soaked
It is taken out after bubble 30min, water flushes three times, and insertion concentration is that DPV scanning is carried out in the Klorvess Liquid of 1M/L, makes after the completion of scanning
Above-mentioned modified electrode is rinsed with ultrapure water, 30min in saturation EDTA solution is then immersed in, finally uses ultrapure water
It is dried after flushing.
The glass-carbon electrode of modification described in step (3) further include graphene oxide modification glass-carbon electrode, graphene oxide/
The glass-carbon electrode of gold nano grain compound modification, the glass-carbon electrode of gold nano grain/tetraphenylporphyrin compound modification and/or
Graphene oxide/tetraphenylporphyrin compound modification glass-carbon electrode.
It is respectively 1.0um with partial size that the glass-carbon electrode preparation method of the graphene oxide modification, which includes: using sand paper,
After polishing with the alumina powder of 0.05um glass-carbon electrode, it is inserted into acetone, each ultrasound 3min in ultrapure water respectively, then uses
Ultrapure water, nitrogen are dry；The yellowish-brown graphene oxide solution that concentration in 5uL step (1) is 1mg/mL is added drop-wise to
Glassy carbon electrode surface of stating that treated, continues 5uL mass fraction is added dropwise after drying and is the chitosan solution of 0.05wt%, then dries
The glass-carbon electrode of graphene oxide modification is obtained afterwards；
The graphene oxide/gold nano grain compound modification glass-carbon electrode preparation method includes: using sand paper
Respectively with after partial size is 1.0um and the alumina powder of 0.05um polishes to glass-carbon electrode, being inserted into acetone respectively, in ultrapure water
Each ultrasound 3min, then uses ultrapure water, and nitrogen is dry；By concentration in 5uL step (1) be 1mg/mL graphene oxide/
Gold nano grain compound is added drop-wise to treated glassy carbon electrode surface, continues dropwise addition 5uL mass fraction after drying and is
The chitosan solution of 0.05wt%, then graphene oxide/gold nano grain compound modification glass-carbon electrode is obtained after drying；
DPV sweep parameter described in step (4) includes: that scanning range is -1.0V -0.15V, impulse amplitude 50mV, vibration
Width is 4mV, burst length 0.2S, sampling period 2S.
One kind electrochemical sensor as made from above-mentioned preparation method.
Compared with prior art, the positive effect of the present invention is that:
(1) electrochemical sensor prepared by the present invention is for detecting heavy metal especially heavy metal Cd, detection sensitivity is high,
High specificity, and quick and precisely；(2) electrochemical sensor of the invention is easy to operate, and price is lower, avoids using large-scale instrument
Device, and live Emergent detection can be carried out.
Detailed description of the invention
Fig. 1 is the working principle diagram that electrochemical sensor of the present invention is used to detect heavy metal Cd；
Fig. 2 be the present invention in graphite oxide it is dilute/gold nano grain/tetraphenylporphyrin nano-complex (a), graphite oxide
The raman spectrum of dilute/gold nano grain compound (b), graphene oxide (c), wherein 828,995,1055,1134,1236cm-1
Place's Raman peaks are the characteristic peaks of tetraphenylporphyrin；
Fig. 3 be graphite oxide it is dilute/electron microscope of gold nano grain compound (b)；
Fig. 4 be graphite oxide it is dilute/energy spectrum diagram of gold nano grain compound (b)；
Fig. 5 is DPV response curve of the glass-carbon electrode of different materials modification to 1mM cadmium ion in 1M KCl solution,
In, graphene oxide/gold nano grain/tetraphenylporphyrin (a), graphene oxide/gold nano grain (b), gold nano grain/tetra-
Phenyl porphyrin (c), chitosan (d), graphene oxide/tetraphenylporphyrin (e)；
Fig. 6 is graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode to 1mM cadmium ion
The continuous five times DPV response curves in 1M KCl solution；
Fig. 7 is that graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode is 1mM to concentration
The DPV response curve of dissimilar metals ion, wherein (a) Fe3+, (b) Na+, (c) Mg2+, (d) Ca2+, (e) Mn2+, (f) Hg2 +, (g) Ag+, (h) Pb2+, (i) Cd2+；
Fig. 8 is that graphene oxide/gold nano grain/tetraphenylporphyrin compound object modification glass-carbon electrode distinguishes concentration
It is the DPV response curve of 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion；
Fig. 9 is that graphene oxide/gold nano grain/tetraphenylporphyrin compound object modification glass-carbon electrode distinguishes concentration
The linear relationship chart of the cadmium ion DPV for being 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM response.
Specific embodiment
Below in conjunction with the drawings and specific embodiments for illustrating the present invention, but it is not intended to limit the scope of the invention.
Embodiment
The electrochemical sensor system of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode
Preparation Method includes the following steps:
(1) it prepares graphene oxide/gold nano grain compound: being first distributed to a certain amount of graphene oxide ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxide of 10ml molten
Liquid mixes in round-bottomed flask with the chlorauric acid solution that 0.04ml concentration is 0.25M/L, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid removes supernatant, obtaining concentration is by above-mentioned black dispersion liquid after being centrifuged 30min under revolving speed is 13000rpm
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) it prepares graphene oxide/gold nano grain/tetraphenylporphyrin compound: taking graphite oxide in 4ml step (1)
5- [4- (4- sulfydryl butoxy)-phenyl] -10,15,20- triphen that alkene/gold nano grain compound and 25uL concentration are 1mM/L
The mixing of base porphyrin, stirs for 24 hours at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating；
(3) glass-carbon electrode of preparation modification: being respectively 1.0um with partial size using sand paper and the alumina powder of 0.05um is to glass
After carbon electrode is polished, it is inserted into acetone, each ultrasound 3min in ultrapure water respectively, then uses ultrapure water, nitrogen is dried；It will
Graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex that 5uL step (2) obtains is added drop-wise to treated
Glassy carbon electrode surface continues to be added dropwise 5uL mass fraction as the chitosan solution of 0.05wt%, then must aoxidize stone after drying after drying
Black alkene/gold nano grain/tetraphenylporphyrin nano-complex modification glass-carbon electrode；
(4) it prepares electrochemical sensor: the modified electrode prepared in step (3) being inserted into 40ul cadmium-ion solution and is soaked
It is taken out after bubble 30min, water flushes three times, and insertion concentration is that DPV scanning is carried out in the Klorvess Liquid of 1M/L, makes after the completion of scanning
Above-mentioned modified electrode is rinsed with ultrapure water, 30min in saturation EDTA solution is then immersed in, finally uses ultrapure water
It is dried after flushing；It is -1.0V -0.15V, impulse amplitude 50mV that wherein DPV sweep parameter, which includes: scanning range, and amplitude is
4mV, burst length 0.2S, sampling period 2S.
Comparative example 1
The preparation method is the same as that of Example 1, the difference is that the glass-carbon electrode of modification is graphene oxide/gold nano grain
(b) glass-carbon electrode modified.
Comparative example 2
The preparation method is the same as that of Example 1, the difference is that the glass-carbon electrode of modification is gold nano grain/tetraphenylporphyrin
(c) glass-carbon electrode modified.
Comparative example 3
The preparation method is the same as that of Example 1, the difference is that the glass-carbon electrode of modification is the glass carbon electricity of chitosan (d) modification
Pole.
Comparative example 4
The preparation method is the same as that of Example 1, the difference is that the glass-carbon electrode of modification is graphene oxide/tetraphenylporphyrin
(e) glass-carbon electrode modified.
Referring to attached drawing 1, it is used to detect the working principle diagram of heavy metal Cd for electrochemical sensor of the present invention.
Referring to attached drawing 2, for graphite oxide in the present invention it is dilute/gold nano grain/tetraphenylporphyrin nano-complex (a), oxygen
Graphite is dilute/gold nano grain compound (b), graphene oxide (c) raman spectrum, wherein 828,995,1055,1134,
1236cm-1Place's Raman peaks are the characteristic peaks of tetraphenylporphyrin；By being compared to its above-mentioned Raman spectrum, in graphite oxide
828,995,1055,1134 can be clearly visible in dilute/gold nano grain/tetraphenylporphyrin nano-complex (a) Raman spectrum,
1236cm-1Locate tetraphenylporphyrin Characteristic Raman peak, with graphite oxide it is dilute/gold nano grain compound (b), graphene oxide
(c) raman spectrum compares, and further illustrates that tetraphenylporphyrin is successfully combined with graphene oxide/gold nano grain, oxygen
Graphite is dilute/and gold nano grain/tetraphenylporphyrin nano-complex is successfully prepared.
Referring to attached drawing 3, be graphite oxide it is dilute/electron microscope of gold nano grain compound (b)；As we can clearly see from the figure
The gold nano grain of membranaceous surface of graphene oxide, show graphite oxide it is dilute/gold nano grain compound is successfully prepared.
Referring to attached drawing 4, be graphite oxide it is dilute/energy spectrum diagram of gold nano grain compound (b)；As we can clearly see from the figure
Contain carbon, oxygen, gold element in the material, further proves that graphene oxide/gold nano grain compound is successfully prepared.
Referring to attached drawing 5, DPV of the 1mM cadmium ion in 1M KCl solution is responded for the glass-carbon electrode of different materials modification
Curve, wherein graphene oxide/gold nano grain/tetraphenylporphyrin (a), graphene oxide/gold nano grain (b), gold nano
Particle/tetraphenylporphyrin (c), chitosan (d), graphene oxide/tetraphenylporphyrin (e)；From the figure, it can be seen that having modified oxygen
Graphite alkene/gold nano grain/tetraphenylporphyrin (a) material glass-carbon electrode is apparently higher than the response of cadmium ion and has modified oxygen
Graphite alkene/gold nano grain (b), gold nano grain/tetraphenylporphyrin (c), chitosan (d) or graphene oxide/tetraphenyl
The glass-carbon electrode of porphyrin (e) material shows to modify graphene oxide/gold nano grain/tetraphenylporphyrin (a) material glass carbon electricity
Pole combines the good characteristic of graphene oxide, gold nano grain, tetraphenylporphyrin, has sensitive response to cadmium ion.
It is graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode to 1mM referring to attached drawing 6
Cadmium ion continuous five times DPV response curves in 1M KCl solution；It can be seen that good reproduction is presented in five DPV tests
Property, show that graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode stability is good, is carrying out cadmium
There is good reproducibility when ion detection.
It is graphene oxide/gold nano grain/tetraphenylporphyrin compound modification glass-carbon electrode to dense referring to attached drawing 7
Degree is the DPV response curve of 1mM dissimilar metals ion, wherein (a) Fe3+, (b) Na+, (c) Mg2+, (d) Ca2+, (e) Mn2 +, (f) Hg2+, (g) Ag+, (h) Pb2+, (i) Cd2+；Cd as we can see from the figure2+(i) DPV response curve differs markedly from it
The response of his metal ion avoids the presence of other metal ions to Cd2+Detection generate interference, guarantee this method preparation glass
Carbon electrode is to Cd2+Sensitive response.
It is graphene oxide/gold nano grain/tetraphenylporphyrin compound object modification glass-carbon electrode pair referring to attached drawing 8
Concentration is respectively the DPV response curve of 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion；It can from figure
Out as concentration of cadmium ions increases, the glass-carbon electrode DPV of this method modification responds enhancing, illustrates DPV signal and concentration of cadmium ions
It presents obvious related.
It is graphene oxide/gold nano grain/tetraphenylporphyrin compound object modification glass-carbon electrode pair referring to attached drawing 9
Concentration is respectively the linear relationship chart of 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion DPV response；From figure
It can be seen that the glass-carbon electrode of this method modification is to the DPV response of the cadmium ion of 0.05-10Mm and concentration of cadmium ions with good
Linear relationship, further demonstrate that this method can detect the cadmium ion within the scope of 0.05-10Mm.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (2)
1. being used for the nanocomposite of specific recognition cadmium ion, which is characterized in that including graphene oxide/gold nano
Grain/tetraphenylporphyrin compound；The preparation method of the nanocomposite the following steps are included:
Graphene oxide is distributed to ultrasound 6h in ultrapure water, obtains the yellowish-brown graphene oxide solution that concentration is 1mg/mL；
The above-mentioned graphene oxide solution of 10ml and 0.04mL concentration is taken to mix in round-bottomed flask for the chlorauric acid solution of 0.25M/L
It closes, and the sodium hydroxide solution of 0.5M/L is added dropwise until pH is 10, room temperature continues ultrasound 0.5h, and 100 DEG C of reflux 1h are obtained black
Color dispersion liquid, 13000rpm are centrifuged 30min, remove supernatant, and it is multiple to obtain graphene oxide/gold nano grain that concentration is 1mg/mL
Close object；
Take the above-mentioned graphene oxide of 4mL/gold nano grain compound and 25uL concentration for 5- [4- (the 4- sulfydryl fourth oxygen of 1mM/L
Base)-phenyl] -10, the mixing of 15,20- Triphenylporphyrins is stirred at room temperature for 24 hours, obtains graphene oxide/gold nano grain/tetraphenyl
Porphyrin nano compound, centrifugal concentrating to get.
2. the preparation method of electrochemical sensor characterized by comprising
(1) it is inserted respectively using sand paper respectively with after partial size is 1.0um and the alumina powder of 0.05um polishes to glass-carbon electrode
Enter acetone, each ultrasound 3min in ultrapure water, then use ultrapure water, nitrogen is dry；Stone will be aoxidized described in 5uL claim 1
Black alkene/gold nano grain/tetraphenylporphyrin nano-complex is added drop-wise to treated glassy carbon electrode surface, continues after drying
The chitosan solution that 5uL mass fraction is 0.05wt% is added dropwise, dries, obtains graphene oxide/gold nano grain/tetraphenylporphyrin
Nano-complex modified glassy carbon electrode；
(2) the insertion 40ul cadmium-ion solution of modified glassy carbon electrode obtained by step (1) being impregnated into 30min, taken out, water flushes three times,
It is inserted into the Klorvess Liquid that concentration is 1M/L and carries out DPV scanning, scanning range is -1.0V-0.15V, impulse amplitude 50mV, vibration
Width is 4mV, burst length 0.2S, sampling period 2S；Again be immersed in after ultrapure water saturation EDTA solution 30min,
Ultrapure water, dry to get；The cadmium ion that gained chemical sensor is 0.05-10mM for detectable concentration.
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| CN106996945A (en) * | 2016-01-23 | 2017-08-01 | 江南石墨烯研究院 | A kind of noble metal decorated method of lead ion sensor |
| CN107064034A (en) * | 2017-05-19 | 2017-08-18 | 深圳市绿恩环保技术有限公司 | The detection method of cadmium in a kind of water |
| CN107219280B (en) * | 2017-07-21 | 2019-07-05 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
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