CN110243878A - One kind is with Bi1-xLaxFeO3Electric potential type acetone sensor, preparation method and applications are blended together for sensitive electrode - Google Patents

One kind is with Bi1-xLaxFeO3Electric potential type acetone sensor, preparation method and applications are blended together for sensitive electrode Download PDF

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CN110243878A
CN110243878A CN201910569830.9A CN201910569830A CN110243878A CN 110243878 A CN110243878 A CN 110243878A CN 201910569830 A CN201910569830 A CN 201910569830A CN 110243878 A CN110243878 A CN 110243878A
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electrode
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卢革宇
刘彤
梁喜双
刘凤敏
刘方猛
孙鹏
高原
闫旭
王晨光
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Jilin University
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Abstract

One kind is with Bi1‑xLaxFeO3For the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor, preparation method and applications, belongs to gas sensor technical field.It is by the Al with Pt heating electrode2O3Ceramic wafer, Ce0.8Gd0.2O1.95Substrate, Pt reference electrode and Bi1‑xLaxFeO3(x=0.1~0.9) sensitive electrode composition；Pt reference electrode and sensitive electrode are separate and symmetrically prepare in Ce0.8Gd0.2O1.95The both ends of upper surface of base plate, Ce0.8Gd0.2O1.95Base lower surface and the Al with Pt heating electrode2O3Ceramic wafer is bonded together.The present invention is tested the acetone in diabetic ketoacidosis patient expiration, and test result shows that device has stable signal to exhaling, and illustrates that the present invention has huge applications prospect in terms of detecting diabetic ketoacidosis patient expiration.

Description

One kind is with Bi1-xLaxFeO3Electric potential type acetone sensor, system are blended together for sensitive electrode Preparation Method and its application
Technical field
The invention belongs to gas sensor technical fields, and in particular to one kind is with Bi1-xLaxFeO3(x=0.1~0.9) is The Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electric potential type acetone (acetone) sensor, preparation method and its in diabetes ketone The application in terms of acetone is detected in disease acid poisoning patient expiration.
Background technique
Diabetes are one of diseases with fastest developing speed in the world.According to the statistics of the World Health Organization (WHO), from 1980 Since, the quantity of diabetic has turned over twice, will have 5.52 hundred million diabetics to the year two thousand thirty whole world.Diabetes are a kind of Life-long disease can lead to death and reduce quality of life.It is to generate insulin in insufficient or bodily tissue by insulin to use Caused by improper.Lasting hyperglycemia and long-term metabolic disorder can lead to the damage of tissue and organ, especially eyes, kidney Dirty and cardiovascular and nervous system damage and its dysfunction and failure.Some serious patients can cause acute concurrent Disease is such as dehydrated, electrolyte disturbance and disturbance of acid-base balance.Diabetic ketoacidosis (DK) is the advanced stage of diabetes.Work as patient When with diabetic ketoacidosis, acetoacetate (AcAc) in body fluid, beta-hydroxy-butanoic acid (β-OHB) and acetone accumulation.Body The concentration of AcAc and β-OHB causes the variation of electrolyte concentration and pH in arterial blood in liquid.Meanwhile AcAc's is spontaneous and non- Enzymatic decarboxylation increases the concentration of acetone in blood.Acetone concentration and blood ketone content according to pervious report, in human exhaled breath It is related with β-OHB content in venous blood, therefore detected in Diabetic ketosis acid by the acetone concentration in detection human exhaled breath Toxication is a kind of effective non-intrusive means.
Currently, the breast rail field of diabetes detection is there are many method, such as Proton-Transfer Reactions-mass spectrum (PTR-MS), Gas chromatography/mass spectrometry (GC/MS), ion mobility spectrometry (IMS) and selection ion flow tube mass spectrum (SIFT-MS).Although these are detected Technology has the very sensitivity of Gao Ling, but they are expensive, and volume is big and not portable.In addition, all these methods require compared with The long time carries out the preparation of sample, cannot achieve the real-time monitoring exhaled to diabetic.Therefore, there is low cost, it is small Type, portability and high performance gas sensor have become the potential method of the breathing detection for diagnosing diabetes.
CeO among the solid electrolyte that (about 600~800 DEG C) of middle warm area work, after doping2Due to its ionic conductance Rate and transference number of ions are high, and performance is stable and receive significant attention, and is used as solid electrolyte material, there is very big potential answer With value.Adulterate Gd2O3CeO2(Ce0.8Gd0.2O1.95) base blendes together electric potential type gas sensor and be divided into two when detecting acetone Process: first is that the oxidation reaction of acetone, occur acetone gas by sensitive electrode layer to three-phase reaction interface (TPB, gas, Sensitive electrode material and Ce0.8Gd0.2O1.95The interface of plate) diffusion during, the oxidation that acetone can occur for this process is anti- It answers, the concentration of acetone at three phase boundary is caused to reduce, the porosity of sensitive oxide electrode determines the reduction degree of acetone concentration. Second is that a pair of of electrochemical reaction (1) and (2) occurs at three-phase reaction interface, the two reactions constitute a local cell, when When the rate of two electrochemical reactions is equal, reach balance, formed on sensitive electrode blend together current potential at this time, blendes together current potential and ginseng Examine detection signal of the potential difference (Δ V) as sensor of electrode, the i.e. response of sensor.Signal magnitude is detected by electrochemistry The rate for reacting (1) and (2) determines, and reaction rate is depending on the microstructure of sensitive electrode material that (for example material is more Permeability, granularity, pattern etc.) and its electrochemistry and chemical catalysis activity.
Reaction equation is as follows:
O2+4e-→2O2- (1)
1/4C3H6O+2O2-→3/4CO2+3/4H2O+4e- (2)
Summary of the invention
The present invention provides a kind of Bi1-xLaxFeO3(x=0.1~0.9) is the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together Electric potential type acetone sensor, preparation method and its application in diabetic ketoacidosis patient exhales in terms of detection acetone. The present invention effectively improves sensor in performances such as the sensitivity of low concentration (1~5ppm) acetone, promotes the type sensor In the functionization of diabetic ketoacidosis detection field.The obtained sensor of the present invention is other than having high sensitivity, also With good repeatability, selectivity and stability.
Acetone sensor according to the present invention is with Bi1-xLaxFeO3(x=0.1~0.9) is sensitive electrode Ce0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor, wherein Ce0.8Gd0.2O1.95As ion conductive layer, Bi is utilized1- xLaxFeO3For sensitive electrode, mentioned by the microscopic appearance and electrochemical catalysis activity of change La substitution amount change material with reaching The purpose of high sensitivity characteristic.In addition, the present invention is tested the acetone in diabetic ketoacidosis patient expiration, test The result shows that device has stable signal to exhaling, illustrate the present invention in the side that detection diabetic ketoacidosis patient exhales Face has huge applications prospect.
One kind of the present invention is with Bi1-xLaxFeO3(x=0.1~0.9) is the Ce of sensitive electrode0.8Gd0.2O1.95Base is mixed At electric potential type acetone sensor, as shown in Figure 1, it is by the Al with Pt heating electrode2O3Ceramic wafer, Ce0.8Gd0.2O1.95Base Plate, Pt reference electrode and sensitive electrode composition；Pt reference electrode and sensitive electrode are separate and symmetrically prepare Ce0.8Gd0.2O1.95The both ends of upper surface of base plate, Ce0.8Gd0.2O1.95Base lower surface and the Al with Pt heating electrode2O3Ceramics Plate is bonded together；It is characterized by: sensitive electrode material is Bi1-xLaxFeO3(x=0.1~0.9), and make by the following method It is standby to obtain:
Weigh Bi (NO3)3·5H2O、La(NO3)3·6H2O and Fe (NO3)3·9H2O is dissolved in deionized water, mixed to this It closes and citric acid is added dropwise in solution and stirs evenly, stirred 2~4 hours at 70~90 DEG C and obtain wet gel；Gained is wet Gel dries in 80~120 DEG C of air and obtains frangible xerogel；Finally xerogel crushing grinding, and at 700~900 DEG C Under the conditions of be sintered 2~4 hours, obtain Bi1-xLaxFeO3(x=0.1~0.9) sensitive electrode material powder；Wherein, Bi (NO3)3·5H2O、La(NO3)3·6H2O and Fe (NO3)3·9H2The dosage molar ratio of O is (1-x): x:1, citric acid and total gold The molar ratio for belonging to ion (La, Bi and Fe) is 0.5~1.5:1.
It is of the present invention with Bi1-xLaxFeO3(x=0.1~0.9) is the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electricity The preparation method of bit-type acetone sensor, its step are as follows:
(1) Pt reference electrode is made: in Ce0.8Gd0.2O1.95One end of upper surface of base plate is close to edge preparation 15~25 The Pt of doubling silk is used Pt slurry to be sticked to the middle position of reference electrode as contact conductor by the strip Pt reference electrode of μ m-thick；? Ce0.8Gd0.2O1.95The other end of upper surface of base plate is the region for preparing strip sensitive electrode close to edge, by the Pt silk of doubling Region Ce is sticked to Pt slurry0.8Gd0.2O1.95The middle position of substrate is as contact conductor, then by Ce0.8Gd0.2O1.95Substrate It is toasted 1~2 hour under infrared lamp, then by Ce0.8Gd0.2O1.95Substrate is sintered 0.5~1.5 hour at 900~1100 DEG C, Contact conductor is set to be firmly sticked in reference electrode and Ce0.8Gd0.2O1.95On substrate, it is finally cooled to room temperature；
(2) Bi is made1-xLaxFeO3(x=0.1~0.9) sensitive electrode: by Bi1-xLaxFeO3(x=0.1~0.9) is sensitive Electrode material and deionized water are mixed into slurry, and the mass concentration of sensitive electrode material is 2~20%；Dip sensitive electrode material Slurry is in Ce0.8Gd0.2O1.95Upper surface of base plate and the symmetrical other side of reference electrode prepare 15~30 μm in a manner of smearing Thick strip Bi1-xLaxFeO3Sensitive electrode；
(3) above-mentioned preparation is had into Pt reference electrode and Bi1-xLaxFeO3The Ce of sensitive electrode0.8Gd0.2O1.95Substrate exists It is sintered 1~3 hour at 600~900 DEG C；Heating rate when high temperature sintering is 1~2 DEG C/min；
(4) it prepares inorganic bond: measuring waterglass (Na2SiO3·9H2O) 2.5~4.5mL, and weigh Al2O3Powder 0.5~1.0g, by waterglass and Al2O3Powder is mixed and stirred for uniformly, inorganic bond needed for being made；
(5) use inorganic bond by Ce0.8Gd0.2O1.95Table and the Al with Pt heating electrode below substrate2O3Pottery Porcelain plate is bonded together；Wherein, the Al with Pt heating electrode2O3Ceramic wafer is in Al2O3Pass through silk-screen printing Pt on ceramic wafer It obtains, the heating plate as device uses；
(6) device bonded welded, encapsulated, thus production obtain it is of the present invention with Bi1-xLaxFeO3 (x=0.1~0.9) is the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together Copper diethlydithiocarbamate.
Ce is used in the present invention0.8Gd0.2O1.95Ion conductive layer of the material as sensor, and use Bi1-xLaxFeO3 For (x=0.1~0.9) perofskite type oxide material as sensitive electrode, the substitution amount by changing La changes sensitive material Electro catalytic activity and micro-structure achieve the purpose that improve sensor sensing characteristic.In addition, the present invention is acquired in Jilin University The expiration of the medical diabetic ketoacidosis patient of two affiliated hospitals, is further demonstrated that by the test exhaled to this kind of patient The sensor of production has can practicability.
Advantages of the present invention:
(1) solid electrolyte-- that sensor utilizes mixes gadolinium ceria (Ce0.8Gd0.2O1.95), have it is excellent from Subconductivity performance and chemical stability, can be in medium temperature (500~800 DEG C) region detection low concentration acetone；
(2) high-performance double negative property Bi is prepared using sol-gel method1-xLaxFeO3(x=0.1~0.9) As sensor sensing electrode material, preparation method is simple, and condition is easy to control, is suitble to the industrialized production of mass.
(3) expiration for testing diabetic ketoacidosis patient, by acetone concentration in the blood sugar concentration and expiration of patient It is associated, show that the sensor has great potential in terms of practical application.
(4) tablet type sensor structure is used, it is small in size, it is easily integrated, is suitable for producing in enormous quantities.
Detailed description of the invention
Fig. 1: Ce of the present invention0.8Gd0.2O1.95Base blendes together the structural schematic diagram of electric potential type acetone sensor.
Each section title: Bi1-xLaxFeO3(x=0.1~0.9) sensitive electrode 1, Ce0.8Gd0.2O1.95Substrate 2, Pt reference Electrode 3, Pt silk 4, inorganic bond 5, Al2O3Ceramic wafer 6, hexagonal tube socket 7.
Fig. 2: Bi obtained by the present invention1-xLaxFeO3The XRD diagram of (x=0.1~0.9) sensitive electrode material is (wherein, horizontal Coordinate is angle, and ordinate is intensity).
As shown in Fig. 2, being Bi1-xLaxFeO3The XRD diagram of (x=0.1~0.9) sensitive electrode material, by with standard spectrogram Comparison, the XRD peak position of material is between BiFeO3Standard card JCPDS#72-2112 and LaFeO3Standard card JCPDS# Between 75-439, and with the increase of La substitution amount, the position of main peak is deviated to the right, this is the result shows that we successfully invent system For the Bi with perovskite structure1-xLaxFeO3(x=0.1~0.9) series sensitive electrode material.
Fig. 3: the SEM figure (a-e) and average particle size particle size histogram (f) of sensitive electrode material prepared by the present invention.
It can be seen from the figure that Bi prepared by the present invention1-xLaxFeO3Having for (x=0.1~0.9) material is loose more The microscopic appearance in hole, the porosity of electrode are conducive to the diffusion and adsorption desorption process of gas.(a-e) be respectively x=0.1,0.3, 0.5,0.7,0.9 when sensitive material SEM figure, with the increase of La substitution amount, the particle size of material is gradually become smaller, suitably Particle size and pore size are conducive to the increase of active site quantity at three phase boundary.Illustration is the enlarged drawing of regional area.
Fig. 4: Bi is utilized1-xLaxFeO3(x=0.1~0.9) is bent as the sensor response log concentration of sensitive electrode material Line (wherein, abscissa is the concentration of acetone, and ordinate is potential difference values) is and with Bi0.5La0.5FeO3For sensitive material preparation Sensor continuous response curve (wherein, abscissa is the time, and ordinate is potential difference values, and operating temperature is 580 DEG C).
As shown in figure 4, being Bi1-xLaxFeO3The response log concentration curve of (x=0.1~0.9) device, the Δ V of device and The logarithm of acetone concentration has good piecewise linear relationship, its slope is defined as to the sensitivity of sensor.With Bi1- xLaxFeO3(x=0.1,0.3,0.5,0.7,0.9) for device prepared by sensitive material according to the numerical value of x be respectively designated as S1, S3, S5, S7, S9 (respectively correspond figure a~figure e).From figure as it can be seen that device S5 to the sensitivity of 1-5ppm and 5-50ppm acetone most Height, value are respectively -17.5mV/decade and -36.7 mV/decade, which shows higher spirit to acetone sensor Sensitivity and lower Monitoring lower-cut.Fig. 4 (f) is that the continuous phase of device S5 answers recovery curve, which shows S5 pairs of device Acetone has quick and stable detection signal.
Fig. 5: Bi is utilized0.5La0.5FeO3The reperformance test curve of sensor (S5) as sensitive electrode material.(its In, abscissa is the time, and ordinate is potential difference values)
As shown in figure 5, being Bi0.5La0.5FeO3Sensor (S5) as sensitive electrode material to 2ppm, 5ppm and The test result of continuous 6 tests in 10ppm acetone, it can be seen from the figure that the response of this 6 times tests changes small, table Funerary objects part has repeatability well.
Fig. 6: Bi is utilized0.5La0.5FeO3The moisture stable linearity curve of sensor as sensitive electrode material.It is (wherein, horizontal Coordinate is the time, and ordinate is potential difference values)
As shown in fig. 6, being Bi0.5La0.5FeO3Device is tested in the humidity stability that relative humidity is 20~80%, from figure In as can be seen that device when relative humidity rises to 80% by 20%, the decline range of response is smaller, it is seen that device has good Good humidity stability.
Fig. 7: Bi is utilized0.5La0.5FeO3Stability curve (wherein, the abscissa of sensor as sensitive electrode material For the time, ordinate is potential difference values).
As shown in fig. 7, being Bi0.5La0.5FeO3Device on day 1 (Initial day), the 15th day and the 30th day it is steady Qualitative test, it can be seen from the figure that device, in 30 days, the variation of response is smaller, it is seen that device has good stability.
Fig. 8: Bi is utilized0.5La0.5FeO3Sensor as sensitive electrode material is to different degrees of diabetic and three The continuous response that a Healthy People is exhaled restores test, and (wherein, abscissa is the time, and ordinate is potential difference values.It (a) is diabetes Patient expiration's test, T2DM and T2DM-1 are two type-II diabetes patients without ketoacidosis symptom, (b) are Healthy People Breath tester.)
As shown in figure 8, to utilize Bi0.5La0.5FeO3Sensor as sensitive electrode material is to different degrees of diabetes The test that patient and three Healthy Peoples are exhaled, test result show that the sensor has the expiration of Healthy People and diabetic There is stable response, the expiration of response and the type-II diabetes patient without ketoacidosis symptom that wherein Healthy People is exhaled Response is below Patients of Diabetes Ketosis Acid Poisoning expiration response, and the response of device is with diabetic ketoacidosis The blood ketone concentration of patient increases and increases that (patient's blood ketone concentration obtains patient's progress blood testing by The Second Hospital of Jilin Universtiy As a result).In general, the diabetic that blood ketone content is more than 0.5mmol/L is known as Patients of Diabetes Ketosis Acid Poisoning, no matter companion Without urine ketone (Urinary Ketone).Therefore, we test internal blood ketone concentration be 0.5mmol/L and urine ketone content be The expiration of the Patients of Diabetes Ketosis Acid Poisoning of one plus sige, sensor are about -4mV, the value to the response of the patient expiration It is that 0.5mmol/L is not accompanied by the patient of urine ketone without significant difference with blood ketone concentration.This shows that acetone is dense in ketosis patient expiration It spends little with the relationship of urine ketone.
Fig. 9: Bi is utilized0.5La0.5FeO3Sensor as sensitive electrode material is in the interval detection of expiration twice in 58 days When sensitivity curve and Patients of Diabetes Ketosis Acid Poisoning exhale in acetone concentration and blood ketone concentration relation curve；
Scheme the sensitivity curve of device when (a) is first time clinical detection, figure (b) is device when the 2nd detection is exhaled The abscissa of sensitivity curve, (a) and (b) is acetone concentration, and ordinate is potential difference values；Scheming (c) is in Diabetic ketosis acid The relation curve of acetone concentration and blood ketone concentration in malicious patient expiration.
It is the 58 days sensitivity curves exhaled when detecting twice in device interval as shown in Fig. 9 (a) (b), it is black on curve Color side's point is patient expiration's value corresponding points on sensitivity curve, and the content of acetone in expiration, Fig. 9 are judged according to its response It (c) is the relation curve of acetone concentration in the blood ketone concentration of patient and expiration, it can be seen from the figure that diabetic ketoacidosis There are positively related relationships for the blood ketone concentration of acetone concentration and patient in patient expiration.Thus it can be seen that this sensor is true It is real that there are very big potentiality in practical applications.
Specific embodiment
Embodiment 1:
Bi is prepared with sol-gel method1-xLaxFeO3(x=0.1~0.9) material, the Bi that 800 DEG C are sintered1- xLaxFeO3(x=0.1~0.9) makes Ce as sensitive electrode material0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor, and Sensor air-sensitive performance is tested, detailed process is as follows:
1. making Pt reference electrode: in the Ce of 2 × 2mm of length and width, thickness 0.2mm0.8Gd0.2O1.95The side of upper surface of base plate Using Pt starch production one layer of 0.5mm × 2mm size, 20 μ m-thicks Pt reference electrode, while with a root long degree be 1cm Pt silk it is right After folding, bending place is starched with Pt and is sticked to extraction electrode lead on reference electrode middle position；In the opposite side of reference electrode, The Pt silk of doubling 1cm is sticked to Ce with Pt slurry0.8Gd0.2O1.95On substrate surface, extraction electrode lead；Then will Ce0.8Gd0.2O1.95Substrate toasts 1 hour under infrared lamp, then by Ce0.8Gd0.2O1.95Substrate is sintered 0.5 hour at 950 DEG C, To exclude the terpinol in Pt slurry, and Pt are fixed, is finally down to room temperature.
2. making Bi1-xLaxFeO3(x=0.1~0.9) sensitive electrode: Bi is prepared with sol-gel method first1- xLaxFeO3(x=0.1~0.9) material.
Weigh Bi (NO respectively in proportion3)3·5H2O、La(NO3)3·6H2O and Fe (NO3)3·9H2O, the weighed Bi of institute (NO3)3·5H2O mass is respectively 1.3097g, 1.1087g, 0.7277g, 0.1456g, La (NO3)3·6H2The quality of O is distinguished For 0.1299g, 0.3897g, 0.6495g, 0.9093g, 1.1691g, Fe (NO3)3·9H2The quality of O is 1.2121g, and molten Solution is in 20ml deionized water, after mixing evenly, weighs 1.2609g citric acid and is added dropwise in above-mentioned solution；It will mix molten Liquid is placed in stirring 3h at 80 DEG C and obtains wet gel；By the above wet gel be placed in 100 DEG C of thermostatic drying chambers dry 10h obtain it is frangible Xerogel, take xerogel to be crushed and be fully ground；Finally ground xerogel is placed in Muffle furnace, in 800 DEG C of conditions Lower sintering 2h, obtained Bi0.9La0.1FeO3、Bi0.7La0.3FeO3、Bi0.5La0.5FeO3、Bi0.3La0.7FeO3、 Bi0.1La0.9FeO3Quality is respectively 0.9174g, 0.8754g, 0.8333g, 0.7913g, 0.7493g.
10mg Bi is taken respectively1-xLaxFeO3100mg deionized water is added in agate mortar in (x=0.1~0.9) powder It is fully ground 0.5h, so that slurry is tuned into, by Bi1-xLaxFeO3(x=0.1~0.9) slurry is symmetrical with reference electrode Ce0.8Gd0.2O1.95The other side of upper surface of base plate coats one layer of 0.5mm × 2mm size, 20 μm of thick sensitive electrodes.
The Ce with reference electrode and sensitive electrode that will be made0.8Gd0.2O1.95Substrate is with the heating rate of 2 DEG C/min It is warming up to 800 DEG C and keeps 2h, be finally down to room temperature.
3. bonding the Al with heating electrode2O3Ceramic wafer.By Al2O3Powder 0.7g and waterglass (Na2SiO3·9H2O) 3mL is configured to inorganic bond, using above-mentioned adhesive by Ce0.8Gd0.2O1.95The lower surface of substrate (does not carry out any operation Al with same size with Pt heating electrode on one side)2O3Ceramic wafer (2 × 2mm of length and width, thickness 0.2mm) is bonded；
4. device welding, encapsulation.Device is welded on hexagonal tube socket, shield is put on, pressing is fixed, completed Ce0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor.
Table 1: with Bi1-xLaxFeO3(x=0.1~0.9) is response of the sensor of sensitive electrode material to 10ppm acetone Value
Sensor is connected on Fluke signal tester, above-mentioned five kinds of sensors are placed in the gas of air, acetone respectively Voltage signal test is carried out in atmosphere；It will be with Bi1-xLaxFeO3The sensor that (x=0.1~0.9) does sensitive electrode material is placed in sky Voltage signal test is carried out in the atmosphere of gas and 10ppm acetone.The results are shown in Table 1, the test result show with Bi0.5La0.5FeO3It is best to the response of acetone for the sensor of sensitive electrode material, therefore herein mainly for this sensor Carry out subsequent test.
Table 2: with Bi0.5La0.5FeO3For sensitive electrode material sensor Δ V with Patients of Diabetes Ketosis Acid Poisoning blood The delta data of ketone concentration
Test is with Bi0.5La0.5FeO3For the Ce of sensitive electrode material0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor pair The gas-sensitive property that diabetes patient exhales
Sensor is connected on Fluke signal tester, sensor is placed in the diabetic ketoacidosis being collected into Voltage signal test is carried out in patient's expiration atmosphere.
Table 2 lists respectively with Bi0.5La0.5FeO3For the Ce of electrode material production0.8Gd0.2O1.95Base blendes together electric potential type biography Potential difference of the sensor in diabetic ketoacidosis patient's expiration atmosphere.As can be seen from the table, with Diabetic ketosis acid The increase of toxic patient blood ketone concentration, the response of device are also continuously increased, and response and blood ketone concentration have strong positive Guan Xing.It can be seen that the present invention has huge application potential in the expiration context of detection of diabetic ketoacidosis.

Claims (3)

1. one kind is with Bi1-xLaxFeO3For the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electric potential type acetone sensor, by having The Al of Pt heating electrode2O3Ceramic wafer, Ce0.8Gd0.2O1.95Substrate, Pt reference electrode and sensitive electrode composition；Pt reference electrode and Sensitive electrode is separate and symmetrically prepares in Ce0.8Gd0.2O1.95The both ends of upper surface of base plate, Ce0.8Gd0.2O1.95Under substrate Surface and the Al with Pt heating electrode2O3Ceramic wafer is bonded together；It is characterized by: sensitive electrode material is Bi1- xLaxFeO3, x=0.1~0.9, and be prepared by the following method,
Weigh Bi (NO3)3·5H2O,La(NO3)3·6H2O,Fe(NO3)3·9H2O is dissolved in deionized water；It is molten to the mixing Citric acid is added dropwise in liquid and stirs evenly, is stirred 2~4 hours at 70~90 DEG C and obtains wet gel；By gained wet gel Drying obtains frangible xerogel in 80~120 DEG C of air；Finally xerogel crushing grinding, and in 700~900 DEG C of conditions Lower sintering 2~4 hours, obtains Bi1-xLaxFeO3Sensitive electrode material powder；Wherein, Bi (NO3)3·5H2O、La(NO3)3· 6H2O、Fe(NO3)3·9H2The dosage molar ratio of O is (1-x): x:1, the molar ratio of citric acid and total metal ion is 0.5~ 1.5:1.
2. one kind described in claim 1 is with Bi1-xLaxFeO3For the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electric potential type acetone The preparation method of sensor, its step are as follows:
(1) Pt reference electrode is made: in Ce0.8Gd0.2O1.95One end of upper surface of base plate prepares 15~25 μ m-thicks close to edge The Pt of doubling silk is used Pt slurry to be sticked to the middle position of reference electrode as contact conductor by strip Pt reference electrode；? Ce0.8Gd0.2O1.95The other end of upper surface of base plate is the region for preparing strip sensitive electrode close to edge, by the Pt silk of doubling Region Ce is sticked to Pt slurry0.8Gd0.2O1.95The middle position of substrate is as contact conductor, then by Ce0.8Gd0.2O1.95Substrate It is toasted 1~2 hour under infrared lamp, then by Ce0.8Gd0.2O1.95Substrate is sintered 0.5~1.5 hour at 900~1100 DEG C, is made Contact conductor is firmly sticked in reference electrode and Ce0.8Gd0.2O1.95On substrate, it is finally cooled to room temperature；
(2) Bi is made1-xLaxFeO3Sensitive electrode: by Bi1-xLaxFeO3Sensitive electrode material and deionized water are mixed into slurry, quick The mass concentration of sense electrode material is 2~20%；Sensitive electrode material paste is dipped in Ce0.8Gd0.2O1.95Upper surface of base plate with The symmetrical other side of reference electrode prepares the strip Bi of 15~30 μ m-thicks in a manner of smearing1-xLaxFeO3Sensitive electrode；
(3) above-mentioned preparation is had into Pt reference electrode and Bi1-xLaxFeO3The Ce of sensitive electrode0.8Gd0.2O1.95Substrate is 600 It is sintered 1~3 hour at~900 DEG C；Heating rate when high temperature sintering is 1~2 DEG C/min；
(4) it prepares inorganic bond: measuring 2.5~4.5mL of waterglass, and weigh Al2O30.5~1.0g of powder, by waterglass with Al2O3Powder is mixed and stirred for uniformly, inorganic bond needed for being made；
(5) use inorganic bond by Ce0.8Gd0.2O1.95Table and the Al with Pt heating electrode below substrate2O3Ceramic wafer is viscous Knot is together；Wherein, the Al with Pt heating electrode2O3Ceramic wafer is in Al2O3It is obtained on ceramic wafer by silk-screen printing Pt , the heating plate as device uses；
(6) device bonded welded, encapsulated, so that production is obtained with Bi1-xLaxFeO3For sensitive electrode Ce0.8Gd0.2O1.95Base blendes together Copper diethlydithiocarbamate.
3. one kind described in claim 1 is with Bi1-xLaxFeO3For the Ce of sensitive electrode0.8Gd0.2O1.95Base blendes together electric potential type acetone Application of the sensor in diabetic ketoacidosis patient exhales in terms of detection acetone.
CN201910569830.9A 2019-06-27 2019-06-27 One kind is with Bi1-xLaxFeO3Electric potential type acetone sensor, preparation method and applications are blended together for sensitive electrode Pending CN110243878A (en)

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Publication number Priority date Publication date Assignee Title
CN110596217A (en) * 2019-09-18 2019-12-20 吉林大学 NiTa2O6All-solid-state acetone sensor used as sensitive electrode for diabetes diagnosis and preparation method thereof
CN110618181A (en) * 2019-09-19 2019-12-27 吉林大学 La2CuMnO6Mixed potential type acetone sensor as sensitive electrode, preparation method and application thereof
CN111892093A (en) * 2020-08-12 2020-11-06 桂林电子科技大学 Microwave absorbing material and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110596217A (en) * 2019-09-18 2019-12-20 吉林大学 NiTa2O6All-solid-state acetone sensor used as sensitive electrode for diabetes diagnosis and preparation method thereof
CN110618181A (en) * 2019-09-19 2019-12-27 吉林大学 La2CuMnO6Mixed potential type acetone sensor as sensitive electrode, preparation method and application thereof
CN111892093A (en) * 2020-08-12 2020-11-06 桂林电子科技大学 Microwave absorbing material and preparation method thereof

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