CN103409657B - A kind of (Zr100-tTit) xCuyRz block amorphous alloy and preparation method and the application on glucose sensor electrode without enzyme - Google Patents

A kind of (Zr100-tTit) xCuyRz block amorphous alloy and preparation method and the application on glucose sensor electrode without enzyme Download PDF

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CN103409657B
CN103409657B CN201310285014.8A CN201310285014A CN103409657B CN 103409657 B CN103409657 B CN 103409657B CN 201310285014 A CN201310285014 A CN 201310285014A CN 103409657 B CN103409657 B CN 103409657B
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amorphous alloy
enzyme
glucose sensor
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CN103409657A (en
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李然
罗学昆
张涛
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Beihang University
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Abstract

The invention discloses one (Zr 100-tti t) xcu yr zblock amorphous alloy and preparation method and the application on glucose sensor electrode without enzyme, should (Zr 100-tti t) xcu yr zt=0 ~ 100 in block amorphous alloy, 40≤x≤80,5≤y≤50,1≤z≤45, R is one or more in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn.Sensor electrode is made up of block amorphous alloy matrix and cellular porous amorphous array layer, the skeleton of described array layer is non-crystal structure, thickness is 1 ~ 100 micron, the diameter of single honeycomb 1 ~ 30 micron, and honeycomb pipe-wall internal surface has adsorbed the Cu particle being of a size of 1 ~ 300 nanometer.The surface of this sensor electrode is generated in-situ cellular porous non-crystal structure layer.Glucose sensor electrode without enzyme of the present invention is without the need to the intervention of enzyme, highly sensitive, and response rapidly, good stability, selectivity is high, simple electrochemical treatment and reusable after losing efficacy, and can be used widely in fields such as blood sugar monitoring, biotechnology, food-processings.

Description

A kind of (Zr100-tTit) xCuyRz block amorphous alloy and preparation method and the application on glucose sensor electrode without enzyme
Technical field
The present invention relates to a kind of block amorphous alloy that can apply on a biosensor, more particularly, refer to one (Zr 100-tti t) xcu yr zblock amorphous alloy and preparation method and the application on glucose sensor electrode without enzyme.The surface of this amorphous glucose sensor electrode without enzyme is generated in-situ honeycomb fashion vesicular structure.
Background technology
Along with the progress of science and technology, the requirement of the mankind to health is more and more higher, in succession develops various technology and equipment and carrys out disease therapy.Highly sensitive glucose sensor, as the important tool of the content of monitoring glucose in solutions, is more and more subject to people's attention.The glucose sensor of current exploitation is mainly divided into and carries enzyme and without the large class of enzyme two.Although carry enzymatic glucose sensor have highly sensitive and excellent selectivity in observation process, but enzyme is very easily inactivation and sex change in immobilization and preservation process, and enzyme is very high to the requirement of monitoring of environmental, be subject to the impact of oxygen, therefore, stability and the repeatability of carrying Enzyme sensor are not good.So, the focus that exploitation has highly sensitive, the enzyme-free glucose sensor of good selectivity becomes research gradually.At present, the glucose sensor electrode without enzyme material of people's exploitation concentrates on precious metal element.Although noble metal electrode shows very high sensitivity for direct-detection glucose; but its be vulnerable in testing process other active substances in chemical reaction intermediate, body fluid (as xitix, uric acid, ethanol and to acyl amino phenol) and the interference of chlorion, sensitivity, response speed and stability significantly decline.Therefore, more stable, sensitiveer and that immunity from interference is stronger enzyme-free glucose sensor is developed significant.
Summary of the invention
An object of the present invention is to provide a kind of new block amorphous alloy material, and namely molar percentage composition is (Zr 100-tti t) xcu yr zblock amorphous alloy, wherein t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100; 40≤x≤80,5≤y≤50,1≤z≤45, R is one or more in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn.
Two of object of the present invention proposes one to prepare (Zr 100-tti t) xcu yr zthe method of block amorphous alloy strip or sheet material.The method is first according to target component (Zr 100-tti t) xcu yr ztake the pure element of quality needed for Zr-Ti-Cu-R, then adopt arc-melting furnace to carry out melting, recycling rapid solidification equipment adopts casting technique to make (Zr 100-tti t) xcu yr zamorphous alloy ribbon or sheet material.
Three of object of the present invention proposes a kind of method preparing cellular porous amorphous glucose sensor electrode without enzyme, and the method is at (Zr 100-tti t) xcu yr zamorphous alloy ribbon or sheet material carry out: first, to (Zr 100-tti t) xcu yr zamorphous alloy ribbon or sheet material carry out shot blasting on surface process; Then, after acetone, alcohol and distilled water ultrasonic cleaning, pre-formed electrode part is obtained; Then pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode, and adopt galvanostatic method corrosion treatment, current density is 3 ~ 10mA/cm 2, the time is 1250 seconds, takes out and after 3 ~ 10 seconds, namely obtains glucose sensor electrode without enzyme through distilled water supersound process.The surface of this glucose sensor electrode without enzyme is cellular porous amorphous array structure, and the skeleton of this array is non-crystal structure, the diameter of single honeycomb 1 ~ 30 micron, and the Cu particle size of honeycomb pipe-wall internal surface absorption is 1 ~ 300 nanometer.The electrode obtained through the inventive method can for the measurement of glucose concn under without enzyme condition, and highly sensitive, the stable performance of measuring, immunity from interference are strong.
At (Zr 100-tti t) xcu yr zthe cellular porous amorphous layer that amorphous alloy ribbon or sheet material prepare, be directly amorphous thin ribbon or plate surface generated in-situ, meet sheet electrodes structure, directly can be used as chip glucose sensor electrode without enzyme.Compare other enzyme-free glucose sensors, simplify making processes.
Cellular porous amorphous glucose sensor electrode without enzyme prepared by the present invention can the oxidation of direct catalysis glucose, have highly sensitive, good stability, reproducible, immunity from interference is strong, the features such as linearity range is wide, therefore, have application prospect very widely in the glucose monitoring of the present invention in blood, urine, food solution and bio-culture solution.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of cellular porous amorphous layer in embodiment 1.
Fig. 2 is the nano particle of cellular porous amorphous layer inner surface of tube wall absorption in embodiment 1.
Fig. 3 is the X-ray diffractogram of cellular porous amorphous layer in embodiment 1.
Fig. 4 is current versus time curve electrode obtained for embodiment 1 being carried out glucose monitoring.
Fig. 4 A is the current versus time curve of the electrode glucose monitoring being added with sodium-chlor.
Fig. 5 be add 0.1mM xitix (AA) continuously, electric current ~ time correlation curve that 0.1mM produces acyl amino phenol (AP) and 1mM glucose solution.
Fig. 6 is the scanning electron microscopic picture of the cellular porous amorphous layer that in embodiment 2, film covers.
Fig. 7 is the current versus time curve that the obtained electrode of embodiment 2 carries out glucose monitoring.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
One (Zr of the present invention 100-tti t) xcu yr zblock amorphous alloy, wherein t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100,40≤x≤80,5≤y≤50,1≤z≤45, R is one or more in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn.
Prepare (Zr of the present invention 100-tti t) xcu yr zamorphous alloy ribbon or sheet material include the following step:
Step one: batching
According to (Zr 100-tti t) xcu yr ztarget component takes each element of Zr, Ti, Cu, R, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%; R is one or more the combination in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn;
Described (Zr 100-tti t) xcu yr zmiddle t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100,40≤x≤80,5≤y≤50,1≤z≤45, and x+y+z=100;
Step 2: melting system (Zr 100-tti t) xcu yr zblock amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain (Zr 100-tti t) xcu yr zblock amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is≤3 × 10 -2pa;
Smelting temperature is 1000 DEG C ~ 3000 DEG C;
Smelting time is 2 ~ 20min;
In order to make (Zr 100-tti t) xcu yr zthe uniform composition of master alloy ingot, carries out the raw material in melt back No. 3 ~ 5 stoves by the melting condition of repeating step two.
Step 3: block amorphous alloy casting
(the Zr that step 2 is prepared 100-tti t) xcu yr zit melts by the induction furnace that quick solidification apparatus put into by block amorphous alloy ingot completely, by spray to cast, solidifies cooling and obtains (Zr 100-tti t) xcu yr zblock amorphous alloy thin plate;
Board size 10mm × the 40mm of non-crystaline amorphous metal thin plate, plate thickness is more than or equal to 1mm;
Or, (the Zr that step 2 is prepared 100-tti t) xcu yr zmaster alloy ingot with after fusing at 600 DEG C ~ 1000 DEG C temperature, revolves with copper wheel the obtained (Zr that quenches in the smelting furnace of rapid solidification equipment 100-tti t) xcu yr zamorphous alloy ribbon; Copper wheel diameter 20cm, rotating speed is 2000 ~ 3000r/min, and strip thickness is 30 ~ 150 microns;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is≤1 × 10 -1pa, induced current 250 ~ 450mA, smelting temperature is 850 ~ 1250 DEG C, and smelting time is 20s ~ 180s;
Spray to cast pressure is 0.01 ~ 0.1MPa;
Speed of cooling is 10 ~ 10 5k/s.
Prepare cellular porous (Zr of the present invention 100-tti t) xcu yr zamorphous glucose sensor electrode without enzyme includes the following step:
The first step: to (Zr 100-tti t) xcu yr znon-crystaline amorphous metal thin plate or amorphous alloy ribbon carry out shot peening, and pressure is 0.1 ~ 1 MPa, and the shot peening time is 1 ~ 5 minute, after in turn after acetone, alcohol washes, then use distilled water ultrasonic cleaning after 5 ~ 10 minutes, obtain pre-formed electrode part;
Second step: pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode;
Adopt galvanostatic method corrosion treatment, current density is 3 ~ 10mA/cm 2, the time is after 1200 ~ 1500 seconds, takes out and after 3 ~ 10 seconds, namely obtains cellular porous amorphous glucose sensor electrode by distilled water supersound process.
Or adopt method and anodic polarization corrosion treatment, sweep velocity is 5 ~ 100mV/min, the final current potential that polarizes is+1.2 ~+1.6V(vs.SCE), time is after 1200 ~ 1500 seconds, take out and after 3 ~ 10 seconds, namely obtain cellular porous amorphous glucose sensor electrode without enzyme by distilled water supersound process.
embodiment 1
(A) Ti is prepared 48.5zr 6cu 37ni 5.5sn 2si 1block amorphous alloy
Step one: batching
According to Ti 48.5zr 6cu 37ni 5.5sn 2si 1target component takes each element of Ti, Zr, Cu, Ni, Sn, Si, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%;
The Ti of 10g processed 48.5zr 6cu 37ni 5.5sn 2si 1needed for block amorphous alloy, the total mass number of each element is: Ti is 3.998g, Zr be 0.942g, Cu be 4.047g, Ni be 0.556g, Sn be 0.409g, Si is 0.048g;
Step 2: melting Ti 48.5zr 6cu 37ni 5.5sn 2si 1block amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain Ti 48.5zr 6cu 37ni 5.5sn 2si 1block amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is 1 × 10 -2pa;
Smelting temperature is 1250 DEG C;
Smelting time is 8min;
In order to make Ti 48.5zr 6cu 37ni 5.5sn 2si 1the uniform composition of master alloy ingot, carries out the raw material in melt back No. 4 stoves by the melting condition of repeating step two.
Step 3: block amorphous alloy casting
The Ti that step 2 is prepared 48.5zr 6cu 37ni 5.5sn 2si 1it melts by the induction furnace that quick solidification apparatus put into by block amorphous alloy ingot completely, by spray to cast, solidifies cooling and obtains Ti 48.5zr 6cu 37ni 5.5sn 2si 1block amorphous alloy thin plate;
Board size 10mm × the 40mm of non-crystaline amorphous metal thin plate, plate thickness is more than or equal to 1mm;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is 1 × 10 -1pa, induced current 300mA, smelting temperature is 900 DEG C, and smelting time is 60s;
Spray to cast pressure is 0.03MPa;
Speed of cooling is 10 2k/s.
(B) cellular porous Ti is prepared 48.5zr 6cu 37ni 5.5sn 2si 1amorphous glucose sensor electrode without enzyme
The first step: to Ti 48.5zr 6cu 37ni 5.5sn 2si 1non-crystaline amorphous metal thin plate carries out shot peening, and pressure is 0.3 MPa, and the shot peening time is 3 minutes, after in turn after acetone, alcohol washes, then use distilled water ultrasonic cleaning after 10 minutes, obtain pre-formed electrode part;
Second step: pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode;
Adopt galvanostatic method corrosion treatment, current density is 7mA/cm 2, the time is after 1200 seconds, takes out and after 5 seconds, namely obtains cellular porous Ti by distilled water supersound process 48.5zr 6cu 37ni 5.5sn 2si 1amorphous glucose sensor electrode.
Through the cellular porous Ti that second step is obtained 48.5zr 6cu 37ni 5.5sn 2si 1amorphous glucose sensor electrode is directly at Ti 48.5zr 6cu 37ni 5.5sn 2si 1the amorphous layer of the surface in situ generation of non-crystaline amorphous metal thin plate, meets sheet electrodes structure, directly can be used as chip glucose sensor electrode without enzyme.Compare other enzyme-free glucose sensors, simplify making processes.
OLYMPUS PM-G3 type optical metallographic microscope carries out the metallographic structure observation and analysis that embodiment 1 obtains product.Embodiment 1 obtains the scanning electron microscopic picture of product as shown in Figure 1, is indicated as cellular structures in figure.Carry out fractograph analysis to the product shown in Fig. 1, honeycomb duct inwall adsorbs the copper nano particles of 1 ~ 300nm, as shown in Figure 2.The diameter of the single honeycomb of described amorphous layer 1 ~ 30 micron, the Cu particle size of honeycomb pipe-wall internal surface absorption is 1 ~ 300 nanometer.
Panalytical X Pert PROX x ray diffractometer x carries out the crystal species analysis that embodiment 1 obtains product, and draws the lattice parameter of each phase according to the position graphical-extrapolation method of diffraction peak.As can be seen from Figure 3 cellular porous amorphous glucose sensor electrode top layer is the composite structure of amorphous and fcc copper.
The electro-chemical test of the cellular porous amorphous enzyme-free glucose sensor that embodiment 1 obtains is comprised the steps:
The configuration of (a) glucose solution
The concentration of the first glucose solution is 0.08mM, is placed in 3 DEG C of refrigerators and preserves.The concentration of the second glucose solution is 0.4mM, is placed in 3 DEG C of refrigerators and preserves.
The Electrochemical Detection of (b) glucose
The Electrochemical Detection of glucose is carry out in the sodium hydroxide solution of 0.1M in concentration.Electrochemistry experiment carries out on VersaSTAT MC Electrochemical System, adopts traditional three-electrode system, and area is 1mm 2pt sheet be supporting electrode, saturated calomel electrode as reference electrode, the cellular porous Ti that second step is obtained 48.5zr 6cu 37ni 5.5sn 2si 1amorphous glucose sensor electrode is as working electrode.Magnetic agitation condition and detect current potential be+0.5V(vs.SCE) time, in 30mL sodium hydroxide solution, be added dropwise to 0.08mM glucose continuous 8 times, more continuous 20 times are added dropwise to 0.4mM glucose, record stablize after electrochemical signals, as shown in Figure 4.The electrode top layer that the present invention obtains is corroded for a long time tempestuously in experience, and point corrosion pit is formed on noncrystal substrate, breed and expand, thus at the uniform cellular porous layer of noncrystal substrate surface in situ generating structure.Therefore, top layer (the i.e. Ti of electrode 48.5zr 6cu 37ni 5.5sn 2si 1non-crystalline material) there is very high catalytic activity, sensitivity, stability and repeatability, as glucose sensor electrode without enzyme material, there is good application prospect.
Or, be add 0.01M sodium-chlor in the sodium hydroxide solution of 0.1M in concentration, mix in backward solution and be added dropwise to 0.08mM glucose continuous 8 times, more continuous 20 times be added dropwise to 0.4mM glucose, the electrochemical signals after record is stable, as shown in Figure 4 A.
By to the current versus time curve shown in Fig. 4 and Fig. 4 A, known current stabilization.The obtained electrode of embodiment 1 is when carrying out blood sugar monitoring, without the need to the intervention of enzyme, highly sensitive, and rapidly, good stability, selectivity is high, simple electrochemical treatment and reusable after losing efficacy in response.
By in the glucose Electrochemical Detection in embodiment 1; when loading current potential is+0.4V(vs.SCE) time; 2 0.1mM xitix (AA), 2 0.1mM are added continuously to acyl amino phenol (AP) and 2 1mM glucose solutions in 0.1M sodium hydroxide solution; electrochemical signals after record is stable, as shown in Figure 5.In figure, the intensity of electrical signal is maximum, then show the single selective to glucose.
In the present invention, the employing method R identical with embodiment 1 chooses alloying constituent during other elements, sees the following form 1: its obtained product is through XRD analysis, and alloying constituent is amorphous alloy material structure.
embodiment 2
Prepare cellular porous Zr 68cu 16ni 8al 8non-crystaline amorphous metal glucose sensor electrode
Step one: batching
According to Zr 68cu 16ni 8al 8target component takes each element of Zr, Cu, Ni, Al, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%;
The Zr of 10g processed 68cu 16ni 8al 8needed for block amorphous alloy, the total mass number of each element is: Zr is 7.847g, Cu be 1.286g, Ni be 0.594g, Al is 0.273g;
Step 2: melting Zr 68cu 16ni 8al 8block amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain Zr 68cu 16ni 8al 8block amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is 1.5 × 10 -2pa;
Smelting temperature is 1700 DEG C;
Smelting time is 5min;
In order to make Zr 68cu 16ni 8al 8the uniform composition of master alloy ingot, carries out the raw material in melt back No. 3 stoves by the melting condition of repeating step two.
Step 3: block amorphous alloy casting
The Zr that step 2 is prepared 68cu 16ni 8al 8it melts by the induction furnace that quick solidification apparatus put into by block amorphous alloy ingot completely, by spray to cast, solidifies cooling and obtains Zr 68cu 16ni 8al 8block amorphous alloy thin plate; Board size 10mm × the 40mm of non-crystaline amorphous metal thin plate, plate thickness is more than or equal to 1mm;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is 1 × 10 -1pa, induced current 380mA, smelting temperature is 1150 DEG C, and smelting time is 60s;
Spray to cast pressure is 0.03MPa;
Speed of cooling is 10 2k/s.
Step 4: to Zr 68cu 16ni 8al 8non-crystaline amorphous metal thin plate carries out shot peening, and pressure is 0.3 MPa, and the shot peening time is 3 minutes, after in turn after acetone, alcohol washes, then use distilled water ultrasonic cleaning after 10 minutes, obtain pre-formed electrode part;
Step 5: pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode;
Adopt method and anodic polarization corrosion treatment, sweep velocity is 35mV/min, and the final current potential that polarizes is+1.5V(vs.SCE), the time is after 1500 seconds, takes out and after 5 seconds, namely obtains cellular porous Zr by distilled water supersound process 68cu 16ni 8al 8amorphous glucose sensor electrode.
The cellular porous Zr obtained to embodiment 2 68cu 16ni 8al 8amorphous glucose sensor electrode carries out performance analysis: electrode top layer is cellular porous amorphous layer, as shown in Figure 6.The diameter of the single honeycomb of described amorphous layer 10 ~ 22 microns, the Cu particle size of honeycomb pipe-wall internal surface absorption is on average in 200 nanometers.Cellular porous amorphous glucose sensor electrode top layer is the composite structure of amorphous and fcc copper.
The electro-chemical test of the cellular porous amorphous enzyme-free glucose sensor that embodiment 2 obtains is comprised the steps:
The configuration of (a) glucose solution
The concentration of the first glucose solution is 0.08mM, is placed in 3 DEG C of refrigerators and preserves.The concentration of the second glucose solution is 0.4mM, is placed in 3 DEG C of refrigerators and preserves.
The Electrochemical Detection of (b) glucose
The Electrochemical Detection of glucose is carry out in the sodium hydroxide solution of 0.1M in concentration.Electrochemistry experiment carries out on VersaSTAT MC Electrochemical System, adopts traditional three-electrode system, and area is 1mm 2pt sheet be supporting electrode, saturated calomel electrode as reference electrode, cellular porous Zr 68cu 16ni 8al 8amorphous glucose sensor electrode is as working electrode.Magnetic agitation condition and detect current potential be+0.5V(vs.SCE) time, in 30mL sodium hydroxide solution, be added dropwise to 0.08mM glucose continuous 8 times, more continuous 20 times are added dropwise to 0.4mM glucose, record stablize after electrochemical signals, as shown in Figure 7.The electrode top layer that the present invention obtains is corroded for a long time tempestuously in experience, and point corrosion pit is formed on noncrystal substrate, breed and expand, thus at the uniform cellular porous layer of noncrystal substrate surface in situ generating structure.Therefore, top layer (the i.e. Zr of electrode 68cu 16ni 8al 8non-crystalline material) there is very high catalytic activity, sensitivity, stability and repeatability, as glucose sensor electrode without enzyme material, there is good application prospect.
embodiment 3
Prepare cellular porous Zr 65cu 15.5ni 10al 7.5pd 2non-crystaline amorphous metal glucose sensor electrode
Step one: batching
According to Zr 65cu 15.5ni 10al 7.5pd 2target component takes each element of Zr, Cu, Ni, Al, Pd, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%;
The Zr of 10g processed 65cu 15.5ni 10al 7.5pd 2needed for block amorphous alloy, the total mass number of each element is: Zr is 7.490g, Cu be 1.244g, Ni be 0.741g, Al be 0.256g, Pd is 0.269g;
Step 2: melting Zr 65cu 15.5ni 10al 7.5pd 2block amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain Zr 65cu 15.5ni 10al 7.5pd 2block amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is 1 × 10 -2pa;
Smelting temperature is 2100 DEG C;
Smelting time is 15min;
In order to make Zr 65cu 15.5ni 10al 7.5pd 2the uniform composition of master alloy ingot, carries out the raw material in melt back No. 3 stoves by the melting condition of repeating step two.
Step 3: block amorphous alloy casting
The Zr that step 2 is prepared 65cu 15.5ni 10al 7.5pd 2master alloy ingot with after fusing at 850 DEG C of temperature, revolves with copper wheel the obtained Zr that quenches in the smelting furnace of rapid solidification equipment 65cu 15.5ni 10al 7.5pd 2amorphous alloy ribbon; Copper wheel diameter 20cm, rotating speed is 2500r/min, and strip thickness is 50 microns;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is 2 × 10 -1pa, induced current 450mA, smelting temperature is 1250 DEG C, and smelting time is 100s;
Spray to cast pressure is 0.05MPa;
Speed of cooling is 10 2k/s.
Step 4: to Zr 65cu 15.5ni 10al 7.5pd 2non-crystaline amorphous metal thin plate carries out shot peening, and pressure is 0.3 MPa, and the shot peening time is 3 minutes, after in turn after acetone, alcohol washes, then use distilled water ultrasonic cleaning after 10 minutes, obtain pre-formed electrode part;
Step 5: pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode;
Adopt method and anodic polarization corrosion treatment, sweep velocity is 35mV/min, and the final current potential that polarizes is+1.5V(vs.SCE), the time is after 1500 seconds, takes out and after 5 seconds, namely obtains cellular porous Zr by distilled water supersound process 68cu 16ni 8al 8amorphous glucose sensor electrode.
The cellular porous Zr obtained to embodiment 3 65cu 15.5ni 10al 7.5pd 2amorphous glucose sensor electrode carries out performance analysis: electrode top layer is cellular porous amorphous layer.The diameter of the single honeycomb of described amorphous layer 30 ~ 60 microns, the Cu particle size of honeycomb pipe-wall internal surface absorption is on average in 200 nanometers.Cellular porous amorphous glucose sensor electrode top layer is the composite structure of amorphous and fcc copper.
The electro-chemical test of the cellular porous amorphous enzyme-free glucose sensor that embodiment 3 obtains is comprised the steps:
The configuration of (a) glucose solution
The concentration of the first glucose solution is 0.08mM, is placed in 3 DEG C of refrigerators and preserves.The concentration of the second glucose solution is 0.4mM, is placed in 3 DEG C of refrigerators and preserves.
The Electrochemical Detection of (b) glucose
The Electrochemical Detection of glucose is carry out in the sodium hydroxide solution of 0.1M in concentration.Electrochemistry experiment carries out on VersaSTAT MC Electrochemical System, adopts traditional three-electrode system, and area is 1mm 2pt sheet be supporting electrode, saturated calomel electrode as reference electrode, cellular porous Zr 65cu 15.5ni 10al 7.5pd 2amorphous glucose sensor electrode is as working electrode.Magnetic agitation condition and detect current potential be+0.5V(vs.SCE) time, in 30mL sodium hydroxide solution, be added dropwise to 0.08mM glucose continuous 8 times, more continuous 20 times are added dropwise to 0.4mM glucose, record stablize after electrochemical signals.The electrode top layer that the present invention obtains is corroded for a long time tempestuously in experience, and point corrosion pit is formed on noncrystal substrate, breed and expand, thus at the uniform cellular porous layer of noncrystal substrate surface in situ generating structure.Therefore, top layer (the i.e. Zr of electrode 65cu 15.5ni 10al 7.5pd 2non-crystalline material) there is very high catalytic activity, sensitivity, stability and repeatability, as glucose sensor electrode without enzyme material, there is good application prospect.

Claims (5)

1. prepare cellular porous (Zr for one kind 100-tti t) xcu yr zthe method of amorphous glucose sensor electrode without enzyme, is characterized in that including the following step:
The first step: to (Zr 100-tti t) xcu yr znon-crystaline amorphous metal thin plate or amorphous alloy ribbon carry out shot peening, and pressure is 0.1 ~ 1 MPa, and the shot peening time is 1 ~ 5 minute, after in turn after acetone, alcohol washes, then use distilled water ultrasonic cleaning after 5 ~ 10 minutes, obtain pre-formed electrode part;
Described (Zr 100-tti t) xcu yr zin R be one or more combination in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn;
Described (Zr 100-tti t) xcu yr zmiddle t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100,40≤x≤80,5≤y≤50,1≤z≤45, and x+y+z=100;
Second step: pre-formed electrode part is placed in 3wt.%NaCl solution, with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode;
Adopt galvanostatic method corrosion treatment, current density is 3 ~ 10mA/cm 2, the time is after 1200 ~ 1500 seconds, takes out and after 3 ~ 10 seconds, namely obtains cellular porous (Zr by distilled water supersound process 100-tti t) xcu yr zamorphous glucose sensor electrode.
2. cellular porous (the Zr of preparation according to claim 1 100-tti t) xcu yr zthe method of amorphous glucose sensor electrode without enzyme, is characterized in that: at the preparation (Zr of the first step 100-tti t) xcu yr zthe step of non-crystaline amorphous metal thin plate is:
Step one: batching
According to (Zr 100-tti t) xcu yr ztarget component takes each element of Zr, Ti, Cu, R, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%; R is one or more the combination in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn;
Described (Zr 100-tti t) xcu yr zmiddle t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100,40≤x≤80,5≤y≤50,1≤z≤45, and x+y+z=100;
Step 2: melting system (Zr 100-tti t) xcu yr zblock amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain (Zr 100-tti t) xcu yr zblock amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is≤3 × 10 -2pa;
Smelting temperature is 1000 DEG C ~ 3000 DEG C;
Smelting time is 2 ~ 20min;
Step 3: block amorphous alloy casting
(the Zr that step 2 is prepared 100-tti t) xcu yr zit melts by the induction furnace that quick solidification apparatus put into by block amorphous alloy ingot completely, by spray to cast, solidifies cooling and obtains (Zr 100-tti t) xcu yr zblock amorphous alloy thin plate;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is≤1 × 10 -1pa, induced current 250 ~ 450mA, smelting temperature is 850 ~ 1250 DEG C, and smelting time is 20s ~ 180s;
Spray to cast pressure is 0.01 ~ 0.1MPa;
Speed of cooling is 10 ~ 10 5k/s.
3. cellular porous (the Zr of preparation according to claim 1 100-tti t) xcu yr zthe method of amorphous glucose sensor electrode without enzyme, is characterized in that: at the preparation (Zr of the first step 100-tti t) xcu yr zthe step of amorphous alloy ribbon is:
Step one: batching
According to (Zr 100-tti t) xcu yr ztarget component takes each element of Zr, Ti, Cu, R, mixes and obtains melting raw material, and the mass percent purity of each element is not less than 99.0%; R is one or more the combination in Au, Ag, Pt, Pd, Ni, La, Ce, Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, B and Sn;
Described (Zr 100-tti t) xcu yr zmiddle t, x, y, z are molecular fraction, t=0 ~ 100, x+y+z=100,40≤x≤80,5≤y≤50,1≤z≤45, and x+y+z=100;
Step 2: melting system (Zr 100-tti t) xcu yr zblock amorphous alloy ingot
Melting raw material is put into vacuum arc fumace and carries out melting, in mass percent purity be under the argon atmosphere of 99.999% melting evenly afterwards take out obtain (Zr 100-tti t) xcu yr zblock amorphous alloy ingot;
Smelting parameter: during melting, the vacuum tightness of vacuum arc fumace is≤3 × 10 -2pa;
Smelting temperature is 1000 DEG C ~ 3000 DEG C;
Smelting time is 2 ~ 20min;
Step 3: block amorphous alloy casting
(the Zr that step 2 is prepared 100-tti t) xcu yr zmaster alloy ingot with after fusing at 600 DEG C ~ 1000 DEG C temperature, revolves with copper wheel the obtained (Zr that quenches in the smelting furnace of rapid solidification equipment 100-tti t) xcu yr zamorphous alloy ribbon;
Induction melting optimum configurations: during melting, the vacuum tightness of vacuum induction furnace is≤1 × 10 -1pa, induced current 250 ~ 450mA, smelting temperature is 850 ~ 1250 DEG C, and smelting time is 20s ~ 180s;
Spray to cast pressure is 0.01 ~ 0.1MPa;
Speed of cooling is 10 ~ 10 5k/s.
4. cellular porous (the Zr of preparation according to claim 1 100-tti t) xcu yr zthe method of amorphous glucose sensor electrode without enzyme, is characterized in that: pre-formed electrode part is placed in 3wt.%NaCl solution, and with pre-formed electrode part for working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode; Adopt method and anodic polarization corrosion treatment, sweep velocity is 5 ~ 100mV/min, and the final current potential vs.SCE that polarizes is+1.2 ~+1.6V, and the time is after 1200 ~ 1500 seconds, takes out and after 3 ~ 10 seconds, namely obtains cellular porous (Zr by distilled water supersound process 100-tti t) xcu yr zamorphous glucose sensor electrode without enzyme.
5. cellular porous (the Zr of preparation according to claim 1 100-tti t) xcu yr zthe method of amorphous glucose sensor electrode without enzyme, is characterized in that: the surface of glucose sensor electrode without enzyme is cellular porous (Zr 100- tti t) xcu yr zamorphous array structure, the diameter of single honeycomb 1 ~ 30 micron, the Cu particle size of honeycomb pipe-wall internal surface absorption is 1 ~ 300 nanometer.
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