CN110297026A - One kind being based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion - Google Patents
One kind being based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion Download PDFInfo
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Abstract
The present invention discloses a kind of based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion, the method includes the following steps: S1, preparation Fe3O4Nano-cluster；S2, preparation Fe3O4@SiO2Microballoon；S3, preparation Fe3O4@SiO2@TiO2Microballoon；S4, preparation Fe3O4@void@TiO2‑Ag+Microballoon；S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement.The present invention has easy to operate, portable, high sensitivity and the excellent properties such as time-consuming is short.
Description
Technical field
The present invention relates to technical field of analytical chemistry, and in particular to one kind is based on superparamagnetic Fe3O4@void@TiO2Structure in situ
Build the optical electro-chemistry detection method of silver ion.
Background technique
With the development of industry, the heavy metal with high toxicity and biological accumulation effect destroys the ecological ring of people's existence
Border.Wherein, silver ion is concerned, Excess free enthalpy silver ion can with DNA and cell membrane interaction, to be made to human health
At serious damage, and electronics is prevented to transmit in cell.In addition, silver ion is due to the bacterium and aquatile to environmental beneficial
It destroys, can do great damage to ecological environment.Environmental Protection Agency (EPA) sets the threshold value of concentration of silver ions as 0.1mg/
L.Therefore, there is an urgent need to develop a kind of methods of silver ion in detection biology and environmental system.
Recently, many analysis methods and strategy be used to detect silver ion, such as atomic absorption spectrography (AAS) (AAS), graphite furnace
Atomic absorption spectrography (AAS) (GFAAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma
Constitution spectrometry (ICP-MS).However, these detection methods are there are equipment valuableness, sample preparation is complicated, time-consuming, needs professional
The defects of operation.In view of these disadvantages, electrochemical techniques and potential measurement are also developed, these methods have sensitive
The advantages that degree, portability and cost-effectiveness, however, their selectivity and stability are still to be improved.In addition, having instrument letter
The greatly research that chromatmetry and Fluorescence Method single, easy to operate, that selectivity is good, at low cost have also caused scientists is emerging
Interest.However, the sensitivity of these methods is not able to satisfy trace analysis requirement.In addition, fluorescent reagent is also by photobleaching, solubility
The influence of difference and complicated organic synthesis and purification process.Therefore, seek structure be simple and convenient to operate, be good portability, sensitive
Spending high, selective good, time-consuming detection method short, that cost performance is high is still an important research work.
Summary of the invention
Goal of the invention: a kind of based on superparamagnetic Fe present invention aims in view of the deficiencies of the prior art, providing3O4@
void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion there is structure to be simple and convenient to operate, high sensitivity, selection
Property it is good, time-consuming short the features such as.
Technical solution: of the present invention a kind of based on superparamagnetic Fe3O4@void@TiO2In-situ construction silver ion it is photoelectrochemical
Detection method is learned, the method includes the following steps:
S1, preparation Fe3O4Nano-cluster；
S2, preparation Fe3O4@SiO2Microballoon；
S3, preparation Fe3O4@SiO2@TiO2Microballoon；
S4, preparation Fe3O4@void@TiO2-Ag+Microballoon: the Fe that will be obtained3O4@SiO2@TiO2Microballoon is dispersed in water, and is added
NaOH solution, stirring, is centrifuged and washes, obtain Fe3O4@void@TiO2-Na+, it is stored in water；To Fe3O4@void@
TiO2-Na+The Ag of various concentration is separately added into suspension+Solion reacts 0.5-2h, 1-5 Magneto separate and water washing,
Obtain Fe3O4@void@TiO2-Ag+Microballoon；
S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement: the Fe that will be obtained3O4@void@TiO2-Ag+Microballoon point
It dissipates in ethyl alcohol, reacts 10-40min, Magneto separate is simultaneously washed, and Fe is obtained3O4@void@TiO2- Ag microballoon, is dispersed in water；It will
The obtained Fe containing not same amount Ag nanoparticle3O4@void@TiO2- Ag suspension distinguishes drop coating in ITO electrode, dries,
Photoelectricity flow measurement, linear equation are carried out, finally, being based on the linear equation, the detection for silver ion；Wherein,
Before electrode modification, 4 centimetres of 1 cm x is cleaned using the mixed solution of hydrogen peroxide, ammonia and water that volume ratio is 1:1:80
ITO electrode, then use ultrapure water, and dry in air.
Preferably, in S4, Fe3O4@SiO2@TiO2The mass volume ratio (mg/ml) of microballoon and water is 2-5:1-5.
Preferably, in S4, Fe3O4@void@TiO2-Na+Suspension and Ag+The volume ratio of solion is 4-10:5-20.
Preferably, in S4,1.5-5.5mol/L NaOH solution is added, stirs 0.5-2h.
Preferably, in S1, Fe3O4Nano-cluster the preparation method is as follows: the NaOH of 30-80mmol is dissolved in 10-40mL's
DEG(diethylene glycol (DEG)) in, under nitrogen protection, mixture 0.5-2h is heated at 100-150 DEG C, the NaOH/DEG solution of generation is cold
But and it is maintained at 40-80 DEG C；By 2-6mmol PAA, 0.2-0.6mmol FeCl3It is heated to the mixture of 10-27mL DEG
180-240 DEG C, after being vigorously stirred 25-65min in nitrogen atmosphere, the NaOH/DEG solution of 0.8-2.5mL, reaction are injected rapidly
Solution slowly becomes black from light yellow, and obtained product ethyl alcohol and ultrapure water are carried out 1-5 by continuous heating 0.5-2h respectively
Secondary washing, obtains Fe3O4Nano-cluster, and it is dispersed in again in the ultrapure water of 1-5mL.
Preferably, in S2, Fe3O4@SiO2Microballoon the preparation method is as follows: in 10-30mL ethyl alcohol and 0.5-2mL ammonium hydroxide
The Fe of 1.5-5mL is added in mixture3O4Suspension, at room temperature after strong stirring 3-8min, by the positive silicic acid of TEOS(of 40-80 μ L
Ethyl ester) it is added into said mixture, and 15-50min is kept, by the Fe of generation3O4@SiO2Nanoparticle is centrifuged,
Ethanol washing three times, and it is dispersed in again in 3-8mL ethyl alcohol.
Preferably, in S3, Fe3O4@SiO2@TiO2Microballoon the preparation method is as follows: by 3-8mL Fe3O4@SiO2Microballoon, 8-
23mg hydroxylated cellulose after 10-30min is mixed in 3-9mL ethyl alcohol, 1.5-6mL acetonitrile and 0.05-0.3mL ammonium hydroxide, is added
0.15-0.45mL TBOT(butyl titanate) ethanol solution, stir 1-4h, by the Fe that generation is collected by centrifugation3O4@SiO2@
TiO2Microballoon, and washed respectively three times with ethyl alcohol and ultrapure water, the NaOH for being then 1.5-4.5mol/L with 10-40mL concentration is molten
Liquid etches 10-40min, then the dry 0.5-2h at 40-80 DEG C, then calcines 1-4h in 500-800 DEG C of nitrogen atmosphere, most
Afterwards, it is dispersed in 3-10mL water.
Compared with prior art, the invention has the benefit that the present invention is based on Ag+-Na+Ion exchange captures silver ion,
The Fe of superparamagnetic3O4@void@TiO2It is used for the building of the optical electro-chemistry sensor of silver ion, superparamagnetic Fe for the first time3O4@void@
TiO2Effectively silver ion can be separated from complex matrices, and silver ion measurement can be carried out in simple buffer solution, greatly
The earth improves detecting and selecting property of optical electro-chemistry.In addition, the detection method also has easy to operate, portable, high sensitivity and consumption
When the superperformances such as short.In addition, the present invention optimizes reaction condition, size uniformity, monodispersed superparamagnetic Fe are synthesized first3O4It receives
Rice cluster；And Fe is eliminated by medium silica shell3O4And TiO2Crystal face mismatch, obtain Fe3O4@SiO2@TiO2It is dual
Nuclear-shell magneto-optic nano structural material；And optimization alkaline etching condition, obtain the complete Fe of pattern3O4@void@TiO2；And pass through reduction
Property ethanol washing, in-situ construction one kind be based on superparamagnetic Fe3O4@void@TiO2Silver ion optical electro-chemistry detection method.
Detailed description of the invention
Fig. 1 is corresponding high resolution transmission electron microscopy in the embodiment of the present invention 1.
Fig. 2 is corresponding element mapping graph in the embodiment of the present invention 1.
Fig. 3 is corresponding X-ray diffraction spectrum figure in the embodiment of the present invention 1.
Fig. 4 is corresponding hysteresis loop figure in the embodiment of the present invention 1.
Fig. 5 is corresponding superparamagnetic behavior schematic diagram in the embodiment of the present invention 1.
Fig. 6 is corresponding electrochemical impedance spectrogram in the embodiment of the present invention 1.
Fig. 7 is corresponding photocurrent response figure in the embodiment of the present invention 1.
Fig. 8 is corresponding photocurrent response test result figure in experimental example 1 of the present invention.
Fig. 9 is corresponding disturbed test result figure in experimental example 2 of the present invention.
Specific embodiment
Technical solution of the present invention is described in detail below by specific embodiments and the drawings, but protection of the invention
Range is not limited to the embodiment.
Embodiment 1
One kind being based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion, the method includes
Following step:
S1, preparation Fe3O4Nano-cluster: the NaOH of 50mmol is dissolved in the DEG of 20mL, under nitrogen protection, is added at 120 DEG C
The NaOH/DEG solution of generation is cooled and maintained at 60 DEG C by hot mixt 1h；By 4mmol PAA, 0.4mmol FeCl3With
The mixture of 17mL DEG is heated to 220 DEG C, after being vigorously stirred 45min in nitrogen atmosphere, injects the NaOH/ of 1.8mL rapidly
DEG solution, reaction solution slowly become black, continuous heating 1h, by obtained product ethyl alcohol and ultrapure moisture from light yellow
It carry out not wash for 3 times, obtain Fe3O4Nano-cluster, and it is dispersed in again in the ultrapure water of 3mL；
S2, preparation Fe3O4@SiO2Microballoon: the Fe of 3mL is added in the mixture of 20mL ethyl alcohol and 1mL ammonium hydroxide3O4Suspension, room
After the lower strong stirring 5min of temperature, the TEOS of 60 μ L is added into said mixture, and keep 30min, by the Fe of generation3O4@
SiO2Nanoparticle is centrifuged, and ethanol washing three times, and it is dispersed in again in 5mL ethyl alcohol；
S3, preparation Fe3O4@SiO2@TiO2Microballoon: by 5mL Fe3O4@SiO2Microballoon, 13mg hydroxylated cellulose, 5mL ethyl alcohol, 3mL
After 20min is mixed in acetonitrile and 0.1mL ammonium hydroxide, the ethanol solution of 0.25mL TBOT is added, 2h is stirred, by being collected by centrifugation
The Fe of generation3O4@SiO2@TiO2Microballoon, and washed respectively three times with ethyl alcohol and ultrapure water, it is then 2.5mol/ with 20mL concentration
The NaOH solution of L etches 20min, then the dry 1h at 60 DEG C, then calcines 2h in 600 DEG C of nitrogen atmosphere, finally, by it
It is dispersed in 5mL water；
S4, preparation Fe3O4@void@TiO2-Ag+Microballoon: the 30mg Fe that will be obtained3O4@SiO2@TiO2Microballoon is dispersed in water,
20mL 2.5mol/L NaOH solution is added, stirs 1h, is centrifuged and washes, obtain Fe3O4@void@TiO2-Na+, stored
In 3mL water；To 100 μ L Fe3O4@void@TiO2-Na+The Ag of 200 μ L various concentrations is separately added into suspension+Ion is molten
Liquid reacts 1h, 3 Magneto separates and water washing, obtains Fe3O4@void@TiO2-Ag+Microballoon；
S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement: the Fe that will be obtained3O4@void@TiO2-Ag+Microballoon point
It dissipates in 100 μ L ethyl alcohol, reacts 20min, Magneto separate is simultaneously washed, and Fe is obtained3O4@void@TiO2- Ag microballoon is scattered in 100 μ L
In water；The Fe containing not same amount Ag nanoparticle that 20 μ L are obtained3O4@void@TiO2- Ag suspension distinguishes drop coating in ITO electricity
It on extremely, dries, carries out photoelectricity flow measurement, linear equation, finally, the linear equation is based on, for silver ion
Detection.
Wherein, Fe obtained in S13O4Shown in the high resolution transmission electron microscopy of nano-cluster such as Fig. 1 (A), in S2
The Fe arrived3O4@SiO2Shown in the high resolution transmission electron microscopy of microballoon such as Fig. 1 (B), Fe obtained in S33O4@SiO2@
TiO2Shown in the high resolution transmission electron microscopy of microballoon such as Fig. 1 (C), Fe obtained in S43O4@void@TiO2-Ag+Microballoon
High resolution transmission electron microscopy such as Fig. 1 (D) shown in, the Fe that S5 is obtained3O4@void@TiO2The high-resolution of-Ag microballoon is saturating
It penetrates shown in electron microscope picture such as Fig. 1 (E) and Fe3O4@void@TiO2The high resolution transmission electron microscopy of-Ag microballoon is put
Big figure is as shown in Fig. 1 (F).Wherein, as shown in Figure 1, Fe3O4The diameter of nano-cluster (A) is about 90nm, by being about 10nm
Fe3O4Nanocrystal composition.Transition shell SiO2(B) Fe is eliminated3O4And TiO2Between lattice mismatch, realize amorphous state
TiO2Cladding and keep Fe3O4The complete structure of nano-cluster；Successfully synthesizing Fe3O4@SiO2@TiO2(C) molten by NaOH after
Liquid etching, obtains Fe3O4@void@TiO2-Na+, pass through Ag+Ion exchange Fe3O4@void@TiO2The Na of middle doping+After ion
To Fe3O4@void@TiO2-Ag+(D), by centrifugation, ethanol washing and in-situ reducing, Fe has been obtained3O4@void@TiO2-Ag
(E).From Fe3O4@void@TiO2- Ag(F) enlarged drawing in it can be seen that the diameter of Ag nanoparticle is about 18nm.
Wherein, Fe obtained in S43O4@void@TiO2-Ag+The element mapping graph of microballoon as shown in Fig. 2, Fig. 2 (A) with
Fe3O4@void@TiO2-Ag+Microballoon is corresponding, and Fig. 2 (B), Fig. 2 (C), Fig. 2 (D), Fig. 2 (E) also reflect respectively Fe, O,
The specific overview of Ti, Ag；The result shows that the element of each core-shell structure copolymer layer exists, and respective outline diameter corresponds to desirable oxidation
Object and silver ion, to demonstrate Fe3O4@void@TiO2-Ag+Successful synthesis.
Wherein, Fe obtained in S13O4The X-ray diffraction spectrum figure of nano-cluster as shown in Fig. 3 (a), obtained in S2
Fe3O4@SiO2The X-ray diffraction spectrum figure of microballoon is as shown in Figure 3 (b), Fe obtained in S33O4@SiO2@TiO2The X- of microballoon
Ray diffraction spectrum is as shown in Figure 3 (c), Fe obtained in S43O4@void@TiO2The X-ray diffraction spectrum figure of-Ag microballoon
As shown in Fig. 3 (d).Wherein, Fig. 3 (a) describes magnetic iron ore Fe3O4(111), (220), (400), (422), (511), (440)
(622) crystal face, it is consistent with its standard card JCPDS19-0629.Fig. 3 (b) describes SiO2It is coated on Fe3O4The X- on surface is penetrated
Ray diffraction diagram, it can be seen that in addition to Fe3O4X-ray diffraction peak intensity reduce other than, do not generate new diffraction maximum, as a result
Show colloid SiO2In Fe3O4Surface successfully coats.Coating amorphous TiO2After, from Fig. 3 (c) as can be seen that Fe3O4
X-ray diffraction peak intensity further reduce, show to have generated Fe3O4@SiO2@TiO2.By sodium hydroxide etch, realize
Ag+-Na+Ion exchange, and restored by ethyl alcohol in situ, obtain Fe3O4@void@TiO2- Ag is obtained in Fig. 3 (d)
Embody, as shown, positioned at 38.1 °, 44.3 °, 64.4 ° and 77.5 ° diffraction maximum correspond to (111), (200), (220) and
(311) the standard card JCPDS04-0783 of crystal face and Ag are consistent, and peak intensity is weaker can be construed to Fe3O4@void@
TiO2There is a small amount of silver in-Ag.The successful preparation of above-mentioned four kinds of compounds is demonstrated above.
Wherein, Fe obtained in S53O4@void@TiO2The hysteresis loop figure of-Ag microballoon is as shown in Figure 4 (A), and Fig. 4 (B) is
The partial enlarged view of Fig. 4 (A).Wherein, as can be seen that curve is without apparent sluggish, remanent magnetism and coercivity, table from Fig. 4 (A)
The substance is illustrated with typical superparamagnetic characteristic；The partial enlarged view of Fig. 4 (B) describes its coercivity and only has 1Oe, further
Demonstrate Fe3O4@void@TiO2The superparamagnetic characteristic of-Ag at room temperature.
Wherein, Fe obtained in S53O4@void@TiO2The superparamagnetic behavior of-Ag microballoon is single as shown in figure 5, as seen from the figure
The Fe of dispersion3O4@void@TiO2- Ag microballoon can carry out quick separating, after removing magnetic field, aggregation by external magnetic field
Fe3O4@void@TiO2- Ag microballoon can rapidly redisperse, further intuitively demonstrate Fe3O4@void@TiO2- Ag microballoon
Superparamagnetic characteristic.
Wherein, Fe obtained in S23O4@SiO2, Fe obtained in S33O4@SiO2@TiO2, Fe obtained in S43O4@
void@TiO2-Ag+, Fe obtained in S53O4@void@TiO2- Ag is containing 0.2mol/L KNO32.5mmol/L [Fe
(CN)6]4-/3-Electrochemical impedance spectrogram in solution is respectively as shown in Fig. 6 (a), Fig. 6 (b), Fig. 6 (c), Fig. 6 (d).From Fig. 6
As can be seen that from fig. 6, it can be seen that working as Fe3O4@SiO2(a) surface coats TiO2Afterwards (b), electronics transfer impedance value reaches most
Greatly, show semiconductor TiO2The transmission of electronics is prevented, as generation Fe3O4@void@TiO2-Ag+(c) after, impedance value is subtracted
It is small, show to have etched SiO2And Ag+Incorporation improve electron transfer speed, further generate Fe3O4@void@TiO2-Ag(d)
Afterwards, electron transfer speed is further promoted.The corresponding photocurrent curve of modified electrode of different materials also demonstrates in figure B
The successful preparation of above-mentioned four kinds of substances.The strategy provides foundation for the photoelectrochemical method detection of silver ion.Wherein, it is obtained in S2
Fe3O4@SiO2, Fe obtained in S33O4@SiO2@TiO2, Fe obtained in S43O4@void@TiO2-Ag+, obtained in S5
Fe3O4@void@TiO2- Ag modifies photocurrent response figure difference of the ITO electrode in 0.1mol/L PBS buffer solution (pH 7.0)
As shown in Fig. 7 (a), Fig. 7 (b), Fig. 7 (c), Fig. 7 (d), which further demonstrates the successful preparation of above-mentioned four kinds of substances.
Experimental example 1
In S4, by the Fe3O4@void@TiO2-Na+Suspension respectively with 0,1,2,4,6,8,10,20,40,60,80,100,
200, the silver ion solution of 400,1000,2000,4000,6000,8000 and 10000pmol/L is reacted, to finally obtaining
Fe3O4@void@TiO2The ITO electrode of-Ag microballoon modification carries out photocurrent response test；Test condition are as follows: 0.1mol/L
PBS buffer solution (pH 7.0), bias potential 0.1V；Shown in test result such as Fig. 8 (A), Fig. 8 (B) is corresponding linear gauging
Curve, as shown in Figure 8, photoelectric current gradually amplify with the increase of concentration of silver ions, Fig. 8 (B) show photoelectric current increment with
Quantitative relationship between silver ion increase；Its dynamic linear response range is 1-6000pmol/L, and detection is limited to 0.5pmol/L, Gao Ling
Sensitivity has benefited from the thermoelectron injection amorphous state TiO that generated in-situ Ag nanoparticle generates2Conduction band.The line of three orders of magnitude
Property range is attributable to amorphous state TiO2The porous structure of shell can support a large amount of silver ion, receive to generate more Ag
Rice corpuscles.In addition, the sensor also has many advantages, such as that structure is simple and convenient to operate, is portable, time-consuming is short, cost performance is high.
Experimental example 2
In 0.1mol/L PBS (pH 7.0), to the Fe3O4@void@TiO2-Na+Microballoon modified electrode carries out photoelectric current
Disturbed test, interfering substance include: 50 times of Fe (NO3)3, 50 times of HAuCl4, 100 times of Ni (NO3)2, 500 times of Zn (NO3)2, 500 times
MgSO4, 500 times of Co (NO3)2, 500 times of CuSO4, 500 times of CdSO4, 500 times of KNO3With the mixture of 50 times of above-mentioned substances；Test
As a result as shown in figure 9, as seen from Figure 9, above-mentioned common ion is no more than 7.6% to the maximum interference of the sensor, it was demonstrated that
The sensor has selectivity well.It has benefited from common metal ion or acid group (AuCl4 -, negatively charged, Bu Nengfa
Raw normal cation exchange) metal nanoparticle with plasma resonance cannot be reduced into.
In the present embodiment, firstly, preparation superparamagnetic Fe3O4Nanoparticle, then in its surface successively coated silica
With amorphous state TiO2, secondly, etching silica shell with NaOH solution, form Fe3O4@void@TiO2.The Fe of preparation3O4@
void@TiO2Pass through Ag+-Na+Then ion exchange capture silver ion by being centrifuged and washing, obtains Fe3O4@void@TiO2-
Ag+, with this, Ag+Ion can steadily be present in Fe3O4@void@TiO2In, form metatitanic acid silver, rather than C-Ag+- C is multiple
Miscellaneous structure.When with ethanol washing with reproducibility, then Fe is generated3O4@void@TiO2-Ag.Then, illumination Ag nanoparticle
TiO can be injected in the thermoelectron of generation2Conduction band, effectively generate the photo-signal of enhancing, the silver ion of capture is more, raw
At Nano silver grain it is more.Finally, enhancing mechanism, invention based on the sub- localized surface plasmons resonance of in-site silver nano-particle
A kind of silver ion optical electro-chemistry sensor not needing oligonucleotides, be simple and convenient to operate with structure, good portability,
The features such as high sensitivity, selectivity are good, time-consuming short, cost performance is high.
Embodiment 2
One kind being based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion, the method includes
Following step:
S1, preparation Fe3O4Nano-cluster: the NaOH of 30mmol is dissolved in the DEG of 10mL, under nitrogen protection, is added at 100 DEG C
The NaOH/DEG solution of generation is cooled and maintained at 40 DEG C by hot mixt 0.5h；By 2mmol PAA, 0.2mmol FeCl3With
The mixture of 10mL DEG is heated to 180 DEG C, after being vigorously stirred 25min in nitrogen atmosphere, injects the NaOH/ of 0.8mL rapidly
DEG solution, reaction solution slowly become black, continuous heating 0.5h, the product ethyl alcohol and ultrapure water that will be obtained from light yellow
1 washing is carried out respectively, obtains Fe3O4Nano-cluster, and it is dispersed in again in the ultrapure water of 1mL；
S2, preparation Fe3O4@SiO2Microballoon: the Fe of 1.5mL is added in the mixture of 10mL ethyl alcohol and 0.5mL ammonium hydroxide3O4It suspends
Liquid at room temperature after strong stirring 3min, the TEOS of 40 μ L is added into said mixture, and keep 15min, by generation
Fe3O4@SiO2Nanoparticle is centrifuged, and ethanol washing three times, and it is dispersed in again in 3mL ethyl alcohol；
S3, preparation Fe3O4@SiO2@TiO2Microballoon: by 3mL Fe3O4@SiO2Microballoon, 8mg hydroxylated cellulose, 3mL ethyl alcohol, 1.5mL
After 10min is mixed in acetonitrile and 0.05mL ammonium hydroxide, the ethanol solution of 0.15mL TBOT is added, 1h is stirred, by being collected by centrifugation
The Fe of generation3O4@SiO2@TiO2Microballoon, and washed respectively three times with ethyl alcohol and ultrapure water, it is then 1.5mol/ with 10mL concentration
The NaOH solution of L etches 10min, then the dry 0.5h at 40 DEG C, then calcines 1h in 500 DEG C of nitrogen atmosphere, finally, will
It is dispersed in 3mL water；
S4, preparation Fe3O4@void@TiO2-Ag+Microballoon: the 20mg Fe that will be obtained3O4@SiO2@TiO2Microballoon is dispersed in water,
10mL 1.5mol/L NaOH solution is added, stirs 0.5h, is centrifuged and washes, obtain Fe3O4@void@TiO2-Na+, stored up
There are in 1.5mL water；To 80 μ L Fe3O4@void@TiO2-Na+The Ag of 100 μ L various concentrations is separately added into suspension+Ion
Solution reacts 0.5h, 1 Magneto separate and water washing, obtains Fe3O4@void@TiO2-Ag+Microballoon；
S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement: the Fe that will be obtained3O4@void@TiO2-Ag+Microballoon point
It dissipates in 80 μ L ethyl alcohol, reacts 10min, Magneto separate is simultaneously washed, and Fe is obtained3O4@void@TiO2- Ag microballoon is scattered in 80 μ L water
In；The Fe containing not same amount Ag nanoparticle that 10 μ L are obtained3O4@void@TiO2- Ag suspension distinguishes drop coating in ITO electrode
On, it dries, carries out photoelectricity flow measurement, linear equation, finally, being based on the linear equation, the inspection for silver ion
It surveys.
Embodiment 3
One kind being based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion, the method includes
Following step:
S1, preparation Fe3O4Nano-cluster: the NaOH of 80mmol is dissolved in the DEG of 40mL, under nitrogen protection, is added at 150 DEG C
The NaOH/DEG solution of generation is cooled and maintained at 80 DEG C by hot mixt 2h；By 6mmol PAA, 0.6mmol FeCl3With
The mixture of 27mL DEG is heated to 240 DEG C, after being vigorously stirred 65min in nitrogen atmosphere, injects the NaOH/ of 2.5mL rapidly
DEG solution, reaction solution slowly become black, continuous heating 2h, by obtained product ethyl alcohol and ultrapure moisture from light yellow
It carry out not wash for 5 times, obtain Fe3O4Nano-cluster, and it is dispersed in again in the ultrapure water of 5mL；
S2, preparation Fe3O4@SiO2Microballoon: the Fe of 5mL is added in the mixture of 30mL ethyl alcohol and 2mL ammonium hydroxide3O4Suspension, room
After the lower strong stirring 8min of temperature, the TEOS of 80 μ L is added into said mixture, and keep 50min, by the Fe of generation3O4@
SiO2Nanoparticle is centrifuged, and ethanol washing three times, and it is dispersed in again in 8mL ethyl alcohol；
S3, preparation Fe3O4@SiO2@TiO2Microballoon: by 8mL Fe3O4@SiO2Microballoon, 23mg hydroxylated cellulose, 9mL ethyl alcohol, 6mL
After 30min is mixed in acetonitrile and 0.3mL ammonium hydroxide, the ethanol solution of 0.45mL TBOT is added, 4h is stirred, by being collected by centrifugation
The Fe of generation3O4@SiO2@TiO2Microballoon, and washed respectively three times with ethyl alcohol and ultrapure water, it is then 4.5mol/ with 40mL concentration
The NaOH solution of L etches 40min, then the dry 2h at 80 DEG C, then calcines 4h in 800 DEG C of nitrogen atmosphere, finally, by it
It is dispersed in 10mL water；
S4, preparation Fe3O4@void@TiO2-Ag+Microballoon: the 50mg Fe that will be obtained3O4@SiO2@TiO2Microballoon is dispersed in water,
50mL 5.5mol/L NaOH solution is added, stirs 2h, is centrifuged and washes, obtain Fe3O4@void@TiO2-Na+, stored
In 5.5mL water；To 200 μ L Fe3O4@void@TiO2-Na+The Ag of 400 μ L various concentrations is separately added into suspension+Ion is molten
Liquid reacts 2h, 5 Magneto separates and water washing, obtains Fe3O4@void@TiO2-Ag+Microballoon；
S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement: the Fe that will be obtained3O4@void@TiO2-Ag+Microballoon point
It dissipates in 200 μ L ethyl alcohol, reacts 40min, Magneto separate is simultaneously washed, and Fe is obtained3O4@void@TiO2- Ag microballoon is scattered in 200 μ L
In water；The Fe containing not same amount Ag nanoparticle that 40 μ L are obtained3O4@void@TiO2- Ag suspension distinguishes drop coating in ITO electricity
It on extremely, dries, carries out photoelectricity flow measurement, linear equation, finally, the linear equation is based on, for silver ion
Detection.
As described above, must not be explained although the present invention has been indicated and described referring to specific preferred embodiment
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (7)
1. one kind is based on superparamagnetic Fe3O4@void@TiO2The optical electro-chemistry detection method of in-situ construction silver ion, feature exist
In the method includes the following steps:
S1, preparation Fe3O4Nano-cluster；
S2, preparation Fe3O4@SiO2Microballoon；
S3, preparation Fe3O4@SiO2@TiO2Microballoon；
S4, preparation Fe3O4@void@TiO2-Ag+Microballoon: the Fe that will be obtained3O4@SiO2@TiO2Microballoon is dispersed in water, and is added
NaOH solution, stirring, is centrifuged and washes, obtain Fe3O4@void@TiO2-Na+, it is stored in water；To Fe3O4@void@
TiO2-Na+The Ag of various concentration is separately added into suspension+Solion reacts 0.5-2h, Magneto separate and water washing, obtains
Fe3O4@void@TiO2-Ag+Microballoon；
S5, preparation Fe3O4@void@TiO2- Ag microballoon and photoelectricity flow measurement: the Fe that will be obtained3O4@void@TiO2-Ag+Microballoon point
It dissipates in ethyl alcohol, reacts 10-40min, Magneto separate is simultaneously washed, and Fe is obtained3O4@void@TiO2- Ag microballoon, is dispersed in water；It will
The obtained Fe containing not same amount Ag nanoparticle3O4@void@TiO2- Ag suspension distinguishes drop coating in ITO electrode, dries,
Photoelectricity flow measurement, linear equation are carried out, finally, being based on the linear equation, the detection for silver ion.
2. optical electro-chemistry detection method according to claim 1, which is characterized in that in S4, Fe3O4@SiO2@TiO2Microballoon with
The mass volume ratio (mg/ml) of water is 2-5:1-5.
3. optical electro-chemistry detection method according to claim 1 or 2, which is characterized in that in S4, Fe3O4@void@TiO2-
Na+Suspension and Ag+The volume ratio of solion is 4-10:5-20.
4. optical electro-chemistry detection method according to claim 1 or 2, which is characterized in that in S4,1.5-5.5mol/L is added
NaOH solution stirs 0.5-2h.
5. optical electro-chemistry detection method according to claim 1 or 2, which is characterized in that in S1, Fe3O4The preparation of nano-cluster
Method is as follows: the NaOH of 30-80mmol being dissolved in the DEG of 10-40mL, under nitrogen protection, is heated at 100-150 DEG C mixed
Object 0.5-2h is closed, the NaOH/DEG solution of generation is cooled and maintained at 40-80 DEG C；By 2-6mmol PAA, 0.2-0.6mmol
FeCl3It is heated to 180-240 DEG C with the mixture of 10-27mL DEG, after being vigorously stirred 25-65min in nitrogen atmosphere, rapidly
The NaOH/DEG solution of 0.8-2.5mL is injected, reaction solution slowly becomes black from light yellow, and continuous heating 0.5-2h is incited somebody to action
To product ethyl alcohol and ultrapure water carry out respectively 1-5 times washing, obtain Fe3O4Nano-cluster, and it is dispersed in 1-5mL again
Ultrapure water in.
6. optical electro-chemistry detection method according to claim 1 or 2, which is characterized in that in S2, Fe3O4@SiO2Microballoon
The preparation method is as follows: the Fe of 1.5-5mL is added in the mixture of 10-30mL ethyl alcohol and 0.5-2mL ammonium hydroxide3O4Suspension, room temperature
After lower strong stirring 3-8min, the TEOS of 40-80 μ L is added into said mixture, and keep 15-50min, by generation
Fe3O4@SiO2Nanoparticle is centrifuged, and ethanol washing three times, and it is dispersed in again in 3-8mL ethyl alcohol.
7. optical electro-chemistry detection method according to claim 1 or 2, which is characterized in that in S3, Fe3O4@SiO2@TiO2It is micro-
Ball the preparation method is as follows: by 3-8mL Fe3O4@SiO2Microballoon, 8-23mg hydroxylated cellulose, 3-9mL ethyl alcohol, 1.5-6mL acetonitrile
After 10-30min is mixed with 0.05-0.3mL ammonium hydroxide, the ethanol solution of 0.15-0.45mL TBOT is added, stirs 1-4h, leads to
Cross the Fe that generation is collected by centrifugation3O4@SiO2@TiO2Microballoon, and washed respectively three times with ethyl alcohol and ultrapure water, then use 10-40mL
The NaOH solution that concentration is 1.5-4.5mol/L etches 10-40min, then the dry 0.5-2h at 40-80 DEG C, then in 500-
1-4h is calcined in 800 DEG C of nitrogen atmosphere, finally, being dispersed in 3-10mL water.
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