CN110108772A - A kind of modified meerschaum modified electrode and the preparation method and application thereof - Google Patents
A kind of modified meerschaum modified electrode and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of modified meerschaum modified electrode and the preparation method and application thereof, specifically including using glucose as carbon source, ethylenediamine is that nitrogen source is modified to sepiolite raw ore progress nitrogen-doped carbon, then increases specific surface area with HF etching and HCl acidification；Original position Ag doping is finally carried out, a kind of Cu of novel sea urchin shape is obtained2O modified meerschaum modified electrode.Nitrogen-doped carbon is modified, HF is etched, Cu2The methods of O assembling, Ag doping improve material specific surface area, enhance electric conductivity, to be obviously improved chemical property；So that modified meerschaum modified electrode is to H2O2Concentration has quick response, and low applies current potential: -0.45V；Wide detection range: 1.0 × 10‑6‑3.295×10‑3M；Low detection limit 2.0 × 10‑8M, while having many advantages, such as that repeatability, reproducibility, stability are good, strong antijamming capability has boundless application prospect.
Description
Technical field
The present invention relates to electrochemical field, in particular to a kind of modified meerschaum modified electrode and preparation method thereof with answer
With.
Background technique
In recent years, using clay as the functional nano-composite material of carrier catalysis, absorption and electrochemical field gradually at
For research hotspot.Introducing the clay minerals such as kaolinite, galapectite, montmorillonite, sepiolite is carrier, and function has not only been effectively fixed
Energy nano particle, improves the agglomeration of reactant, and in absorption or catalytic process, and association is generated between clay and functional material
Same-action it significantly further improves the comprehensive performance of reactant.However, due to the poorly conductive of mineral, it is therefore necessary to
Enhance the electric conductivity of clay, by method of modifying appropriate to expand it in the research and application of electrochemical field.
Sepiolite (Sepiolite) is a kind of natural nano clay mineral, due to its specialty fibers form, high-ratio surface
Product, non-toxic, strong adsorptivity and cheap price, are commonly used for the carrier of assembling functional material.However, although some researchers
Attempt the electric conductivity that sepiolite is improved by physical or chemical modification, but result and unsatisfactory.Pekin is prepared for one kind
16000 Ω sepiolite clay carbon paste electrode of high impedance, for ascorbic acid quantitative analysis (Ionics, 2017,23,3487-
3495).Erdem using scpiolitc and single-walled carbon nanotube it is compound have developed it is a kind of with 700 Ω impedance graphite electrodes
DNA sensor (Analyst, 2012,137,4001-4004).Yan is in the anatase with high dielectric constant and semiconducting behavior
The sepiolite over-assemble spherical shape Cu of type titanium dioxide nano-particle (1-10nm) modification2O nanoparticle (70-300nm), has synthesized resistance
Resist the novel H for 526.5 Ω2O2Sensor (Journal of Electroanalytical Chemistry, 2018,827,
1).But the impedance of the clay modified electrode of sepiolite is still very high, the suitable mineral modified method of selection promotes leading for sepiolite
Electrically have become the key of clay modified application of electrode.
Summary of the invention
The present invention provides a kind of modified meerschaum modified electrodes and the preparation method and application thereof, and its purpose is to improve
The mass transfer ability of electrode surface and the active site of electrochemical reaction, further enhance electrochemical response.
In order to achieve the above object, the present invention provides following scheme:
The present invention provides a kind of preparation method of modified meerschaum modified electrode, includes the following steps:
(1) it sepiolite and the glucose of quality such as takes soluble in water, ethylenediamine is added, in hot bath down toward water after stirring
Divide and be all evaporated, finally carries out calcination processing under an inert atmosphere, obtain CNSEP powder；Wherein the quality of ethylenediamine is Hai Pao
2~2.5 times of stone；
(2) CNSEP powder obtained by step (1) is performed etching with HF, then is filtered, washed and is dried, finally use HCl
It is acidified, obtains ACNSEP powder；
It (3) is in mass ratio 1:8~10:7~8 by ACNSEP powder obtained by step (2) and copper source and surfactant
Ratio mixing, then adjust pH value to alkalescent, hydrazine hydrate be then added and is restored, finally filtered, washed and is dried,
Obtain Cu2O/ACNSEP composite powder；
(4) by Cu obtained by step (3)2O/ACNSEP composite powder and AgNO3It is dissolved in organic solvent, wherein Cu2O/
ACNSEP composite powder and AgNO3Mass concentration ratio be 1:0.02~0.04；Then it is stirred to react under an inert atmosphere, most
After filtered, washed and dried, obtain Ag/Cu2O/ACNSEP powder；
(5) by Ag/Cu obtained by step (4)2The modification of O/ACNSEP powder is prepared into Ag/Cu to glassy carbon electrode surface2O/
ACNSEP/GCE modified electrode.
Preferably, calcination processing temperature described in step (1) is 500~700 DEG C.
Preferably, copper source described in step (3) is CuCl2.2H2O、CuSO4.5H2O or Cu (NO3)2.3H2O；The surface
Activating agent is polyvinylpyrrolidone or cetyl trimethylammonium bromide.
Preferably, pH value is adjusted to alkalescent with NaOH solution in step (3).
Preferably, the concentration of hydrazine hydrate described in step (3) is 80~85%, and adding manner is to be added dropwise.
Preferably, organic solvent described in step (4) is the mixed solution of dehydrated alcohol and deionized water.
Preferably, dry described in step (4) is specially the dry 3-5h at 40~50 DEG C.
Preferably, step (5) is specially by Ag/Cu obtained by step (4)2O/ACNSEP powder is in dehydrated alcohol, deionization
It is uniformly dispersed in the mixed solution that water is formed with Nafion reagent three, then liquid relief to glassy carbon electrode surface is prepared into Ag/
Cu2O/ACNSEP/GCE modified electrode.
The present invention also provides a kind of modified meerschaum modified electrode, the modified meerschaum modified electrode is by above-mentioned any one
Item method is prepared.
The present invention also provides modified meerschaum modified electrode made from the above method or above-mentioned modified meerschaum modified electrodes
In detection H2O2In application.
Above scheme of the invention have it is following the utility model has the advantages that
(1) present invention is using the sepiolite with good stability, hydrophily and dispersibility as carrier, and the effect of mineral is not only
Promote Cu2The assembling and dispersion of O functional material, are conducive to the promotion of electric conductivity, while modified meerschaum and function has also been introduced
The synergistic effect of energy storeroom, is conducive to further increase electrochemical response.Meanwhile sepiolite is in China's rich reserves, price
It is cheap；
(2) present invention passes through nitrogen-doped carbon modification, HF etching, Cu2The methods of O assembling, Ag doping have been obviously improved electrification
Learn performance；Ag adulterates Cu2O, not only controllable Cu2The pattern of O obtains a kind of Cu of novel sea urchin shape2O can also enhance conduction
Property and increasing specific surface area, dramatically increase electro-chemical activity site, effectively improve modified meerschaum modified electrode electric conductivity and
Electrochemical response；
(3) H that the present invention is prepared with modified meerschaum modified electrode2O2Sensor fast response time, with low application electricity
Position: -0.45V；Wide detection range: 1.0 × 10-6-3.295×10-3M；Low detection limit 2.0 × 10-8M, have repeatability,
The advantages that reproducibility, stability are good, strong antijamming capability has boundless application prospect.
Detailed description of the invention
Fig. 1 is Ag/Cu in the embodiment of the present invention 12The flow chart of O/ACNSEP/GCE modified electrode；
Fig. 2 is the XRD spectrum of each substance in the embodiment of the present invention 1；
Fig. 3 is the N of each substance in the embodiment of the present invention 12Adsorption-desorption curve and corresponding graph of pore diameter distribution: (a)
CNSEP；(b)ACNSEP；(c)Cu2O/ACNSEP；(d)Ag/Cu2O/ACNSEP；
Fig. 4 is the TEM map of each substance in the embodiment of the present invention 1: (a) CNSEP, (b) and (c) ACNSEP, (d) Cu2O/
ACNSEP, (e) and (f) Ag/Cu2O/ACNSEP；And HRTEM map: (g) Cu2O/ACNSEP, (h) Ag/Cu2O/ACNSEP；
Fig. 5 is H containing 1mmol/L in the embodiment of the present invention 12O2PBS buffer solution in, sweep speed be 50mV/s under SEP/
The CVs curve of GCE, CNSEP/GCE, Bare GCE, ACNSEP/GCE electrode；(b) H containing 1mmol/L2O2PBS buffer solution in,
Sweep speed is Ag/Cu under 50mV/s2O/GCE、Cu2O/CAN/GCE、Cu2O/ACNSEP/GCE、Ag/Cu2O/ACNSEP/GCE
The CVs curve of electrode；
Fig. 6 be in the embodiment of the present invention 1 in the potassium ferricyanide containing 5mmol/L/potassium ferrocyanide 0.1mol/LKCl solution not
EIS with electrode schemes, and illustration is corresponding equivalent-circuit model；(b) EIS enlarged drawing of the Different electrodes in high frequency region；
Fig. 7 be in the embodiment of the present invention 1 a) in PBS buffer solution (pH=7.4) in Ag/Cu2Apply on O/ACNSEP electrode-
0.45V's applies current potential, and H is continuously added dropwise during being stirred continuously2O2The chronoa mperometric plot that solution obtains；(b) stablize electricity
Current density is to H2O2The calibration curve of concentration；
Fig. 8 is in the embodiment of the present invention 1 in Ag/Cu210 reduction currents are continuously detected on O/ACNSEP/GCE electrode
Density histogram；(b) different Ag/Cu are prepared respectively under same experimental conditions2Reduction peak electricity on O/ACNSEP/GCE electrode
Flow histogram；(c)Cu2Reduction peak current 7 on O/CNASEP/GCE electrode, after 14,21 days compares, 4 identical Ag/Cu2O/
The standard deviation of reduction peak current density is indicated with error bar on ACNSEP/GCE electrode；(d)Ag/Cu2O/ACNSEP/GCE electrode
In PBS buffer solution (pH=7.0), 100 times of H are sequentially added2O2Concentration interfering substance (ascorbic acid, sucrose, glucose,
Fructose, oxalic acid) ampere response.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
Embodiment 1
(1) 0.2g SEP is taken, 0.2g glucose and 50mL deionized water are added in beaker, then accurately pipette 0.4g second two
Amine is evaporated under 80 DEG C of water bath conditions after 8h is sufficiently stirred, and obtained sample calcines 5h under 500 DEG C of inert atmospheres, is obtained
Nitrogen-doped carbon modified meerschaum (CNSEP).
(2) it takes the CNSEP 0.2g of preparation to be added in beaker, adds 5mL HF (mass fraction 40%) and sufficiently react
By vacuum filtration washing, drying.Powder 0.1g obtained is taken again, and 50mL 6mol/L concentration HCl is added, is acidified under stiring
5h is handled, obtains the CNSEP (ACNSEP) of HF etching, dense HCl acidification through filtering and washing.
(3) 0.02g ACNSEP compound is weighed in conical flask, sequentially adds 0.15g PVP (polyvinylpyrrolidine
Ketone) it is used as surfactant and 0.1785g CuCl2.2H2O pipettes 200mL deionized water as copper source, then with graduated cylinder, holds
Continuous stirring is for 24 hours uniformly mixed sample.The 6M NaOH solution that 1.2mL is added dropwise (adjusts pH value to weak base to mixed solution
Property), persistently stirring 15min to solution colour becomes blue.It is added dropwise 797.5 μ L's 80% again under 80 DEG C of water bath conditions
Hydrazine hydrate (reducing agent) continues stirring until solution colour and stablizes.Through suction filtration, washing, it is dried in vacuo up to group on CNASEP fiber
Fill Cu2Compound (the Cu of O nano particle2O/ACNSEP)。
(4) it is added in three-necked flask using 100mL deionized water and 100mL dehydrated alcohol as solvent, adds Cu2O/
ACNSEP and AgNO3, making its mass concentration is respectively 0.5g/L and 0.016g/L.It is passed through enough N2, stir under an inert atmosphere
24h.Next day filtering and washing, dry 3h obtains the modified meerschaum base assembling Cu of Ag doping at 40 DEG C2O nanocomposite
(Ag/Cu2O/ACNSEP)。
(5) by Ag/Cu made from step (4)2O/ACNSEP modified electrode is applied in PBS buffer solution to H2O2In detection, and
Test result.
Synthetic route is as shown in Figure 1.Take Ag/Cu2O/ACNSEP 8mg, 475 μ L dehydrated alcohols, 475 μ L deionized waters and
50 μ L Nafion reagents are uniformly dispersed after ultrasonic 1h, and liquid-transfering gun pipettes 10 μ L and is added drop-wise to pretreated glass-carbon electrode, room temperature
Under be evaporated after obtain Ag/Cu2O/ACNSEP/GCE sensor.
For the image composition inside analysis substance, XRD characterization is carried out to different samples, as a result as shown in Fig. 2 (a), (b).
SEP XRD spectrum after pretreatment and sepiolite raw ore (Mg4Si6O15(OH)2.6H2O) card (PDF 29-1492) unanimously,
Occur an apparent spike, corresponding CaCO at 29.6 °3(PDF05-0586) (104) crystal face, illustrating SEP, there are CaCO3It is miscellaneous
Matter.Nearby there is a wide diffraction maximum at 26.6 ° by N doped carbon is modified, corresponds to unformed C (006) crystal face.HF is carved
After erosion and dense HCl acidification, sample ACNSEP is remarkably reinforced at 26.6 ° of peak, and XRD spectrum and SiO2Card (PDF 46-
1045) corresponding, SiO is generated after illustrating the fibre structure etching of CNSEP2。Cu2O/ACNSEP and Ag/Cu2O/ACNSEP with
Cu2O card (05-0667) coincide, and shows the generation of cuprous oxide.Meanwhile Ag/Cu2The XRD spectrum of O/ACNSEP goes out at 38.1 °
Now weaker peak corresponds to (111) crystal face of Ag nano particle (PDF 04-0783).For research sepiolite prepared by material
It influences, Cu in analysis chart 2 (b)2O/ACN sample map, finds no Cu2The diffraction maximum of O, this may be because the hydrophilic of sepiolite
Property and dispersibility are more advantageous to Cu2The assembling of O particle.Ag/Cu2Cu is clearly present in the map of O2The diffraction of O and Ag nano particle
Peak, with Cu2O/ACN map comparative illustration is merely that cannot effectively assemble Cu on carrier in CN2O nano particle, such as Cu2O/
Shown in ACNSEP map, the cuprous nano material of combined oxidation can just only be obtained as carrier using modified meerschaum.
Preferably to study influence to material structure after HF engraving, dense HCl acidification and Ag doping, to CNSEP,
ACNSEP、Cu2O/ACNSEP and Ag/Cu2Tetra- kinds of samples of O/ACNSEP carry out BET test, corresponding N2Adsorption-desorption curve is such as
Shown in Fig. 3 (a)-(d).The IV of mesoporous solid material generation is belonged to according to four kinds of samples of shape of adsorption-desorption curve
Type adsorption equilibrium thermoisopleth.In higher relative pressure area, capillary condensation occurs for adsorbate, and thermoisopleth rises rapidly, at this
Hysteresis can be observed in range, since the thermoisopleth obtained when desorption is not overlapped with when absorption, and desorption isotherm is located at
Above adsorption isotherm, hysteresis loop is generated.It is related with the size and shape in hole that hysteresis is desorbed, by studying desorption isotherm
It can obtain the pore-size distribution (Fig. 3 illustration) and pore structure parameter (table 1) of respective sample.Meanwhile according to it is international purely with application
Chemical combined meeting (IUPAC) regulation, four kinds of samples do not show any absorption limitation in higher relative pressure region, sluggish
Ring is H3 type.Sample specific surface area is respectively CNSEP (64.147m from small to large2/g)、ACNSEP(111.509m2/g)、
Cu2O/ACNSEP(128.666m2/ g) and Ag/Cu2O/ACNSEP(178.983m2/g).It can be seen that CNSEP by HF engraving,
Specific surface area increases nearly twice after dense HCl acidification, is conducive to next step Cu2+Absorption and cuprous oxide nano particle group
Dress；Specific surface area further increases after Ag nano particle etching, is conducive to electrode material and is in close contact with electrolyte to promote to pass
Matter, and significantly improve the active site of electro-catalysis.
The specific surface area and pore structure parameter of the different samples of table 1
More intuitively to understand function after the influence and Ag doping of HF etching, concentrated hydrochloric acid acidification to sepiolite nanofibrous structures
It can nano material Cu2The pattern of O particle changes, CNSEP, ACNSEP, Cu2O/ACNSEP、Ag/Cu2The TEM map of O/ACNSEP
As shown in Figure 4.CNSEP still maintains the fibre structure of sepiolite in Fig. 4 (a), illustrates that sepiolite structure has good heat steady
It is qualitative.As shown in Fig. 4 (b) (c), when CNSEP is after HF etching, concentrated hydrochloric acid acidification, the fiber surface of sepiolite occurs a large amount of
Apparent aperture can significantly increase the specific surface area of sepiolite, generate more active sites promote next step mineral surfaces with
Cu2+Combination, be conducive to the assembling of cuprous oxide functional material and the raising of chemical property.Work as Ag doping in Fig. 4 (e) (f)
Afterwards, Cu2The pattern of O becomes apparent sea urchin shape from the rescinded angle octahedron of Fig. 4 (d), this is relative to sample Cu2O/ACNSEP ratio
The reason of surface area significantly increases restores H for electro-catalysis2O2More active sites are provided.According to interplanar distance meter in Fig. 4 (g)
Calculation obtains 0.25nm, with Cu2(111) oikocryst face of O is consistent, it was demonstrated that in Cu2There are Cu by O/ACNSEP2O ingredient.Similarly Ag/
Cu2In the HRTEM figure of O/ACNSEP, calculates interplanar distance and obtain 0.25nm, 0.21nm, 0.23nm, correspond respectively to Cu2O's
(111) oikocryst face, Cu2(111) oikocryst face of (200) crystal face of O, Ag, shows Cu2The generation of O and Ag.
Fig. 5 (a), (b) are that different modifying electrode is containing 1mmol/LH2O2PBS buffer solution in CVs comparison, sweep speed
It is 50mV/s.The reduction peak current density of electrode is relative to composite Cu in Fig. 5 (b) in Fig. 5 (a)2O nano particle functional material
Modified electrode is unobvious, this shows Cu2The load of O is more advantageous to H2O2Electrochemical Detection.Specifically, in Fig. 5 (a) due to
The poorly conductive of scpiolitc, SEP/GCE electrode does not have peak current appearance, and changes by the nitrogen-doped carbon that high-temperature calcination obtains
Property sepiolite, there is sintering phenomenon, specific surface area is smaller, CNSEP/GCE electrode also without apparent peak current occur.
CNSEP is after HF is etched and dense HCl is acidified, and specific surface area increases by about one time as shown in BET result, this may advantageously facilitate electrode material
Mass transfer between material and electrolyte, therefore faint reduction peak current density (22.53 μ A/ are observed on ACNSEP/GCE electrode
cm2).In Fig. 5 (b), to explore SEP mineral in H2O2Effect in electro-catalysis, passes through Ag/Cu2O/GCE(59.31μA/cm2) with
Ag/Cu2O/ACNSEP/GCE(271.58μA/cm2)、Cu2O/ACN/GCE(76.27μA/cm2) and Cu2O/ACNSEP/GCE
(135.98μA/cm2) two groups of reduction peak current density comparisons, it is loud that discovery SEP as the addition of carrier can significantly increase electrochemistry
It answers, this is primarily due to sepiolite good hydrophily and dispersibility in aqueous solution, peomotes Cu2O nano particle is more
Disperse well, to improve chemical property.Meanwhile Cu2O/ACNSEP/GCE and Ag/Cu2O/ACNSEP/GCE compare it is found that
Chemical property is obviously improved after Ag doping, not only due to the good electric conductivity of Ag may advantageously facilitate the electricity between material and electrolyte
Son transmitting, and to Cu after Ag doping2The pattern of O has an impact, and is transformed into sea urchin shape by rescinded angle octahedron, specific surface area is significant
Increase, with H2O2The active site of reaction increases, this is the main reason for chemical property improves.
More effectively to study H2O2In Ag/Cu2The reaction process of O/ACNSEP/GCE electrode surface electro-catalysis reduction,
K containing 5mM3[Fe(CN)6] 0.1M KCl solution in apply a constant potential, to Different electrodes use electrochemical impedance spectroscopy
(EIS) the nyquist curve that method measures is as shown in Figure 6.In general, the semicircle in curve medium-high frequency area is by charge transfer process
Control, corresponding to the resistance between active material and electrolyte, and the straight line of low frequency range is controlled by diffusion process, with Warburg
Impedance is related.Based on the equivalent-circuit model as shown in illustration in Fig. 6, these complicated impedance spectrums can be fitted well, show not
Same electrode has similar interface behavior.Rs represents the resistance of electrolyte between working electrode and platinum electrode, and electric charge transfer
The sizableness of resistance (Rct) reflects the electric conductivity of electrode material in half circular diameter.Table 2 shows Different electrodes impedance
Equivalent Circuit Fitting data, wherein the Rs difference of Different electrodes is fluctuated in a small range of 10 Ω, shows Electrochemical Test Procedure
Middle electrolyte is with good stability.Compared with other modified electrodes, Ag/Cu2The Rct (72.3 of O/ACNSEP/GCE electrode
Ω) value is minimum, shows that the electrode has excellent electric conductivity.The Rct of Different electrodes, which is compared, to be proved, nitrogen-doped carbon is compound to be changed
Property, assembling Cu2O nanoparticle and Ag doping are conducive to improve the electric conductivity of material.By comparing Ag/Cu2O/GCE
(165.9 Ω) and Ag/Cu2O/ACNSEP/GCE(72.3Ω)、Cu2O/ACN/GCE (248.2 Ω) and Cu2O/ACNSEP/GCE
(114.8 Ω) this two groups Rct value, has found that while that sepiolite is poor as the electric conductivity of mineral itself, but after addition sepiolite
Be conducive to instead improve material electric conductivity, this is because sepiolite has excellent stability in aqueous solution, hydrophily and
Dispersibility, it is consistent with CVs result.Meanwhile Cu2O/ACNSEP/GCE (114.8 Ω) and Ag/Cu2O/ACNSEP/GCE(72.3Ω)
For impedance comparison it is found that impedance value substantially reduces after Ag doping again, this is one of the reason of chemical property is obviously improved.
The Equivalent Circuit Fitting data of 2 Different electrodes impedance of table
Chronoamperometry is as common electrochemical Characterization, for measuring the range of linearity, sensitivity and the detection limit of electrode
Equal chemical properties.As shown in Fig. 7 (a), it is -0.45V using current potential, is continuously added to the H of various concentration2O2Solution, using Ag/
Cu2The chronoa mperometric plot that O/ACNSEP electrode is obtained as working electrode.In the case where application current potential is -0.45V, Ag/Cu2O/
ACNSEP/GCE electrode is to H2O2Concentration has quick response, and the 90% of stabling current can be reached in 1s.The data of Fig. 7 (b)
From Fig. 7 (a), it can be clearly seen that in H2O2Concentration is in the range of 1 μM to 3.295mM, current density and H2O2Concentration is in
Existing good linear relationship (R2=0.9991), corresponding Calibration equation is Ip (μ Acm-2)=- 111.2199C (mM)-
41.0032.By can be calculated, the sensitivity of modified electrode is about 111.22 μ AmM-1·cm-2, detect and be limited to 0.02 μM
(S/N=3).
Difference H in recent years2O2The chemical property comparison of sensor is as shown in table 3.It can be seen that Ag/Cu2O/
ACNSEP/GCE electrode is relative to other clay-based H2O2Sensor either precious metal sensor, the range of linearity, detection limit and
Response time etc. still has apparent advantage, wherein detection limit 2.0 × 10-8M is to use electrification in current document report
Learn the minimum concentration that detection technique can be detected.Show the electrode for H in actual sample2O2Detection have it is outstanding
Advantage.
3 difference H of table2O2The comparison of sensor chemical property
Repeatability, reproducibility, stability and the selectivity of electrode are an important factor for judging electrode performance.Such as Fig. 8 (a) institute
Show, in H containing 2mM2O2PBS buffer solution in, continuous scanning Ag/Cu210, O/ACNSEP/GCE electrode circulations, all CV curves
Reduction peak current density relative standard deviation (RSD) is 1.66%, shows Ag/Cu2Electro-catalysis restores on O/ACNSEP/GCE electrode
H2O2Repeatability preferably.Measure five identical Ag/Cu2Shown in the result of O/ACNSEP/GCE electrode such as Fig. 8 (b), gained reduction
The RSD of peak current density is 1.88%, illustrates electrode to H2O2Electro-catalysis reduction have good reproducibility.It is individually positioned in
7,14 and 21 days Ag/Cu in low temperature drying environment2O/ACNSEP/GCE electrode, the H of measurement2O2Reduction peak current density such as Fig. 8
(c) shown in, in storage, performance response has faint decline (1.24%) after a week, but storage is still unfavorable for electrochemistry inspection too long
It surveys, therefore testing electrode used therein is current existing system.To investigate Ag/Cu2O/ACNSEP/GCE electrode is to H2O2The selection of substance
Property, reach stabling current density when electric current is in 400s in PBS buffer solution, measurement may be had an impact by sequentially adding
Interfering substance, such as ascorbic acid, sucrose, glucose, fructose, oxalic acid, concentration H2O2100 times, as a result such as Fig. 8 (d) institute
Show.Only H2O2Just there is significant current density change after addition, and response current fluctuating range is smaller after interfering substance is added,
Illustrate Ag/Cu2O/ACNSEP/GCE electrode is to H2O2It has good selectivity.
Embodiment 2
(1) 0.2g SEP is taken, 0.2g glucose and 50mL deionized water are added in beaker, then accurately pipette 0.5g second two
Amine is evaporated under 80 DEG C of water bath conditions after 8h is sufficiently stirred, and obtained sample calcines 4h under 700 DEG C of inert atmospheres, is obtained
Nitrogen-doped carbon modified meerschaum (CNSEP).
(2) it takes the CNSEP 0.2g of preparation to be added in beaker, adds 5mL HF (mass fraction 40%) and sufficiently react
By vacuum filtration washing, drying.Powder 0.1g obtained is taken again, and 50mL 6mol/L concentration HCl is added, is acidified under stiring
5h is handled, obtains the CNSEP (ACNSEP) of HF etching, dense HCl acidification through filtering and washing.
(3) 0.02g ACNSEP compound is weighed in conical flask, sequentially adds 0.16g CTAB (cetyl front three
Base ammonium bromide) it is used as surfactant and 0.2g CuSO4.5H2O pipettes 200mL deionized water as copper source, then with graduated cylinder,
Lasting stirring is for 24 hours uniformly mixed sample.Be added dropwise the 6mol/L NaOH solution of 1.2mL to mixed solution (adjust pH value to
Alkalescent), persistently stirring 15min to solution colour becomes blue.797.5 μ L are added dropwise again under 80 DEG C of water bath conditions
85% hydrazine hydrate (reducing agent) continues stirring until solution colour and stablizes.Through suction filtration, washing, it is dried in vacuo up to CNASEP fibre
Tie up over-assemble Cu2Compound (the Cu of O nano particle2O/ACNSEP)。
(4) it is added in three-necked flask using 100mL deionized water and 100mL dehydrated alcohol as solvent, adds Cu2O/
ACNSEP and AgNO3, making its mass concentration is respectively 0.5g/L and 0.01g/L.It is passed through enough N2, stir under an inert atmosphere
24h.Next day filtering and washing, dry 5h obtains the modified meerschaum base assembling Cu of Ag doping at 50 DEG C2O nanocomposite
(Ag/Cu2O/ACNSEP)。
Embodiment 3
(1) 0.2g SEP is taken, 0.2g glucose and 50mL deionized water are added in beaker, then accurately pipette 0.45g second
Diamines is evaporated under 80 DEG C of water bath conditions after 8h is sufficiently stirred, and obtained sample calcines 5h under 600 DEG C of inert atmospheres, is obtained
To nitrogen-doped carbon modified meerschaum (CNSEP).
(2) it takes the CNSEP 0.2g of preparation to be added in beaker, adds 5mL HF (mass fraction 40%) and sufficiently react
By vacuum filtration washing, drying.Powder 0.1g obtained is taken again, and 50mL 6mol/L concentration HCl is added, is acidified under stiring
5h is handled, obtains the CNSEP (ACNSEP) of HF etching, dense HCl acidification through filtering and washing.
(3) 0.02g ACNSEP compound is weighed in conical flask, sequentially adds 0.14g CTAB (cetyl front three
Base ammonium bromide) it is used as surfactant and 0.16g CuSO4.5H2O pipettes 200mL deionization as copper source, then with graduated cylinder
Water, lasting stirring are for 24 hours uniformly mixed sample.The 6mol/L NaOH solution that 1.2mL is added dropwise (adjusts pH to mixed solution
It is worth to alkalescent), persistently stirring 15min to solution colour becomes blue.797.5 μ L are added dropwise again under 80 DEG C of water bath conditions
85% hydrazine hydrate (reducing agent) continues stirring until solution colour and stablizes.Through suction filtration, washing, it is dried in vacuo up to CNASEP fibre
Tie up over-assemble Cu2Compound (the Cu of O nano particle2O/ACNSEP)。
(4) it is added in three-necked flask using 100mL deionized water and 100mL dehydrated alcohol as solvent, adds Cu2O/
ACNSEP and AgNO3, making its mass concentration is respectively 0.5g/L and 0.02g/L.It is passed through enough N2, stir under an inert atmosphere
24h.Next day filtering and washing, dry 4h obtains the modified meerschaum base assembling Cu of Ag doping at 45 DEG C2O nanocomposite
(Ag/Cu2O/ACNSEP)。
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified meerschaum modified electrode, which comprises the steps of:
(1) it sepiolite and the glucose of quality such as takes soluble in water, adds ethylenediamine, it is complete down toward moisture in hot bath after stirring
Portion is evaporated, and finally carries out calcination processing under an inert atmosphere, obtains CNSEP powder；Wherein the quality of ethylenediamine is the 2 of sepiolite
~2.5 times；
(2) CNSEP powder obtained by step (1) is performed etching with HF, then is filtered, washed and is dried, finally carried out with HCl
Acidification, obtains ACNSEP powder；
(3) be in mass ratio by ACNSEP powder obtained by step (2) and copper source and surfactant 1:8~10:7~8 ratio
Example mixing, then pH value is adjusted to alkalescent, hydrazine hydrate is then added and is restored, finally filtered, washed and is dried, obtained
Cu2O/ACNSEP composite powder；
(4) by Cu obtained by step (3)2O/ACNSEP composite powder and AgNO3It is dissolved in organic solvent, wherein Cu2O/ACNSEP
Composite powder and AgNO3Mass concentration ratio be 1:0.02~0.04；Then it is stirred to react, finally carries out under an inert atmosphere
Suction filtration, washing and drying, obtain Ag/Cu2O/ACNSEP powder；
(5) by Ag/Cu obtained by step (4)2The modification of O/ACNSEP powder is prepared into Ag/Cu to glassy carbon electrode surface2O/ACNSEP/
GCE modified electrode.
2. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that described in step (1)
Calcination processing temperature is 500~700 DEG C, and the calcination processing time is 4~5h.
3. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that described in step (3)
Copper source is CuCl2.2H2O、CuSO4.5H2O or Cu (NO3)2.3H2O；The surfactant is polyvinylpyrrolidone or 16
Alkyl trimethyl ammonium bromide.
4. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that used in step (3)
NaOH solution adjusts pH value to alkalescent.
5. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that described in step (3)
The concentration of hydrazine hydrate is 80~85%, and adding manner is to be added dropwise.
6. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that described in step (4)
Organic solvent is the mixed solution of dehydrated alcohol and deionized water.
7. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that described in step (4)
Dry is specially dry 3~5h at 40~50 DEG C.
8. the preparation method of modified meerschaum modified electrode according to claim 1, which is characterized in that step (5) is specially
By Ag/Cu obtained by step (4)2The mixing that O/ACNSEP powder is formed in dehydrated alcohol, deionized water and Nafion reagent three
It is uniformly dispersed in solution, then liquid relief to glassy carbon electrode surface is prepared into Ag/Cu2O/ACNSEP/GCE modified electrode.
9. a kind of modified meerschaum modified electrode, which is characterized in that the modified meerschaum modified electrode is by claim 1~8
Any one the method is prepared.
10. a kind of modified meerschaum modified electrode as made from claim 1~8 any one the method or such as claim
The 9 modified meerschaum modified electrodes are in detection H2O2In application.
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