CN108548860A - Trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene - Google Patents
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Abstract
The invention discloses a kind of trivalent arsenic electrochemical detection methods based on trithiocyanuric acid/reduced graphene, belong to electrochemical sensing technical field.Using trithiocyanuric acid and graphene oxide as raw material, trithiocyanuric acid/reduced graphene nanocomposite is prepared using a step sodium borohydride reduction, it is coated onto electrode surface and trithiocyanuric acid/reduced graphene modified electrode is made, sulfydryl in trithiocyanuric acid can carry out selective enrichment by pozzuolite key to trivalent arsenic, the bigger serface of reduced graphene also contributes to the current density of electro-chemical test with excellent electric conductivity, and the sensitivity and selective enumeration method of trivalent arsenic in environmental water sample are realized by Square wave anodic stripping voltammetry method.
Description
Technical field
The present invention relates to a kind of trivalent arsenic electrochemical detection methods based on trithiocyanuric acid/reduced graphene, belong to electricity
Chemical sensitisation technical field.
Background technology
With the continuous propulsion of modernization industry level, heavy metal contaminants problem, especially arsenic pollution already become generation
The environmental problem of criticality.Currently, all detecting arsenic in the water environment of many countries and regions in the world, concentration range is more than the world
The drinking water standard limit value (10ppb) of health organization.Arsenic mainly exists in the form of inorganic arsenic that is, trivalent in drinking water
The toxicity of arsenic (As (III)) and pentavalent arsenic (As (V)), wherein As (III) is maximum.Therefore, particularly heavy to the detection of As (III)
It wants.It is square with atomic absorption spectrography (AAS), atomic fluorescence method, inductively coupled plasma mass spectrometry, ultraviolet-visible spectrophotometry etc.
Method is compared, and Electrochemical Detection heavy metal element has many advantages, such as that equipment is simple and convenient to operate and high sensitivity, in food, is defended
There is important application value in the fields such as life, environment.
Stripping voltammetry includes two stages, i.e. enrichment process and process in leaching to the detection process of heavy metal.In current potential
I-E curves are recorded in scanning process, a Stripping Currents peak is corresponded to per metal ion species, pass through peak height and tested ion concentration
Relationship carries out quantitative analysis to the heavy metal ion in solution.This detection method has that high sensitivity, instrument be simple, operation side
Just the advantages that, detection limit is low, anti-interference.In recent years, contacting increasingly between the Electrochemical Detection and sorbing material of heavy metal
Closely.As (III) there is strong affinity therefore will be greatly improved to As using rich sulfydryl nanometer material modified electrode sulfydryl
(III) sensitivity detected and selectivity.Contain 1,3,5-triazines parent nucleus and three sulfydryls in trithiocyanuric acid (TTCA) structure,
For the common raw material of industry, facilitates, is easy to get and is inexpensive.According to structural analysis, TTCA can be used for the selective preenrichment to As (III),
But in the field of electrochemical detection of heavy metal and it there are no related application.In addition, two-dimension nano materials are considered as a kind of possibility
It is widely used in the novel metalloid material in pollutant monitoring field, has strong adsorption capacity, large specific surface area, electric conductivity excellent
The advantages that different, there is very important status in electrochemical sensing field.In order to improve the Electrochemical Detection side of heavy metal ion
The sensitivity of method, the characteristic of present invention combination TTCA and graphene prepare trithiocyanuric acid/reduced graphene (TTCA/rGO) and receive
Nano composite material establishes the trivalent arsenic electrochemical detection method based on TTCA/rGO modified electrodes, for the sensitive of trivalent arsenic
Property, accuracy and selective enumeration method.
Invention content
The object of the present invention is to provide the trivalent arsenic Electrochemical Detection sides based on trithiocyanuric acid/reduced graphene
Method, it has the advantages that detection is sensitive, accurate, selectivity is good, simple and quick.
The invention is realized in this way the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene,
It is characterized in that, trithiocyanuric acid/reduced graphene nanocomposite is coated on gold electrode surfaces, manufactured three polysulfides cyanogen
Acid/reduced graphene modified gold electrode is used as reference electrode, platinum filament to electrode, by work as working electrode, silver/silver chlorate
Make electrode, reference electrode and electrode is placed in together in the NaAc_HAc buffer solution containing trivalent arsenic, working electrode surface
Contain a large amount of sulfydryl in trithiocyanuric acid/reduced graphene of modification, by arsenic-sulfide linkage by the trivalent arsenic-selective in solution
Preenrichment is to electrode surface；Apply certain voltage on the working electrode (s by electrochemical workstation, preenrichment is in working electrode table
The trivalent arsenic in face is reduced to zeroth order, then is scanned test using Square wave anodic stripping voltammetry method so that the zero of electrode surface
Valence arsenic rapid oxidation is trivalent arsenic, and to generate anodic stripping voltammetry peak, the reduced graphene of working electrode surface modification has
Big specific surface area and excellent electric conductivity can be improved the electron transport rate of electrode surface reaction and then enhance Anodic Stripping
Volt-ampere peak-to-peak signal；With the increase of trivalent arsenic concentration in sample, the trivalent arsenic for being attached to working electrode surface increases, the sun of generation
Pole Stripping Voltammetry peak current enhances therewith, and anodic stripping voltammetry peak current and trivalent arsenic concentration are in a linear relationship, can be used for three
The Sensitive Detection of valence arsenic, detection limit realize the accuracy of trivalent arsenic and selectivity in environmental water sample and examine down to 0.054ppb
It surveys.
Preferably, a concentration of 0.1M of the NaAc_HAc buffer solution, pH 5；Apply on the working electrode (s
The size of certain voltage is -0.5V, and the time is 120 seconds；The scanning potential range of the Square wave anodic stripping voltammetry method be-
0.36V~+0.4V.
Preferably, above-mentioned trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is by following
It is prepared by step：
(1) preparation of trithiocyanuric acid/reduced graphene nanocomposite；
(2) electrode pre-processes：The alumina paste that gold electrode is successively first 1.0,0.3,0.05 μm with grain size is in chamois leather upthrow
Light to electrode surface be in minute surface, by electrode respectively volume ratio be 1:1 HNO3:H2O, distinguish 1 point of ultrasound in ethyl alcohol and ultra-pure water
Clock, then electrode is placed in the sulfuric acid of 0.5M and carries out cyclic voltammetry scan in -0.3V~+1.5V potential ranges, until obtaining
Stable cyclic voltammetric peak, then cleans electrode with ultra-pure water, nitrogen drying；
(3) trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is prepared：By 2 μ L, 100 μ g/mL steps
(1) trithiocyanuric acid/reduced graphene nanocomposite drop coating prepared is handling clean gold electrode table through step (2)
Face, naturally dry, is made trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode at room temperature.
Further preferably, the preparation method of trithiocyanuric acid/reduced graphene nanocomposite is：0.4g is aoxidized into stone
Black alkene is added in 50mL dimethylformamides and ultrasonic disperse, adds 10g trithiocyanuric acids and at room temperature magnetic agitation 2
Hour, it is then slowly added into excess sodium borohydrate and fully restores said mixture to black, after stirring 2 hours, filter, ultra-pure water
Cleaning, obtains trithiocyanuric acid/reduced graphene nanocomposite after vacuum drying.
From the foregoing, it will be observed that the present invention also provides trithiocyanuric acid/reduced graphene nanocomposite modified gold electrodes
Preparation method.
From the foregoing, it will be observed that the present invention also provides the preparation methods of trithiocyanuric acid/reduced graphene nanocomposite.
The solution have the advantages that：The characteristic of present invention combination trithiocyanuric acid and graphene, prepare trithiocyanuric acid/
Reduced graphene nanocomposite realizes that trivalent arsenic exists using a large amount of sulfydryls contained in trithiocyanuric acid by arsenic-sulfide linkage
The selective preenrichment of electrode surface, while using the bigger serface of reduced graphene and excellent electric conductivity, improving electricity
The electron transport rate and then enhancing electrochemical measurement signal of pole surface reaction are established accordingly and are based on trithiocyanuric acid/reduction stone
The trivalent arsenic electrochemical detection method of black alkene nanocomposite realizes sensitivity, accuracy and selectivity to trivalent arsenic
Detection, has a good application prospect.
Description of the drawings
Fig. 1 is the preparation of TTCA/rGO and the Electrochemical Detection schematic diagram to As (III).
Fig. 2 is that the SEM of (A) GO and (B) TTCA/rGO schemes.
Fig. 3 is Fourier transform infrared spectroscopy figure：(a) GO, (b) TTCA, (c) TTCA/rGO, (d) TTCA/rGO absorption As
(III)。
Fig. 4 is (A) EIS figures and (B) CV figures：(a) naked gold electrode, (b) GO/AuE, (c) TTCA/rGO/AuE.
Fig. 5 is SWASV responses：(a) TTCA/rGO/AuE is in 0ppbAs (III) solution, (b) naked gold electrode, (c) GO/
AuE and (d) TTCA/rGO/AuE are in 5ppbAs (III) solution.
Fig. 6 is that (A) TTCA/rGO/AuE responds the SWASV of various concentration As (III)；(B) SWASV electric currents and As
(III) the linear relationship curve of concentration.
Fig. 7 is the selective figure that TTCA/rGO/AuE detects As (III).
Specific implementation mode
The present invention is further elaborated in the following with reference to the drawings and specific embodiments, and the present invention is not limited thereto；
Embodiment 1
The preparation of trithiocyanuric acid/reduced graphene nanocomposite
0.4g graphene oxides (GO) are added in 50mL dimethylformamides simultaneously ultrasonic disperse, add 10g trimerizations
Thiocyanic acid (TTCA) and at room temperature magnetic agitation 2 hours are then slowly added into excess sodium borohydrate and fully restore above-mentioned mixing
Object is to black, and after stirring 2 hours, filtering, ultra-pure water cleaning obtains trithiocyanuric acid/reduced graphene after vacuum drying
(TTCA/rGO) nanocomposite.The preparation process of TTCA/rGO is as shown in Figure 1.
TTCA/rGO nanocomposites are characterized using scanning electron microscope (SEM) and Fourier transform infrared spectroscopy,
From Figure 2 it can be seen that GO is in thin slice accordion (Fig. 2A), and after GO surface modifications TTCA, obtained TTCA/rGO nanocomposites
Surface obviously become coarse (Fig. 2 B), show that a large amount of TTCA have loaded to graphene surface.Fig. 3 is to GO, TTCA, TTCA/
There is 3431cm in the infrared spectrum of GO in the infrared spectrum characterization of TTCA/rGO after rGO and absorption As (III)-1(O-H),
1636cm-1(C=C) and 1053cm-1(C-O-C), show that GO is synthesized successfully (Fig. 3 a)；After GO area loads TTCA, occur
2552cm-1(S-H) and 746cm-1(C-S), (Fig. 3 b) consistent with the infrared spectrum of TTCA, shows that TTCA successfully loads to graphite
Alkene surface, in addition, GO is in 1053cm-1(C-O-C) characteristic peak at disappears, and shows that GO is reduced, further demonstrates that and be made
TTCA/rGO nanocomposites (Fig. 3 c)；In order to further confirm the interaction of As (III) and TTCA/rGO, we are to inhaling
TTCA/rGO after attached As (III) has carried out IR Characterization, by Fig. 3 d as it can be seen that 2552cm-1(S-H) absorption peak almost disappears,
This is because the effect between sulfydryl and As (III) greatly consumes the sulfydryl in TTCA/rGO nanocomposites, in turn
Show that the sulfydryl in TTCA/rGO can be used for the enrichment to As (III).
Embodiment 2
The preparation of TTCA/rGO nanocomposite modified electrodes
The alumina paste that gold electrode is successively first 1.0,0.3,0.05 μm with grain size is polished to electrode surface on chamois leather and is in
Minute surface, by electrode respectively volume ratio be 1:1 HNO3:H2O, distinguish ultrasound 1 minute in ethyl alcohol and ultra-pure water, then electrode is set
Cyclic voltammetry scan is carried out in -0.3V~+1.5V potential ranges in the sulfuric acid of 0.5M, until obtaining stable cyclic voltammetric
Peak then cleans electrode with ultra-pure water, nitrogen drying；By the TTCA/rGO drop coatings of 2 μ L, 100 μ g/mL at gold electrode (AuE)
Surface is dried at room temperature, and TTCA/rGO nanocomposites modified gold electrode (TTCA/rGO/AuE) is made.
TTCA/rGO modified electrodes are characterized using electrochemical AC impedance method (EIS) and cyclic voltammetry (CV)
(Fig. 4).By Fig. 4 A as it can be seen that electron transmission resistance (Ret) very little of naked gold electrode (curve a) shows that electrode has been handled totally；
After GO is modified on the surfaces AuE, the Ret of GO/AuE increases (curve b), this is because electronegative GO passes through electrostatic repulsion
Hinder electronegative [Fe (CN) in solution6]3-/4-Electron transmission occurs close to electrode surface；But the Ret of TTCA/rGO/AuE
It is substantially reduced that (curve c), this is because in the preparation process of TTCA/rGO, GO is improved by sodium borohydride reduction for rGO
The electron transmission ability of TTCA/rGO.CV characterization results (Fig. 4 B) are consistent with EIS results.
In order to further verify the feasibility that TTCA/rGO nanocomposites detect As (III), we devise one
Control series are tested, and as seen from Figure 5, when As (III) is not present in sample, TTCA/rGO/AuE does not have the dissolution of As (III)
Volt-ampere peak current (curve a)；When, there are when 5ppb As (III), ((curve c) does not have curve b) naked gold electrode with GO/AuE in sample
There is the Stripping Voltammetry peak current of As (III), still, TTCA/rGO/AuE then occurs apparent As's (III) at+0.047V
Stripping Voltammetry peak, this is because the preenrichment of the excellent conductive capability and sulfydryl of TTCA/rGO nanocomposites to As (III)
Performance.In conclusion TTCA/rGO nanocomposite modified electrodes prepared by the present invention can be used for the enrichment to As (III) and
Sensitivity Electrochemical Detection.
Embodiment 3
TTCA/rGO nanocomposite modified electrodes measure As (III)
The optimal pH selected for 5.0 and deposition voltage be -0.5V under conditions of, the As (III) of various concentration is carried out
Detection.Electro-chemical test is carried out using three-electrode system：TTCA/rGO/AuE is working electrode, and silver/silver chloride electrode is reference
Electrode, platinum filament are to electrode.NaAc_HAc buffer solution (0.1M, pH 5) to contain various concentration As (III) is that test is molten
Liquid, by the voltage 120 seconds of electrochemical workstation application -0.5V on the working electrode (s, preenrichment in working electrode surface three
Valence arsenic is reduced to zeroth order, then is carried out in -0.36V~+0.4V potential ranges using Square wave anodic stripping voltammetry method (SWASV)
Scanning so that the zeroth order arsenic rapid oxidation of electrode surface is trivalent arsenic, and Stripping Voltammetry peak occurs at+0.047V in As (III), with
The increase of As (III) concentration, dissolution peak point current gradually increases (Fig. 6 A), painted according to peak current intensity and As (III) concentration
Working curve (Fig. 6 B) processed, peak current intensity have good linear relationship with As (III) concentration within the scope of 0.2-10ppb,
Linearly dependent coefficient R2It is 0.99, detection is limited down to 0.054ppb.
Embodiment 4
Selectivity is to evaluate the important indicator of detection method performance quality, we have carried out a series of control experiments.To
Following interfering ion As (V) of 100ppb, Cu are separately added into 10ppbAs (III)2+, Hg2+, Cd2+, Pb2+, Ca2+, Zn2+, Mg2 +, K+, Na+With 1mM Cl-, SO4 2-, CO3 2-, NO3 -, PO4 3-, as seen from Figure 7,10ppb As (III) coexist with disturbance ion
When dissolution peak current it is almost consistent with the dissolution peak current of 10ppb As (III).The above result shows that the method for the present invention is to As
(III) detection has good selectivity.
In order to further investigate the practicability of the method for the present invention, we are using standard addition method to the water sample packet in multiple sources
The As (III) included in tap water, Ganjiang River Shui Herun small stream lake water is tested, and the equal parallel determination of all samples three times, obtains
The rate of recovery be 98.0%-105.5%, it is consistent with ICP-MS test results, show the method for the present invention to As in environmental water sample
(III) detection has good practicability.
Claims (10)
1. the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene, which is characterized in that by three polysulfide cyanogen
Acid/reduced graphene nanocomposite is coated on gold electrode surfaces, manufactured trithiocyanuric acid/reduced graphene modification gold electricity
Pole is placed in working electrode, reference electrode and together electrode the Acetic acid-sodium acetate buffering containing trivalent arsenic as working electrode
In solution, contain a large amount of sulfydryl in trithiocyanuric acid/reduced graphene of working electrode surface modification, it will by arsenic-sulfide linkage
Trivalent arsenic-selective preenrichment in solution is to electrode surface；Apply certain electricity on the working electrode (s by electrochemical workstation
Pressure, preenrichment is reduced to zeroth order in the trivalent arsenic of working electrode surface, then is scanned using Square wave anodic stripping voltammetry method
Test so that the zeroth order arsenic rapid oxidation of electrode surface is trivalent arsenic, to generate anodic stripping voltammetry peak；Anodic stripping voltammetry
Peak current and trivalent arsenic concentration are in a linear relationship, for the Sensitive Detection to trivalent arsenic.
2. the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene, feature exist as described in claim 1
In trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is prepared according to the following steps：
(1) preparation of trithiocyanuric acid/reduced graphene nanocomposite；
(2) electrode pre-processes：It is in minute surface that gold electrode, which is polished to electrode surface, by electrode respectively in salpeter solution, ethyl alcohol and ultrapure
It is ultrasonic in water, then electrode is placed in sulfuric acid solution and carries out cyclic voltammetry scan in -0.3V~+1.5V potential ranges, until
Stable cyclic voltammetric peak is obtained, then cleans electrode with ultra-pure water, nitrogen drying；
(3) trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is prepared：Three polysulfides prepared by step (1)
Cyanic acid/reduced graphene nanocomposite drop coating is handling clean gold electrode surfaces through step (2), dries at room temperature,
Trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is made.
3. the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene, feature exist as described in claim 1
In a concentration of 0.1M of the NaAc_HAc buffer solution, pH 5.
4. the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene, feature exist as described in claim 1
In the size for applying certain voltage on the working electrode (s is -0.5V, and the time is 120 seconds.
5. the trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene, feature exist as described in claim 1
In the scanning potential range of the Square wave anodic stripping voltammetry method is -0.36V~+0.4V.
6. the preparation method of trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode, it is characterized in that：Steps are as follows
(1) preparation of trithiocyanuric acid/reduced graphene nanocomposite；
(2) electrode pre-processes：It is in minute surface that gold electrode, which is polished to electrode surface, by electrode respectively in salpeter solution, ethyl alcohol and ultrapure
It is ultrasonic in water, then electrode is placed in sulfuric acid solution and carries out cyclic voltammetry scan, until obtaining stable cyclic voltammetric peak, then
Electrode is cleaned with ultra-pure water, nitrogen drying；
(3) trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is prepared：Three polysulfides prepared by step (1)
Cyanic acid/reduced graphene nanocomposite drop coating is handling clean gold electrode surfaces through step (2), dries at room temperature,
Trithiocyanuric acid/reduced graphene nanocomposite modified gold electrode is made.
7. the preparation method of trithiocyanuric acid as claimed in claim 6/reduced graphene nanocomposite modified gold electrode,
It is characterized in that：In step (3), a concentration of 2 μ L, the 100 μ g/mL of trithiocyanuric acid/reduced graphene nanocomposite.
8. the preparation method of trithiocyanuric acid as claimed in claim 6/reduced graphene nanocomposite modified gold electrode,
It is characterized in that：Electrode is placed in sulfuric acid solution and carries out cyclic voltammetry scan in -0.3V~+1.5V potential ranges.
9. the preparation method of trithiocyanuric acid/reduced graphene nanocomposite, it is characterized in that：It adds graphene oxide into
In dimethylformamide and ultrasonic disperse, trithiocyanuric acid and at room temperature magnetic agitation are added, excess is then slowly added into
Sodium borohydride fully restores said mixture to black, stirs, filtering, and ultra-pure water cleaning obtains three polysulfide cyanogen after vacuum drying
Acid/reduced graphene nanocomposite.
10. the preparation method of trithiocyanuric acid as claimed in claim 9/reduced graphene nanocomposite, it is characterized in that：
The mass ratio of graphene oxide and trithiocyanuric acid is 4:100.
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| CN112611791A (en) * | 2020-11-10 | 2021-04-06 | 中南林业科技大学 | Au modified electrode, preparation thereof and application thereof in As (III) detection |
| RU2758975C1 (en) * | 2021-01-11 | 2021-11-03 | федеральное государственное бюджетное образовательное учреждение высшего образования "Алтайский государственный университет" | Safe voltammetric method for the determination of arsenic ions using a gold electrode |
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