CN107356656A - It is a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene - Google Patents

It is a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene Download PDF

Info

Publication number
CN107356656A
CN107356656A CN201710564407.0A CN201710564407A CN107356656A CN 107356656 A CN107356656 A CN 107356656A CN 201710564407 A CN201710564407 A CN 201710564407A CN 107356656 A CN107356656 A CN 107356656A
Authority
CN
China
Prior art keywords
electrode
graphite alkene
cadmium
electrochemical
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710564407.0A
Other languages
Chinese (zh)
Other versions
CN107356656B (en
Inventor
胡广志
姜如愿
夏木西卡玛尔·买买提
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN201710564407.0A priority Critical patent/CN107356656B/en
Publication of CN107356656A publication Critical patent/CN107356656A/en
Application granted granted Critical
Publication of CN107356656B publication Critical patent/CN107356656B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, the electrochemical sensor being related in this method is made up of working electrode, Ag/AgCl reference electrodes, the Pt silks of polysulfide/graphene Nafion modifications to electrode, electrolytic cell and electrochemical workstation, electrochemical techniques：Differential pulse anodic stripping voltammetry.The sensor is 2.0 300 μ gL to the detection range of cadmium ion‑1, the detection range to lead ion is 1.0 300 μ gL‑1；Detection limit is respectively 0.67 μ gL‑1With 0.17 μ gL‑1Below 4.5 times and 59 times of the quasi- value of the given guidelines for drinking water quality of the World Health Organization；Show preferable reappearance, stability and interference free performance simultaneously；Running water cadmium, lead ion content detection in, sensor detected representation goes out good sensitivity and repeatability.The sensor can exactly, rapidly and can scene detect cadmium, lead ion content simultaneously, therefore there is preferable actual application prospect.

Description

It is a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene
Technical field
The present invention relates to a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, electrochemical techniques：Differential pulse Anodic stripping voltammetry.
Background technology
Many advantages, such as graphene is because of its good electric conductivity, Large ratio surface, more avtive spot, in hypertoxic heavy metal ion Electrochemical analysis field receive significant attention.But most of functional modification avtive spot of graphene is located at the side of graphite Edge, the basal plane carbon for accounting for graphene major part atom are then not participating in effective enrichment of heavy metal.For graphene carbon Basal plane makes full use of problem, carries out the high sensitivity heavy metal electrochemical sensing research based on graphene composite nano material. Functional modification agent using inexpensive polysulfide as graphene, utilizes the extensive chemical suction-operated between sulphur and heavy metal ion Reach quick, the effective enriching heavy metal ion of heavy metal ion, stone is modified by the polysulfide for investigating different chain length The factors such as accumulation ability, selectivity and the stability of black alkene material heavy metal ion, research functional modification process is to graphite The influence of sensing capabilities, sensitivity and the selectivity of alkene sensor etc., discloses polysulfide function graphite from molecular level The absorption mechanism and electron transmission mechanism of alkene material heavy metal ion, establish high sensitivity, high-selectivity heavy metal electrochemistry New material and method and technology are sensed, the detection and improvement for hypertoxic heavy metal ion in environment provide new theoretical clue and experiment Foundation.
Heavy metal (mercury, lead, cadmium, arsenic, cadmium, thallium etc.) pollutes the problem of environmental pollution for having become most serious in the world today One of.With developing rapidly for industrial and agricultural production and being continuously increased for population, the row of various industry and mining and sanitary wastewater, waste residue etc. Put, the environment such as soil for the survival of mankind, water body is all in various degree by heavy metal pollution, dirt of the heavy metal to environment Dye has the characteristics that irreversibility, chronicity, cumulative bad and latency, and its pollution control cost is high.
According to the relevent statistics, the arable land in China 1/6 has been subjected to heavy metal pollution (300,000,000 mu) at present, annual by pollution grain Up to 12,000,000 tons, direct economic loss was up to 20,000,000,000 RMB in 2006.Slow down what is threatened caused by heavy metal pollution One of one important means is to establish efficient, quick, sensitive detection technique, meets environment real time monitoring requirement, and multistage Examine the active demand of detection department.
The Heavy metal method of main flow is absorption spectrum and emission spectrometry based on atom spectrum technology at present, is utilized Atom or Ions Absorption or transmitting special spectrum have high sensitivity, selectivity so as to measure the analysis method of constituent content Good, the advantages that analyze speed is fast, strong antijamming capability, from last century mid-term be increasingly becoming heavy metal analysis standard method it One.And advantage of lower cost, AAS and fluorescent spectrometry based on molecular spectroscopy techniques, be using heavy metal ion with Compound can absorb after combining or launch special wavelength light and is measured, and this method has that instrument is simple, method is reliable, application The features such as scope is wide, turn into one of wider method of popularization degree.In addition with biochemical analysis, mass spectrography, efficient liquid phase Chromatography etc..Although above-mentioned detection method is each advantageous, there is also some shortcomings part, such as required expensive equipment, running cost With high, detection time length etc., it is difficult to meet quick, in situ detection heavy metal be actually needed.Compared to traditional Instrumental Analysis Technology, electrochemical method are certain electrical parameter (resistance, electric current, current potential, electricity etc.) in chemical bath using heavy metal ion Certain relation be present with test substance concentration and be measured in change, have instrument simply, high sensitivity, it is cheap, exist in real time Line monitor many advantages, such as, and sensor be easy to miniaturization, it is integrated and automation, can meet heavy metal analysis scene, Quickly, developing direction and the requirement of measurement in real time, online, are continuously and automatically changed.The core of electrochemical gaging content of beary metal Part is design and made with high selectivity, highly sensitive electrode sensing material.Based on early the pole of mercury metal electrode technology Volt-ampere analysis is composed, 10 detection device for multi metallic elements such as cadmium (Cd), lead (Pb), copper (Cu), arsenic (As), chromium (Cr) can be determined, is examined Survey limit and also reach ng/mL levels.Because using hypertoxic metal mercury electrode, this method has certain harm and appearance to operator's health Easily cause secondary environmental pollution.Developing novel electrode that is green, pollution-free, meeting modern environment protection requirement in recent years turns into weight The study hotspot of electrochemical metal detection field.For this, people successfully develop the bismuth film electrode of part substitution mercury film electrode and answered Determined for the hypersensitive anodic stripping voltammetry of cadmium and lead.Compared with body phase material, nano material has that specific surface area is big, surface Can be high, avtive spot is more the advantages that, there is higher heavy metal accumulation ability.The bismuth nanoparticle modification membrane electrode of nanoscale 0.03ppb thallium ions even can be detected.Hu Shengshui seminars of Wuhan University are real with anthraquinone/clay nanocomposites success The electrochemistry of ppb concentration rank lead and cadmium is showed while has determined；Panpan Dai et al. ferroso-ferric oxide iron oxide nano-granules Sub- modified electrode realizes the high sensitivity lead ion detection of iodide ion induction, and test limit is reduced into 0.04nM；Hou Huina etc. Electrochemical gaging while people is successfully realized lead and copper using gold/silicon nanowires modified electrode.The conduction of above-mentioned nano material Property is not very good, it is necessary in electrode surface uniform load to meet electrode conductivuty test request, therefore to electrode material Technology of preparing requires higher.Carbon nanomaterial also has easy preparation, electric conductivity good except the general characteristic with nano material The advantages that good, received significant attention in heavy metal Electroanalytical Chemistry field in recent years.Hongqun Luo et al. researchs are found CNT can be efficiently modified electrochemical response signal of the bismuth film electrode to cadmium ion；Then can be with based on carbon nano tube compound material Effectively improve the adsorption analysis performance of heavy metal.
Graphene in carbon nanomaterial is high conductivity single layer of carbon atom layers of the Geim in discovery in 2004, has superelevation Electron transfer rate and bigger serface (2600m2/g).The heterogeneous electron transfer rate of the border carbon atom of graphene, office The domain density of states, fault of construction and number of functional groups are above the carbon atom in middle part, organic as electrochemical catalysis The avtive spot of small molecule is studied applied to electrochemical sensing.The graphene of edge carboxylated can apply to heavy metal lead and cadmium While pulse voltammetry determine, test limit respectively reaches 0.02 and 0.2nM, but the bottom surface in single-layer graphene middle part Carbon atom does not participate in heavy metal ion enrichment process.Abraham etc. is by double (diphenylphosphoryl group benzene) the function fossils of 1,2- Black alkene is applied to the electric potential type lead ion sensor of structure graphene, and test limit reaches 25nM, and sensitivity is improved into two quantity Level.In addition, inorganic nano material, the composite of such as gold, bismuth, CNT and graphene can improve graphene heavy metal sensing The detection sensitivity of device.The organic high molecular polymers such as poly-dopamine, Nafion, chitosan can also improve graphene electrochemistry The sensing capabilities of heavy metal sensor, but it is difficult to avoid that high molecular polymer influences electronics in stone in the reunion of graphenic surface The transmission on black alkene surface, its heavy metal sensing capabilities is caused to be difficult to reach optimal representation.
Based on Such analysis, to improve heavy-metal electrochemical sensor sensitivity, not only need real on graphene basal plane Existing single dispersing fixes heavy metal capture group, and captures group heavy metal ion and also retain stronger absorption bonding action. If mono dispersed functionalized modification is carried out to graphene basal plane using sulfur-containing compound, and based on sulphur atom heavy metal element Strong interaction adsorbs heavy metal ion, realizes that heavy metal atom is effectively enriched with graphenic surface, and a huge sum of money will be greatly enhanced Belong to the sensitivity of sensor, so as to obtain some very valuable results.The polysulfide modification of graphenic surface Though there is a small amount of report, on modification principle, heavy metal electrochemistry of the different chain length polysulfide on graphene basal plane carbon Sensing capabilities and the research of electron transmission mechanism, relevant report that so far there are no.
For it is current the problem of, the present invention provide polysulfide/graphene cadmium lead electrochemical sensor preparation method, This method prepares grapheme material using wet chemistry method, by adjusting addition, reaction time and the reaction temperature of sulphur simple substance, adjusts The chain length of polysulfide is controlled, forms different chain length polysulfide (S2, S3, S4And S5) modification graphene composite material, explore sulphur Optimal structure-activity relationship between chain length and graphene-supported amount, investigate the composite electric conductivity, than surface, hydrophobicity and Chemical stability, and regulate and control electric conductivity, hydrophilic and hydrophobic and the polysulfide of composite in graphenic surface load capacity.
Passed by contrasting graphene, polysulfide and polysulfide/graphene composite material heavy metal ion electrochemical Perceptual energy, studies the physicochemical characteristic of composite basal plane carbon and the structure-activity relationship of heavy metal electrochemical sensing performance, discloses sulphur chain Length and sensitivity of the load capacity to different heavy metal ion and the objective law of selectivity.By optimize solution buffer system and Adjust pH value of solution, optimize the stability and selectivity of heavy metal sensor, establish the heavy metal ion based on new material in real time, The new method and technique of line sensing.
The content of the invention
Present invention aims at, there is provided it is a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, related in this method And electrochemical sensor be working electrode, Ag/AgCl reference electrodes, Pt silks by the modification of polysulfide/graphene-Nafion Electrode, electrolytic cell and electrochemical workstation are formed, electrochemical techniques：Differential pulse anodic stripping voltammetry.The sensor pair The detection range of cadmium ion is 2.0-300 μ gL-1, the detection range to lead ion is 1.0-300 μ gL-1；Detection limit is respectively 0.67μgL-1With 0.17 μ gL-1Below 4.5 times and 59 times of the quasi- value of the given guidelines for drinking water quality of the World Health Organization；Table simultaneously Reveal preferable reappearance, stability and interference free performance；Running water cadmium, lead ion content detection in, sensor detection table Reveal good sensitivity and repeatability.The sensor can exactly, rapidly and can scene simultaneously detect cadmium, lead ion contains Amount, therefore there is preferable actual application prospect.
It is of the present invention a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, the electrification being related in this method Learn sensor be by the modification of polysulfide/graphene-Nafion working electrode, Ag/AgCl reference electrodes, Pt silks to electrode, Electrolytic cell and electrochemical workstation composition, concrete operations follow these steps to carry out：
A, prepared by graphene oxide carrier：
It is prepared by graphite oxide Hummers methods：Under ice-water bath and stirring condition, by 1g sodium nitrate and 2g high-purity squama The mixture of piece graphite is added in the 46mL concentrated sulfuric acid, and 6g potassium permanganate is then slowly added under the conditions of ice-water bath and makes solution Temperature is 0 DEG C, after then controlling 35 DEG C of temperature to be stirred 30 minutes in oil bath, is slowly added to 88mL deionized water, then control Solution temperature is 98 DEG C, stir 15 minutes in oil bath, the addition 10mL30% hydrogenperoxide steam generator and cold under stirring But to room temperature, finally mixture is filtered, washed, freeze-drying, that is, obtains graphite oxide powder；
B, the preparation of graphene oxide suspension：
The graphite oxide 80.0mg that step a is obtained accurately is weighed, is dissolved in 40mL deionized waters and is made into 2mg/mL suspensions, Ultrasonic agitation is scattered 50 minutes, and pH 7-8 are adjusted with 1mol/L potassium hydroxide solution；
C, the preparation of polysulfide/graphene composite material：
0.385g vulcanized sodium is dissolved into 7mL deionized water and forms sodium sulfide solution, adds 0.1536g sulphur Powder, is stirred by ultrasonic until solution becomes clear, and its reaction equation is：
Na2S+ (x-1) S=Na2Sx (x=2,3,4,5)
Then under nitrogen protection, the clear solution is added dropwise to graphene oxides of the step b by ultrasonic disperse In suspension, and flowed back 24 hours under the conditions of 80 DEG C of temperature, resulting solution is through filtering, washing, then carry out ultrasonic disperse in In 80mL water, 0.7mL hydrazine hydrate is added under nitrogen protection, continues to flow back 24 hours at 80 DEG C of temperature, by products therefrom Washing, through excess temperature, 110 DEG C are dried in vacuo 12 hours, obtain mixing sulfur graphite alkene composite；
D, the preparation of sulfur graphite alkene electrode is mixed：
By bare electrode respectively with 1.0,0.3 and 0.05 μm of Al2O3Powder polishes, then respectively in ethanol and deionized water Middle ultrasonic cleaning 3min, then use N2The water of electrode surface is dried up, mixes sulfur graphite alkene composite 1.5mg by what step c was obtained It is scattered in volume ratio 1:In 4 isopropyl alcohol and water, ultrasonic time 30min, 1.5mg/ml suspension is made into, by 4 μ L hanging drops On pyrolytic graphite electrode surface, obtain mixing sulfur graphite alkene electrode (1) after spontaneously drying at room temperature；
F, sulfur graphite alkene determination of electrode cadmium lead is mixed
Sulfur graphite alkene electrode (1), Ag/AgCl reference electrodes (2), Pt silks will be mixed to be connected to one end of electrode (3) On electrochemical workstation (1), sulfur graphite alkene electrode (1), Ag/AgCl reference electrodes (2), Pt silks are mixed to the other ends of electrode (3) It is individually positioned in electrolytic cell (4), 0.1M 10ml, pH 4.5 HAc-NaAc electrolyte is added in electrolytic cell (4), then divides 50 μ g/L Cd is not added dropwise2+And Pb2+Solution, with chronoamperometry, parameter setting：Accumulating potential -1.2V；Enrichment time 240s, Stir speed (S.S.)：400 turns/min, stand 10s, differential pulse anodic stripping voltammetry parameter setting：Onset potential -1.0V；Terminate Potential：- 0.4V, Cd2+、Pb2+Dissolution peak peak position is respectively -0.82V and -0.58V, records concentration C d2+、Pb2+Dissolution peak Peak current intensity, clean chrono-amperometric, parameter setting：Clean current potential 0.6V；Scavenging period 60s, after cleaning, it is continuously increased Cd2+、 Pb2+Concentration, the peak current intensity for recording various concentrations circulate measurement successively, and electrochemistry is drawn according to peak current intensity and concentration Analyze cadmium, lead working curve.
It is of the present invention a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, it is differential pulse anode Stripping voltammetry.The synthesising mesoporous carbon of soft template method needs substantial amounts of reagent, complex steps.Detection model of the sensor to cadmium ion Enclose for 2.0-300 μ gL-1, the detection range to lead ion is 1.0-300 μ gL-1；Detection limit is respectively lower than that WHO is given to be drunk Water refers to 4.5 times and 59 times of standard value；Show preferable reappearance, stability and interference free performance simultaneously；In running water cadmium, lead In the detection of ion concentration, sensor detected representation goes out good sensitivity and accuracy.The sensor can exactly, rapidly With can scene detect cadmium, lead ion content simultaneously, therefore there is preferable actual application prospect, reaction mass used is industry Conventional raw material, facilitates, is easy to get, be inexpensive.
Mix sulfur graphite alkene composite modified electrode measure heavy metal ion：
Sulfur graphite alkene composite will be mixed and be fixed to glassy carbon electrode surface, fixed concentration is added in electrolyte buffer solution Heavy metal ion, electrochemical gaging is carried out using Anodic stripping voltammetry or pulse voltammetry heavy metal ion, Detect the Stripping Voltammetry current strength of heavy metal ion and the corresponding relation of concentration of heavy metal ion.
Mix selectivity and stability influence of the sulfur graphite alkene composite to hypertoxic heavy metal ion：
Investigation mixes sulfur graphite alkene composite under various environmental conditions, different metal cation (such as Fe2+/3+, Cu2+, Co2 +, Pb2+, Cd2+, Ni2+, Ca2+, Mg2+, Al3+Deng) whether severe jamming is produced to mixing sulfur graphite alkene composite modification membrane electrode, How the sensitivity of electro-chemical test and the selectivity of sensor are influenceed.Mix the stability of sulfur graphite alkene composite electrode (service life) is the essential condition of determining electrode practical value：Investigate mix the response signal of sulfur graphite alkene composite electrode with Holding time, the structure-activity relationship of frequency of use, assess the practicality for mixing sulfur graphite alkene composite electrode.
Compared with existing technique, the method for the invention has obvious different：
1. utilize graphene basal plane：
The organic high molecular polymers such as poly-dopamine, Nafion, chitosan can improve graphene electrochemical heavy metals biography The sensing capabilities of sensor, but it is difficult to avoid that high molecular polymer influences electronics in graphenic surface in the reunion of graphenic surface Transmission, cause its heavy metal sensing capabilities to be difficult to reach optimal representation.In addition some micromolecular compounds, as cyclodextrin, The micromolecular compounds such as Cys, ionic liquid can pass through covalent bonding or strong physical absorption and graphene edge carbon On functional group's effect, be efficiently modified the heavy metal analysis performance of graphene sensor.It is but big on graphene basal plane Moieties carbon atom is not fully utilized then, to improve heavy-metal electrochemical sensor sensitivity, not only needs in graphene Realize that single dispersing fixes heavy metal capture group on basal plane, and capture group heavy metal ion and also retain stronger adsorption bond Cooperation is used.
2. polysulfide/graphene heavy metal sensor method is established：
Mono dispersed functionalized modification is carried out to graphene basal plane using sulfur-containing compound, and based on sulphur atom heavy metal member The strong interaction absorption heavy metal ion of element, realizes that heavy metal atom is effectively enriched with graphenic surface, weight is greatly enhanced The sensitivity of metal sensor, obtain some very valuable results.The a small amount of report of polysulfide modification of graphenic surface Road, but the research of the modification heavy metal electrochemical sensing performance on polysulfide on graphene basal plane carbon, so far there are no Relevant report.
3. the detection limit of sensor is low：
It is respectively 3 μ gL that WHO, which provides the acceptable Cmax of cadmium in drinking water, lead content,-1With 10 μ gL-1, and utilize this The described sensor cadmium of invention, lead minimum detectability are respectively 0.67 μ gL-1With 0.17 μ gL-1.Its cadmium, lead detection limit difference are low 4.5 times and 59 times of the acceptable Cmax of cadmium, lead content in drinking water.
Brief description of the drawings：
Fig. 1 is that the present invention mixes the synthesis of sulfur graphite alkene composite and Electrochemical Detection flow chart
Fig. 2 is that the present invention mixes sulfur graphite alkene composite electron microscope, wherein (a) scanning electron microscope (SEM) photograph (b) transmission electron microscope picture (c) EDS energy spectrum diagrams
Fig. 3 is the photoelectron spectroscopy figure that the present invention mixes sulfur graphite alkene composite, wherein (a) x-ray photoelectron spectroscopy figure, (b) High-resolution S 2p figures
Fig. 4 is cadmium of the present invention, lead differential pulse anodic stripping voltammetry figure, wherein (a) is sensor cadmium working curve, (b) it is cadmium lead working curve
Embodiment
Below by specific embodiment, the invention will be further described：
A, prepared by graphene oxide carrier：
It is prepared by graphite oxide Hummers methods：Under ice-water bath and stirring condition, by 1g sodium nitrate and 2g high-purity squama The mixture of piece graphite is added in the 46mL concentrated sulfuric acid, and 6g potassium permanganate is then slowly added under the conditions of ice-water bath and makes solution Temperature is 0 DEG C, then controls 35 DEG C of temperature, after being stirred 30 minutes in oil bath, is slowly added to 88mL deionized water, control is molten Liquid temperature degree is 98 DEG C, is stirred 15 minutes in oil bath, and 10mL30% hydrogenperoxide steam generator and cooling are added under stirring To room temperature, finally mixture is filtered, washed, freeze-drying, obtains graphite oxide powder；
B, the preparation of graphene oxide suspension：
The graphite oxide powder 80mg that step a is obtained accurately is weighed, is dissolved in 40mL deionized waters, it is suspended to be made into 2mg/mL Liquid, ultrasonic disperse 50 minutes, pH 7-8 are adjusted with 1mol/L potassium hydroxide solution；
C, the preparation of polysulfide/graphene composite material：
0.385g vulcanized sodium is dissolved into 7mL deionized water and forms sodium sulfide solution, adds 0.1536g sulphur Powder, until clarifying transparent solution, its reaction equation is ultrasonic agitation：
Na2S+ (x-1) S=Na2Sx (x=2,3,4,5)
Then under nitrogen protection, the clear solution is added dropwise to graphene oxides of the step b by ultrasonic disperse In suspension, and flowed back 24 hours under the conditions of 80 DEG C of temperature, resulting solution is through deionized water filtration washing 3-5 times, then carries out Ultrasonic disperse adds 0.7mL hydrazine hydrate under nitrogen protection in 80mL water, continues to flow back 24 hours at 80 DEG C of temperature, Products therefrom is washed, through excess temperature, 110 DEG C are dried in vacuo 12 hours, that is, obtain mixing sulfur graphite alkene composite, materials synthesis Figure such as Fig. 1, characterizes such as Fig. 2 and Fig. 3
D, the preparation of sulfur graphite alkene electrode is mixed：
Bare electrode is respectively with 1.0,0.3 and 0.05 μm of Al2O3Powder polishes, then respectively in ethanol and deionized water It is cleaned by ultrasonic 3min, then uses N2The water of electrode surface is dried up, mixes 1.5mg points of sulfur graphite alkene composite by what step c was obtained Dissipate in volume ratio 1:In 4 isopropyl alcohol and water, ultrasonic time 30min, 1.5mg/ml suspension is made into, 4 μ L hanging drops are existed Pyrolytic graphite electrode surface, obtain mixing sulfur graphite alkene electrode 1 after spontaneously drying at room temperature；
F, sulfur graphite alkene determination of electrode cadmium lead is mixed：
Sulfur graphite alkene electrode 1, Ag/AgCl reference electrodes 2, Pt silks will be mixed electrochemistry is connected to one end of electrode 3 On work station 1, mix sulfur graphite alkene electrode 1, Ag/AgCl reference electrodes 2, Pt silks and electrolysis is individually positioned in the other end of electrode 3 In pond 4, added in electrolytic cell 4 in 0.1M 10ml, pH 4.5 HAc-NaAc electrolyte, then 50 μ g/L Cd is added dropwise respectively2+ And Pb2+Solution, with chronoamperometry, parameter setting：Accumulating potential -1.2V；Enrichment time 240s, stir speed (S.S.)：400 turns/ Min, stand 10s, differential pulse anodic stripping voltammetry parameter setting：Onset potential -1.0V；Terminate potential：- 0.4V, Cd2+、 Pb2+Dissolution peak peak position is respectively -0.82V and -0.58V, records concentration C d2+、Pb2+Dissolution peak to peak current intensity, cleaning Chrono-amperometric, parameter setting：Clean current potential 0.6V；Scavenging period 60s, after cleaning, it is continuously increased Cd2+、Pb2+Concentration, record The peak current intensity of various concentrations circulates measurement successively, and electrochemical analysis cadmium, Qian Gongzuo are drawn according to peak current intensity and concentration Curve is shown in Table 1：
Table 1
Embodiment 2
Pass through detection of the method for the present invention to water sample：
With laboratory, originally water sample is made into pH=5.0 HAc-NaAc solution, takes 10mL, heavy metal addition is (μ g/ L)：0th, 50,100, peak current intensity under various concentrations is recorded, is surveyed 3 times respectively, further according to the linear equation calculating rate of recovery and relatively Standard deviation is shown in Table 2；
Table 2
As can be seen from the table：Heavy metal recovery rate illustrates of the present invention be based between 95.8%-103.8% The cadmium lead electrochemical detection method for mixing sulfur graphite alkene can be used for detecting the cadmium lead concentration in water sample, have preferable result.

Claims (1)

  1. It is 1. a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene, it is characterised in that the electrochemistry being related in this method passes Sensor is working electrode, Ag/AgCl reference electrodes, Pt silks by polysulfide/graphene-Nafion modifications to electrode, electrolysis Pond and electrochemical workstation composition, concrete operations follow these steps to carry out：
    A, prepared by graphene oxide carrier：
    It is prepared by graphite oxide Hummers methods：Under ice-water bath and stirring condition, by 1g sodium nitrate and 2g high-purity scale stone The mixture of ink is added in the 46mL concentrated sulfuric acid, and 6g potassium permanganate is then slowly added under the conditions of ice-water bath and makes solution temperature For 0 DEG C, after then controlling 35 DEG C of temperature to be stirred 30 minutes in oil bath, 88mL deionized water is slowly added to, then control solution Temperature is 98 DEG C, is stirred 15 minutes in oil bath, and 10mL30% hydrogenperoxide steam generator is added under stirring and is cooled to room Temperature, finally mixture is filtered, washed, freeze-drying, that is, obtain graphite oxide powder；
    B, the preparation of graphene oxide suspension：
    The graphite oxide 80.0mg that step a is obtained accurately is weighed, is dissolved in 40mL deionized waters and is made into 2mg/mL suspensions, ultrasound It is dispersed with stirring 50 minutes, pH 7-8 is adjusted with 1 mol/L potassium hydroxide solution；
    C, the preparation of polysulfide/graphene composite material：
    0.385g vulcanized sodium is dissolved into 7mL deionized water and forms sodium sulfide solution, adds 0.1536g sulphur powder, Ultrasonic agitation becomes clear until solution, then under nitrogen protection, the clear solution is added dropwise into step b and passed through In the graphene oxide suspension of ultrasonic disperse, and flowed back 24 hours under the conditions of 80 DEG C of temperature, resulting solution is washed through filtering Wash, then carry out ultrasonic disperse in 80mL water, add 0.7mL hydrazine hydrate under nitrogen protection, continue in 80 DEG C of temperature next time Stream 24 hours, products therefrom is washed, and through excess temperature, 110 DEG C are dried in vacuo 12 hours, that is, obtain mixing sulfur graphite alkene composite；
    D, the preparation of sulfur graphite alkene electrode is mixed：
    By bare electrode respectively with 1.0,0.3 and 0.05 μm of Al2O3Powder polishes, then respectively in ethanol and deionized water It is cleaned by ultrasonic 3min, then uses N2The water of electrode surface is dried up, mixes mg points of sulfur graphite alkene composite 1.5 by what step c was obtained Dissipate in volume ratio 1:In 4 isopropyl alcohol and water, ultrasonic time 30min, 1.5 mg/ml suspension are made into, 4 μ L hanging drops are existed Pyrolytic graphite electrode surface, obtain mixing sulfur graphite alkene electrode after spontaneously drying at room temperature（1）；
    F, sulfur graphite alkene determination of electrode cadmium lead is mixed
    Sulfur graphite alkene electrode will be mixed（1）, Ag/AgCl reference electrodes（2）, Pt silks are to electrode（3）One end be connected to electrification Learn work station（1）On, mix sulfur graphite alkene electrode（1）, Ag/AgCl reference electrodes（2）, Pt silks are to electrode（3）The other end difference It is placed on electrolytic cell（4）In, in electrolytic cell（4）Middle addition 0.1M 10 ml, pH 4.5 HAc-NaAc electrolyte, then distinguish 50 μ g/L Cd is added dropwise2+And Pb2+Solution, with chronoamperometry, parameter setting：The V of accumulating potential -1.2；Enrichment time 240s, Stir speed (S.S.)：400 turns/min, stand 10 s, differential pulse anodic stripping voltammetry parameter setting：The V of onset potential -1.0；Eventually Only potential：- 0.4 V, Cd2+、Pb2+Dissolution peak peak position is respectively -0.82 V and -0.58 V, records concentration C d2+、Pb2+'s Dissolution peak to peak current intensity, clean chrono-amperometric, parameter setting：Clean the V of current potential 0.6；The s of scavenging period 60, after cleaning, constantly Increase Cd2+、Pb2+Concentration, the peak current intensity for recording various concentrations circulates measurement successively, according to peak current intensity and concentration Draw electrochemical analysis cadmium, lead working curve.
CN201710564407.0A 2017-07-12 2017-07-12 Cadmium-lead electrochemical detection method based on sulfur-doped graphene Active CN107356656B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710564407.0A CN107356656B (en) 2017-07-12 2017-07-12 Cadmium-lead electrochemical detection method based on sulfur-doped graphene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710564407.0A CN107356656B (en) 2017-07-12 2017-07-12 Cadmium-lead electrochemical detection method based on sulfur-doped graphene

Publications (2)

Publication Number Publication Date
CN107356656A true CN107356656A (en) 2017-11-17
CN107356656B CN107356656B (en) 2020-01-17

Family

ID=60292501

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710564407.0A Active CN107356656B (en) 2017-07-12 2017-07-12 Cadmium-lead electrochemical detection method based on sulfur-doped graphene

Country Status (1)

Country Link
CN (1) CN107356656B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108061748A (en) * 2017-12-07 2018-05-22 哈尔滨商业大学 For detecting the preparation method of the nanometer bismuth oxide graphene composite film electrode of lead ion and cadmium ion
CN110297034A (en) * 2019-06-12 2019-10-01 重庆工商大学融智学院 A kind of dynamic change and prediction technique of urban ecological environment
CN111208182A (en) * 2020-03-11 2020-05-29 山东理工大学 Preparation method of electrochemical sensor for simultaneously detecting lead and cadmium heavy metals in soil

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103018302A (en) * 2012-12-04 2013-04-03 南京化工职业技术学院 Method for modifying and detecting trace heavy metal by glassy carbon electrode
CN104591134A (en) * 2013-10-30 2015-05-06 青岛泰浩达碳材料有限公司 Rapid preparation method for oxidized graphite
CN205091287U (en) * 2015-11-11 2016-03-16 中国科学院上海微系统与信息技术研究所 Nitrogen oxide gas sensor based on sulfur doping graphite alkene
CN105670618A (en) * 2016-02-25 2016-06-15 浙江理工大学 Sulfur-doping graphene quantum dot, preparation method of sulfur-doping graphene quantum dot and application of silver ion detection
CN105911120A (en) * 2016-04-13 2016-08-31 中国科学院过程工程研究所 Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103018302A (en) * 2012-12-04 2013-04-03 南京化工职业技术学院 Method for modifying and detecting trace heavy metal by glassy carbon electrode
CN104591134A (en) * 2013-10-30 2015-05-06 青岛泰浩达碳材料有限公司 Rapid preparation method for oxidized graphite
CN205091287U (en) * 2015-11-11 2016-03-16 中国科学院上海微系统与信息技术研究所 Nitrogen oxide gas sensor based on sulfur doping graphite alkene
CN105670618A (en) * 2016-02-25 2016-06-15 浙江理工大学 Sulfur-doping graphene quantum dot, preparation method of sulfur-doping graphene quantum dot and application of silver ion detection
CN105911120A (en) * 2016-04-13 2016-08-31 中国科学院过程工程研究所 Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YI CHEN 等: "Low-temperature and one-pot synthesis of sulfurized graphene nanosheets via in situ doping and their superior electrocatalytic activity for oxygen reduction reaction", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
ZHENGSHAN TIAN 等: "Facile synthesis of highly conductive sulfur-doped reduced graphene oxide sheets", 《PHYS.CHEM.CHEM.PHYS.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108061748A (en) * 2017-12-07 2018-05-22 哈尔滨商业大学 For detecting the preparation method of the nanometer bismuth oxide graphene composite film electrode of lead ion and cadmium ion
CN110297034A (en) * 2019-06-12 2019-10-01 重庆工商大学融智学院 A kind of dynamic change and prediction technique of urban ecological environment
CN110297034B (en) * 2019-06-12 2021-08-27 重庆工商大学融智学院 Dynamic change and prediction method for urban ecological environment
CN111208182A (en) * 2020-03-11 2020-05-29 山东理工大学 Preparation method of electrochemical sensor for simultaneously detecting lead and cadmium heavy metals in soil

Also Published As

Publication number Publication date
CN107356656B (en) 2020-01-17

Similar Documents

Publication Publication Date Title
Zhou et al. Individual and simultaneous electrochemical detection toward heavy metal ions based on L-cysteine modified mesoporous MnFe2O4 nanocrystal clusters
Bagheri et al. Simultaneous electrochemical determination of heavy metals using a triphenylphosphine/MWCNTs composite carbon ionic liquid electrode
Lu et al. A screen-printed carbon electrode modified with a bismuth film and gold nanoparticles for simultaneous stripping voltammetric determination of Zn (II), Pb (II) and Cu (II)
Chaiyo et al. Electrochemical sensors for the simultaneous determination of zinc, cadmium and lead using a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode
Li et al. A novel design of engineered multi-walled carbon nanotubes material and its improved performance in simultaneous detection of Cd (II) and Pb (II) by square wave anodic stripping voltammetry
Yi et al. Recent developments in electrochemical detection of cadmium
Ghanei-Motlagh et al. Application of N, S-dual-doped carbon/sepiolite clay hybrid material for electrochemical detection of mercury (II) in water resources
Xiong et al. Electrochemical detection of ultra-trace Cu (II) and interaction mechanism analysis between amine-groups functionalized CoFe2O4/reduced graphene oxide composites and metal ion
CN108318568A (en) A kind of electrochemical sensor and preparation method for Sensitive Detection heavy metal cadmium ion
Han et al. Mesoporous MnFe2O4 nanocrystal clusters for electrochemistry detection of lead by stripping voltammetry
Ashkenani et al. Determination of cadmium (II) using carbon paste electrode modified with a Cd-ion imprinted polymer
CN109164151A (en) A kind of CoNiO of trace detection copper ion2The method of nanometer-material-modified glass-carbon electrode
Lu et al. A glassy carbon electrode modified with graphene, gold nanoparticles and chitosan for ultrasensitive determination of lead (II)
CN112730552B (en) Modified screen printing electrode and application thereof
Chen et al. Simultaneous determination of dihydroxybenzene isomers using glass carbon electrode modified with 3D CNT-graphene decorated with au nanoparticles
CN107356656A (en) It is a kind of based on the cadmium lead electrochemical detection method for mixing sulfur graphite alkene
Chen et al. Influence of Ag, Sb, Bi and Zn impurities on electrochemical and flotation behaviour of galena
Niu et al. Applications of electrochemical techniques in mineral analysis
Hui et al. Graphene oxide/multi-walled carbon nanotubes/gold nanoparticle hybridfunctionalized disposable screen-printed carbon electrode to determine Cd (II) and Pb (II) in soil
Hu et al. An electrochemical sensor based on ion imprinted PPy/rGO composite for Cd (II) determination in water
Zhang et al. Copper/hexagonal boron nitride nanosheet composite as an electrochemical sensor for nitrite determination
Zhu et al. Two-dimensional BCN nanosheets self-assembled with hematite nanocrystals for sensitively detecting trace toxic Pb (II) ions in natural water
Seifi et al. Highly sensitive and simultaneous electrochemical determination of lead and cadmium ions by poly (thionine)/MWCNTs-modified glassy carbon electrode in the presence of bismuth ions
Pu et al. Performance comparison of simultaneo us detection Heavy-Metal ions based on carbon materials electrochemical sensor
Wang et al. A portable screen-printing electrode modified by COFDATA-TP with abundant carboxyl and secondary amine groups for simultaneous detection of Hg2+, Cu2+, Pb2+, and Cd2+

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant