CN110470708A - A kind of trace copper ionic light electrochemical detection method based on the pointed carbonitride of three dimensional needle - Google Patents
A kind of trace copper ionic light electrochemical detection method based on the pointed carbonitride of three dimensional needle Download PDFInfo
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Abstract
The invention belongs to environmental monitoring technology fields, provide a kind of trace copper ionic light electrochemical detection method based on the pointed carbonitride of three dimensional needle.It by ion thermal method, mixes co-melting salt and secondary heat treatment is carried out to original carbonitride, form three-dimensional branched structure in conjunction with ice water quenching measure, and branch, to external radiation, top is in class tip-like.3DBC-C is prepared using electrophoretic deposition3N4/ FTO optoelectronic pole measures with/without the photocurrent response variation under light radiation parameter by the way that the copper ion solution of various concentration to be added in electrolyte system, the quantitative detection to micro copper ion concentration can be realized.Due to the advantage of the pointed carbonitride of three dimensional needle itself, the specific surface area such as increased, excellent light absorpting ability etc. is conducive to the separation of Pair production, to realize high photoelectric conversion efficiency, the photoelectric sensor constructed based on the material is made to have high sensitivity.
Description
Technical field
The invention belongs to environmental monitoring technology fields, are related to a kind of trace copper ionic light based on the pointed carbonitride of three dimensional needle
Electrochemical sensing detection method.
Background technique
With the continuous development of China's industry, empty gas and water, soil receive heavy metal ion pollution.Heavy metal pollution
Different from the pollution of other organic compounds, the former has the characteristics that enriching makes it be difficult to be degraded in the environment, into life
It will retain, accumulate and migrate after state system, to cause damages.Moreover, the advantageous or harmful of metal depends not only on metal
Type, physicochemical property, but also depend on metal existing for concentration and chemical form, even if if beneficial metallic element concentration
Can also animals and plants be made to be poisoned more than a certain standard value, or even dead.Heavy metal ion be once absorbed by the body will with it is intracorporal
Strong interaction occurs for protein and various enzymes, and micro heavy metal ion will not cause harm to the human body, but if body
Interior concentration of heavy metal ion is excessively high, can change other required gold in the stereochemical structure of enzyme, the charge in activated centre or replacement enzyme
Belong to ion, inactivates enzyme.Furthermore, it is also possible to be enriched in some organs of the human body, if it exceeds the limit that human body is resistant to,
Great toxic action can be generated to human body, such as well-known " minamata disease " is exactly by containing methyl chloride in edible fish
Caused by mercury, " Itai-itai diseases " are then caused by cadmium pollution.Therefore, monitoring toxic metal ions are environmental protection and disease prevention, control
The major issue for the treatment of.However, since there are the interference matrix components of high concentration in most of biologies and environmental sample, to micro heavy
The highly selective and Sensitive Detection of metal is still a challenging research field.
Conventional heavy metal detection method, it is general although detection accuracy is high, sensitivity is good such as spectroscopic methodology and mass spectrography
The problems such as instrument and equipment is expensive, operating cost is high and inconvenient to carry, this makes them unsuitable for carrying out real-time online store-through
Continuous detection.And some detection methods also need more complicated sample pretreatment process, to be brought in actually detected application
More trouble.In recent years, electrochemical analysis techniques and biosensor technique are because it is with traditional heavy metal analysis skill
Plurality of advantages not available for art, for example, it is easy to carry, and instrument and equipment is simple, testing cost is relatively relatively low, quickly grows.This
Outside, also have many advantages, such as that sensitivity is good, the range of linearity is wide, strong antijamming capability, it is often more important that it is automated in real time to realize
On-line monitoring provides possibility.
Currently, all kinds of electrochemical sensors are studied for the detection of various heavy metal ion, and obtain good inspection
Survey effect, including electrochemistry (Biosensors and Bioelectronics (2015) 63:276-286,
Electrochimica Acta (2016) 190:480-489), optical electro-chemistry (Biosensors and Bioelectronics
(2016) 77:936-941, Sensors and Actuators B:Chemical (2018) 254:910-915), electrochemistry hair
The platforms such as light (Analytical Chemistry (2016) 88,11:6004-6010).Wherein, optical electro-chemistry detection method equipment
Simply, it is easy to micromation and high sensitivity, has become a kind of analysis method of great application potential.
The core of photoelectric sensor is photoelectric functional material therein.In addition to traditional TiO2Outside inorganic semiconductor material,
Nearest graphite phase carbon nitride material is also gradually introduced in light with advantages such as its unique semiconductor energy band structure, high stabilities and urges
Change field, and it is used for catalysis oxidation organic pollutant, catalysis produces (Chemical Reviews (2016) 116:7159- such as hydrogen
7329,Applied Catalysis B:Environmental(2019)246:120-128).However, utilizing conventional method height
It is bulk structure that warm, which handles carbonitride made from rich nitrogen presoma, and not only specific surface area is small, but also photo-generated carrier is to compound
Rate is fast, so that the photo-catalysis capability of carbonitride is unsatisfactory.Similarly, quick photo-generate electron-hole pair is compound
Rate also inhibits the photoelectron transfer efficiency of optical electro-chemistry sensor.It in addition to element doping, constructs outside hetero-junctions, changes material
Pattern itself is also a kind of a kind of practical approach for improving its light and urging property.Existing document report (Nature (2016) 537:
382, Advanced Materials (2014) 26:5043-5049), needle point pattern has the characteristic of aggregation electronics, passes through simultaneously
Biggish specific surface area can not only be obtained by constructing three-dimensional branched structure, can also improve light absorption energy by extended optical path
Power, to realize high photoelectric conversion efficiency.Therefore, the present invention realizes trace copper in water body using the pointed carbonitride of three dimensional needle
The photoelectric sensing of ion detects, and response quickly and has highly sensitive and highly selective, and application prospect is extensive.
Summary of the invention
The present invention solves complicated traditional detection of heavy metal ion method pretreatment process, operating cost height, time-consuming, resists and do
The deficiencies of immunity is poor provides a kind of simple, quick, high selection using the pointed carbonitride of three dimensional needle with excellent photoelectric property
The method of micro copper ion in the accurate detection water body of property.
In the present invention, the pointed carbon nitride material of three dimensional needle, and the quantitative inspection of copper ion are synthesized using ion heat treatment method
It surveys and photocurrent response measurement is carried out by traditional three-electrode system to realize.Under excited by visible light, the optoelectronic pole of preparation
(3DBC-C3N4/ FTO) photoelectron is generated, the copper ion in solution promotes the separation of Pair production as electron acceptor, from
And obtain photocurrent response.Therefore, the size of photocurrent response is positively correlated with the logarithm of copper ion concentration in a certain range, from
And foundation is provided for the quantitative analysis of copper ion.And due to occur electron transmission behavior premise be suitable level-density parameter with
And the strong suction-operated between copper ion and material, ensure that the optoelectronic pole material for detection specificity.
Technical solution of the present invention:
A kind of trace copper ionic light electrochemical detection method based on the pointed carbonitride of three dimensional needle, steps are as follows:
(1) the pointed carbonitride of three dimensional needle: reference literature (ACS Applied Materials&Interfaces is prepared
(2019) 11,19:17467-17474) using the preparation of the two-step method progress pointed carbonitride of three dimensional needle.
(2)3DBC-C3N4The preparation of/FTO optoelectronic pole: the pointed carbonitride of three dimensional needle that step (1) obtains is added to isopropyl
In alcohol, concentration of the pointed carbonitride of three dimensional needle in isopropanol is 0.15~0.5g/L, while magnesium nitrate is added, the end of magnesium nitrate
Concentration≤10g/L is uniformly mixed, and obtains electrophoretic deposition solution；In two electrode electro Chemical systems, FTO electro-conductive glass piece is made
For working electrode, platinum electrode, which is used as, immerses in above-mentioned deposition solution electrode, and sedimentation time is 3~5 minutes, and voltage is 80~
3DBC-C is made in 100V3N4/ FTO optoelectronic pole, taking-up are placed on ventilation and spontaneously dry for use；
(3) quantitative detection of copper ion: photoelectric sensor use traditional three-electrode system, using saturated calomel electrode as
Reference electrode, platinum electrode are to electrode, the 3DBC-C of preparation3N4/ FTO photoelectricity extremely working electrode, addition various concentration copper from
The phosphate buffer (0.1M, pH=6.9) of son is used as electrolyte solution；Using xenon lamp as light source；It is molten to electrolyte before experiment
It is passed through 10 minutes high pure nitrogens in liquid to remove dissolved oxygen, and carries out the survey of photoelectric current under conditions of being continually fed into nitrogen
Amount.Under optimum experimental condition, once opening/closing lamp circulation, the photocurrent response measured under different copper ion concentrations change every 10s
And it records.
Beneficial effects of the present invention:
(1) when deposited between be 3 minutes, pH value of solution 6.9, deposition materials concentration be 0.15mg/mL and applying bias-
When 0.2V, for the photoelectric sensing system to the Monitoring lower-cut of copper ion up to 0.38nM, detection range is 1~100nM, meets WHO
Potable water guidelines.
(2) the big specific surface area that the pointed carbon nitride material of the three dimensional needle has, excellent light absorpting ability, quick separating
The property of photo-generate electron-hole pair there is the photoelectric sensor of high-photoelectric transformation efficiency to be of great significance building.
(3) the photoelectric sensing platform based on the pointed carbon nitride material of the three dimensional needle can be real by being coupled different aptamers
Now to the detection of various biomolecules.
Detailed description of the invention
Fig. 1 is the photoelectric sensing detection mechanism schematic diagram of the present invention based on tip-like carbonitride.
Fig. 2A is the standard working curve that the photoelectric sensing system that method of the invention obtains is applied to copper ion detection.
Fig. 2 B is that the photoelectric sensing system that method of the invention obtains is applied to the range of linearity of copper ion detection and linear
Equation.
Specific embodiment
A specific embodiment of the invention is illustrated below in conjunction with attached drawing and technical solution.
Embodiment 1
Configure the measurement of Copper in Water Samples content:
(1) it prepares the pointed carbonitride of three dimensional needle: carrying out the preparation of the pointed carbonitride of three dimensional needle using two-step method.Step is such as
Under: it takes 10g melamine in the crucible with cover of 50mL, is put into Muffle furnace, be warming up to 550 DEG C with 10 DEG C of speed per minute,
Keep the temperature 4 hours afterwards.After sample is cooled to room temperature, obtained yellow powder is original carbonitride.Then, the above-mentioned Huang of 1g is taken
Color powder sample mixes (mass ratio 9:11) with two kinds of co-melting salt of 6gLiCl and KCl, is fully ground, is placed on another crucible
In.It is heated using vacuum tube furnace and under argon atmosphere.The rate of heat addition is 5 DEG C per minute, to 550 DEG C of subsequent continuation of insurance temperature
4 hours.It after sample is cooled to actual temp, takes out, is quenched with ice water immediately.Finally, using high purity water repeatedly
After cleaning, dry 12h, obtains final sample in 60 DEG C of baking ovens.
(2)3DBC-C3N4The preparation of/FTO optoelectronic pole: carbon nitride material made from the step of taking 3mg (1) is added to 20mL
Isopropanol solvent in, and the magnesium nitrate of 10mg is added, is uniformly mixed, obtain electrophoretic deposition solution.FTO electro-conductive glass piece is made
It is immersed in above-mentioned deposition solution for working electrode after being powered 3 minutes and takes out (electrophoresis apparatus voltage is set as 100V), be placed in ventilation
It spontaneously dries stand-by.
(3) quantitative detection of copper ion: photoelectric sensor use traditional three-electrode system, using saturated calomel electrode as
Reference electrode, platinum electrode are to electrode, the 3DBC-C of preparation3N4/ FTO photoelectricity extremely working electrode and the additional addition of selection
The phosphate buffer (0.1M, pH=6.9) of various concentration copper ion is used as electrolyte solution.(wherein, additionally into buffer
It adds different amounts of copper ion: taking 100 μ L difference copper ion concentration solution, be added in phosphate buffer and mix, final volume
For 5mL).Using xenon lamp as light source.10 minutes high pure nitrogens are passed through to reaction system solution to remove dissolved oxygen, and are being continued
It is passed through the measurement that photoelectric current is carried out under conditions of nitrogen.Once opening/closing lamp recycles every 10s, measures under different copper ion concentrations
Photocurrent response changes and records.
(4) drafting of standard working curve
With the increase of copper ions in sample concentration, photo-current intensity of reaction system under the conditions of having light in step (3)
It is continuously increased, within the scope of 1-100nM, the density of photocurrent of system response and the logarithm of copper ion concentration have good linear pass
System, linearly dependent coefficient R2=0.99 (Fig. 2).
(5) measurement of Determined Copper in Aqueous Solution is configured:
The water sample for being 50nM with high purity water solution allocation copper ion concentration.Sample is used to step (3) method to detect,
The standard working curve that testing result and step (4) obtain compares, and calculates the concentration of copper ion.Experimental result measures copper ion
Content 47.8nM, the rate of recovery 95%.Relative standard deviation RSD is 1.86% (n=3).
Embodiment 2
The measurement of tap water copper ions in sample content:
(1) it prepares the pointed carbonitride of three dimensional needle: carrying out the preparation of the pointed carbonitride of three dimensional needle using two-step method.Step is such as
Under: it takes 10g melamine in the crucible with cover of 50mL, is put into Muffle furnace, be warming up to 550 DEG C with 10 DEG C of speed per minute,
Keep the temperature 4 hours afterwards.After sample is cooled to room temperature, obtained yellow powder is original carbonitride.Then, the above-mentioned Huang of 1g is taken
Color powder sample mixes (mass ratio 9:11) with two kinds of co-melting salt of 6gLiCl and KCl, is fully ground, is placed on another crucible
In.It is heated using vacuum tube furnace and under argon atmosphere.The rate of heat addition is 5 DEG C per minute, to 550 DEG C of subsequent continuation of insurance temperature
4 hours.It after sample is cooled to actual temp, takes out, is quenched with ice water immediately.Finally, using high purity water repeatedly
After cleaning, dry 12h, obtains final sample in 60 DEG C of baking ovens.
(2)3DBC-C3N4The preparation of/FTO optoelectronic pole: carbon nitride material made from the step of taking 3mg (1) is added to 20mL
Isopropanol solvent in, and the magnesium nitrate of 10mg is added, is uniformly mixed, obtain electrophoretic deposition solution.FTO electro-conductive glass piece is made
It is immersed in above-mentioned deposition solution for working electrode after being powered 3 minutes and takes out (electrophoresis apparatus voltage is set as 100V), be placed in ventilation
It spontaneously dries stand-by.
(3) quantitative detection of copper ion: photoelectric sensor use traditional three-electrode system, using saturated calomel electrode as
Reference electrode, platinum electrode are to electrode, the 3DBC-C of preparation3N4/ FTO photoelectricity extremely working electrode and the additional addition of selection
The phosphate buffer (0.1M, pH=6.9) of various concentration copper ion is used as electrolyte solution.(wherein, additionally into buffer
It adds different amounts of copper ion: taking 100 μ L difference copper ion concentration solution, be added in phosphate buffer and mix, final volume
For 5mL).Using xenon lamp as light source.10 minutes high pure nitrogens are passed through to reaction system solution to remove dissolved oxygen, and are being continued
It is passed through the measurement that photoelectric current is carried out under conditions of nitrogen.Once opening/closing lamp recycles every 10s, measures under different copper ion concentrations
Photocurrent response changes and records.
(4) drafting of standard working curve
With the increase of copper ions in sample concentration, photo-current intensity of reaction system under the conditions of having light in step (3)
It is continuously increased, within the scope of 1-100nM, the density of photocurrent of system response and the logarithm of copper ion concentration have good linear pass
System, linearly dependent coefficient R2=0.99 (Fig. 2).
(5) measurement of Determined Copper in Aqueous Solution is configured:
Since copper ion being not detected in originally water sample, therefore use recovery testu.With tap water sample preparation copper from
Sub- solution, concentration are 2.5 μM.The originally water sample of 100 μ L mark-ons is taken to mix with the phosphate buffer solution of 4900 μ L, mixed liquor
Middle copper ion concentration is 50nM.Sample is used to step (3) method to detect, the standard that testing result is obtained with step (4)
Working curve comparison, calculates the concentration of copper ion.Experimental result measures content of copper ion 48.5nM, the rate of recovery 96%.Phase
It is 4.75% (n=3) to standard deviation RSD.
Embodiment 3
The measurement of river copper ions in sample content:
(1) it prepares the pointed carbonitride of three dimensional needle: carrying out the preparation of the pointed carbonitride of three dimensional needle using two-step method.Step is such as
Under: it takes 10g melamine in the crucible with cover of 50mL, is put into Muffle furnace, be warming up to 550 DEG C with 10 DEG C of speed per minute,
Keep the temperature 4 hours afterwards.After sample is cooled to room temperature, obtained yellow powder is original carbonitride.Then, the above-mentioned Huang of 1g is taken
Color powder sample mixes (mass ratio 9:11) with two kinds of co-melting salt of 6gLiCl and KCl, is fully ground, is placed on another crucible
In.It is heated using vacuum tube furnace and under argon atmosphere.The rate of heat addition is 5 DEG C per minute, to 550 DEG C of subsequent continuation of insurance temperature
4 hours.It after sample is cooled to actual temp, takes out, is quenched with ice water immediately.Finally, using high purity water repeatedly
After cleaning, dry 12h, obtains final sample in 60 DEG C of baking ovens.
(2)3DBC-C3N4The preparation of/FTO optoelectronic pole: carbon nitride material made from the step of taking 3mg (1) is added to 20mL
Isopropanol solvent in, and the magnesium nitrate of 10mg is added, is uniformly mixed, obtain electrophoretic deposition solution.FTO electro-conductive glass piece is made
It is immersed in above-mentioned deposition solution for working electrode after being powered 3 minutes and takes out (electrophoresis apparatus voltage is set as 100V), be placed in ventilation
It spontaneously dries stand-by.
(3) quantitative detection of copper ion: photoelectric sensor use traditional three-electrode system, using saturated calomel electrode as
Reference electrode, platinum electrode are to electrode, the 3DBC-C of preparation3N4/ FTO photoelectricity extremely working electrode and the additional addition of selection
The phosphate buffer (0.1M, pH=6.9) of various concentration copper ion is used as electrolyte solution.(wherein, additionally into buffer
It adds different amounts of copper ion: taking 100 μ L difference copper ion concentration solution, be added in phosphate buffer and mix, final volume
For 5mL).Using xenon lamp as light source.10 minutes high pure nitrogens are passed through to reaction system solution to remove dissolved oxygen, and are being continued
It is passed through the measurement that photoelectric current is carried out under conditions of nitrogen.Once opening/closing lamp recycles every 10s, measures under different copper ion concentrations
Photocurrent response changes and records.
(4) drafting of standard working curve
With the increase of copper ions in sample concentration, photo-current intensity of reaction system under the conditions of having light in step (3)
It is continuously increased, within the scope of 1-100nM, the density of photocurrent of system response and the logarithm of copper ion concentration have good linear pass
System, linearly dependent coefficient R2=0.99 (Fig. 2).
(5) measurement of Determined Copper in Aqueous Solution is configured:
The filter membrane that river sample first passes through 0.2 μm is filtered to remove suspended solid.Take 100 μ L river samples and 4900 μ L
Phosphate buffer solution mixing, copper ion concentration calculates to be 25.26nM according to ICP-MS result in mixed liquor.Sample is used for
Step (3) method is detected, and the standard working curve that testing result is obtained with step (4) compares, and calculates the dense of copper ion
Degree.Experimental result measures content of copper ion 28.51nM, the rate of recovery 113%.Relative standard deviation RSD is 3.90% (n=3).
Claims (1)
1. a kind of trace copper ionic light electrochemical detection method based on the pointed carbonitride of three dimensional needle, which is characterized in that step is such as
Under:
(1) the pointed carbonitride of three dimensional needle is prepared；
(2)3DBC-C3N4The preparation of/FTO optoelectronic pole: the pointed carbonitride of three dimensional needle that step (1) obtains is added to isopropanol
In, concentration of the pointed carbonitride of three dimensional needle in isopropanol is 0.15~0.5g/L, while magnesium nitrate is added, and the end of magnesium nitrate is dense
Degree≤10g/L is uniformly mixed, and obtains electrophoretic deposition solution；In two electrode electro Chemical systems, using FTO electro-conductive glass piece as
Working electrode, platinum electrode, which is used as, immerses in above-mentioned deposition solution electrode, and sedimentation time is 3~5 minutes, and voltage is 80~
3DBC-C is made in 100V3N4/ FTO optoelectronic pole, taking-up are placed on ventilation and spontaneously dry for use；
(3) quantitative detection of copper ion: photoelectric sensor uses traditional three-electrode system, using saturated calomel electrode as reference
Electrode, platinum electrode are to electrode, the 3DBC-C of preparation3N4/ FTO photoelectricity extremely working electrode, addition various concentration copper ion
0.1M, pH=6.9 phosphate buffer are as electrolyte solution；Using xenon lamp as light source；10 points are passed through into electrolyte solution
The high pure nitrogen of clock to remove dissolved oxygen, and under conditions of being continually fed into nitrogen carry out photoelectric current measurement；Every 10s is primary
Opening/closing lamp circulation, measures the photocurrent response under different copper ion concentrations and changes and record.
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| CN111122552A (en) * | 2019-12-11 | 2020-05-08 | 南京大学 | Method for monitoring cell to secrete copper ions by single-particle electrochemiluminescence imaging technology |
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Application publication date: 20191119 |