CN113788502B - Material preparation and detection method for distinguishing phosphate ion concentration in water environment - Google Patents
Material preparation and detection method for distinguishing phosphate ion concentration in water environment Download PDFInfo
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Abstract
The invention relates to a material preparation and detection method for judging phosphate ion concentration in a water environment, which takes foamed nickel as a carrier, mixes mixed salt containing nickel ions and cobalt ions under magnetic stirring under the condition of hexamethylenetetramine to obtain a uniform solution, then adds sodium dodecyl sulfate, carries out magnetic stirring again to obtain the uniform solution, transfers the uniform solution to a high-pressure reaction kettle, keeps the uniform solution for 8 to 12 hours under the condition of 80 to 120 ℃, and obtains nickel-cobalt layered double hydroxides containing intercalation ions through washing, filtering and drying. And testing the response of the nickel-cobalt layered double hydroxide containing the intercalation ions in the solution containing the phosphate ions with different concentrations by using an electrochemical impedance spectrum of an electrochemical workstation to obtain a Bode curve, and comparing the Bode curve with a standard curve of a sample to be tested to obtain a phosphate ion concentration range. The concentration range of phosphate ions can be directly obtained, the detection cost of the ion concentration is greatly reduced, and real-time on-site detection is realized.
Description
Technical Field
The invention relates to a material preparation and detection method for distinguishing phosphate ion concentration in a water environment, which can be applied to, but not limited to, detection of phosphate ions with different concentrations in water environments such as industrial and agricultural water, domestic water, river and lake, sewage discharge and the like.
Background
Phosphorus is one of the essential elements of living bodies, but is also a main cause for water eutrophication. The primary standard of the total phosphorus content is 0.5mg/L as specified in the Integrated wastewater discharge Standard (GB 8978-1996). The environmental quality Standard for surface Water (GB 3838-2002) stipulates that the total phosphorus content is 0.02mg/L for class I, 0.1mg/L for class II, 0.2mg/L for class III, 0.3mg/L for class IV and 0.4mg/L for class V. The detection of the phosphorus content in the water body is extremely important based on national standards. In the currently used detection methods, such as inductively coupled plasma atomic emission spectrometry (ICP-AES) or inductively coupled plasma mass spectrometry (ICP-MS), and X-ray fluorescence (such as proton-excited X-ray fluorescence (PIXE)), although these measurement methods have high accuracy, they require expensive and heavy test instruments, and are not suitable for field detection. In order to reduce the cost of detecting the ion concentration and realize the on-site real-time detection, it is necessary to invent a rapid material and method for detecting the ion concentration.
Layered Double Hydroxides (LDHs) belong to the multi-metal clay materials, have a hydrotalcite-like structure, and are layered compounds composed of positively charged main layer plates and interlayer anions through the interaction of non-covalent bonds. The general structural formula is as follows: [ M ] A 1-x 2+ M x 3+ (OH) 2 ] x+ [A n- ] x/n ·mH 2 O, wherein M 2+ And M 3+ Respectively represent divalent and trivalent metal cations, the LDHs are represented by M 3+ Partially substituted for M in hydroxide 2+ Wherein M is 2+ And M 3+ The closer the ionic radius is, the more easily a stable laminate is formed; wherein A is n- Expressed as interlayer anion, and formed by intercalation of interlayer anion and water molecule between layers for maintaining electric neutrality, and common interlayer anion is OH - 、NO 3 - 、Cl - And CO 3 2- And so on. LDHs are typical representatives of inorganic layered materials, and because interlayer anions have the characteristics of interchangeability, adjustable interlayer spacing and the like, the LDHs have wide application prospects in the fields of adsorption, electrocatalysis, drug release, energy storage devices and the like. Until now, LDHs are not researched and reported to be used for detecting the concentration of phosphate ions in a water environment.
Electrochemical impedance spectroscopy is an electrochemical measurement method using a small-amplitude sine wave potential or current as a disturbance signal. Because the system is disturbed by the small-amplitude electric signal, on one hand, the system can be prevented from being greatly influenced, on the other hand, the disturbance and the response of the system are approximately in a linear relation, and the mathematical processing of the measurement result is simplified. Meanwhile, the electrochemical impedance spectrum method is a frequency domain measuring method, and the electrode system is researched by using the impedance spectrum with a wide frequency range obtained by measurement, so that more dynamic information and electrode interface structure information can be obtained with other conventional electrochemical methods. The early application of electrochemical impedance spectroscopy is mainly to research the dielectric properties of liquids and metal oxides, and in recent years, electrochemical impedance spectroscopy plays an increasingly important role in a plurality of electrochemical processes, however, the application of electrochemical impedance spectroscopy in phosphate ion concentration detection is yet to be developed and researched.
Disclosure of Invention
Because the traditional ion concentration detection scheme is expensive and complex in process, real-time detection cannot be realized, and in order to reduce the ion concentration detection cost and realize real-time detection, a rapid material and a rapid method for detecting the ion concentration are needed to be invented.
The technical scheme of the invention is as follows:
a material preparation method for distinguishing phosphate ion concentration in a water environment is characterized by adopting a one-step hydrothermal method to synthesize nickel-cobalt layered double hydroxide, taking foamed nickel as a carrier, magnetically stirring and mixing mixed salt containing nickel ions and cobalt ions under the condition of hexamethylenetetramine to obtain a uniform solution, then adding sodium dodecyl sulfate, magnetically stirring again to obtain the uniform solution, transferring the uniform solution to a high-pressure reaction kettle, keeping the uniform solution at the temperature of 80-120 ℃ for 8-12 h, washing, filtering and drying to obtain the nickel-cobalt layered double hydroxide containing intercalation ions.
The molar ratio of the nickel ions to the cobalt ions is 1-2: 1.
the molar ratio of the nickel-cobalt metal ions to the sodium dodecyl sulfate is 2-3: 3.
the magnetic stirring speed is 500-600 r/min.
The interlayer spacing of the nickel-cobalt layered double hydroxide containing the intercalation ions is 0.8-1.2 nm.
A detection method for distinguishing the concentration of phosphate ions in a water environment; and testing the response of the nickel-cobalt layered double hydroxide containing the intercalation ions in the solution containing the phosphate ions with different concentrations by using an electrochemical impedance spectrum of an electrochemical workstation to obtain a Bode curve, and comparing the Bode curve with a standard curve of a sample to be tested to obtain a phosphate ion concentration range. The invention fully utilizes the characteristics of adjustable interlayer spacing of the layered double hydroxides and the like, and obtains the nickel-cobalt layered double hydroxides containing intercalation ions by adding the sodium dodecyl sulfate as the intercalating agent, wherein the interlayer spacing is 0.8-1.2 nm, and the interlayer spacing can be regulated and controlled to realize the specific action with phosphate ions, and the nickel-cobalt layered double hydroxides prepared by the method can be used for detecting the concentration of the phosphate ions.
The invention fully utilizes the characteristics of adjustable interlayer spacing of Layered Double Hydroxides (LDHs) and the like, utilizes long-chain anions to increase the interlayer spacing of the LDHs, selects the molar ratio of nickel cobalt metal ions to Sodium Dodecyl Sulfate (SDS) to be 2/3-3/3, uses Hexamethylenetetramine (HMT) as an alkali source to be 3.3/1 of the molar ratio of nickel cobalt metal ions, keeps the mixture for 8-12 h under the hydrothermal condition of 80-120 ℃, prepares NiCo-LDHs-SDS with the interlayer spacing of 0.8-1.2 nm, regulates the interlayer spacing of the LDHs to realize the specific action with phosphate ions, and the material prepared by the method can be used for detecting the concentration of the phosphate ions. Along with the increase of the concentration of phosphate ions in the aqueous solution, the electrochemical properties of the interface can be changed by the intercalation effect of the LDHs and the phosphate ions, and the impedance change of the LDHs in the aqueous solution is detected by using an electrochemical impedance spectrum. Different Bode curves are obtained through analysis, specific responses of phosphate ions with different concentrations and LDHs are reflected according to phase angle deviation and amplitude change, and a phosphate ion concentration range (lower than 0.01mg/L, 0.01-0.1 mg/L, 0.1-0.3 mg/L, 0.6 mg/L) can be obtained through comparison with a standard curve (0.01 mg/L, 0.1-0.1 mg/L, 0.1-0.3 mg/L, 0.3-0.6 mg/L and higher than 0.6 mg/L) of the embodiment of the invention, so that a simple and feasible method for detecting the phosphate ion concentration is realized.
The invention takes the total phosphorus concentration regulated by the integrated wastewater discharge standard (GB 8978-1996) and the surface water environmental quality standard (GB 3838-2002) as a standard, and different phosphate radical concentration gradients of 0.01mg/L, 0.1mg/L, 0.3mg/L and 0.6mg/L are set. And (3) carrying out electrochemical impedance spectrum test on the layered double hydroxide in a water sample to be tested by using an electrochemical workstation, and drawing a Bode curve on the obtained data. The curve is compared with a standard curve for analysis, the concentration range (lower than 0.01mg/L, 0.01-0.1 mg/L, 0.1-0.3 mg/L, 0.3-0.6 mg/L and higher than 0.6 mg/L) of phosphate ions can be directly obtained, the ion concentration detection cost is greatly reduced, and real-time on-site detection is realized.
Drawings
FIG. 1 is a Bode (phase angle) low frequency histogram of NiCo-LDH-SDS/NF at 0.01-0.6mg/L (samples including examples 1 and 3).
At standard concentrations of 0.01mg/L, 0.1mg/L, 0.3mg/L, 0.6mg/L and the like, the impedance spectrum Bode diagram of NiCo-LDH-SDS/NF is a partial enlarged view of the phase angle part in the low frequency region, and the sample to be tested of examples 1 and 3 is shown as the curve in FIG. 1 as a standard curve in the implementation process of the invention.
FIG. 2 is a Bode (amplitude) low frequency histogram of NiCo-LDH-SDS/NF at 0.01-0.6mg/L (containing the samples of example 2).
Under the standard concentrations of 0.01mg/L, 0.1mg/L, 0.3mg/L, 0.6mg/L and the like, the impedance spectrum Bode diagram of NiCo-LDH-SDS/NF is a partial enlarged view of the low-frequency region of the amplitude part, which is taken as a standard curve in the implementation process of the invention, and the curve of the sample to be tested in the example 2 is shown in the graph in FIG. 2.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, it is obvious that the drawings needed to be used in the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are the embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Example 1:
in the embodiment, foamed nickel with the thickness of 0.3mm is cut into pieces with the thickness of 2cm multiplied by 2cm, the pieces are soaked for 15min by using 1mol/L dilute hydrochloric acid, the surface oxidation layer is removed, and finally the pieces are washed for 3 to 5 times by using deionized water and dried for 12h at the temperature of 60 ℃ in a vacuum drying oven.
3mmol of nickel sulfate heptahydrate, 2mmol of cobalt sulfate heptahydrate and 16.5mmol of hexamethylenetetramine are weighed, dissolved in 40ml of deionized water and mixed uniformly under magnetic stirring (500-600 r/min).
6mmol sodium dodecyl sulfate is added into the solution, and magnetic stirring is carried out again (500-600 r/min) until a uniform solution is obtained.
The uniformly mixed solution was transferred to a hydrothermal kettle having a volume of 200ml, and the pretreated nickel foam was placed, followed by heating to 80 ℃ in a muffle furnace and maintaining for 12 hours.
And (3) cooling the hydrothermal kettle to room temperature, ultrasonically treating the obtained material in ethanol until the surface active substances are uniformly loaded, washing the material for 3-5 times by using deionized water, and finally drying the material in a vacuum drying oven at 60 ℃ for 12 hours.
Taking a to-be-tested aqueous solution sample containing phosphate ions with unknown concentration, carrying out electrochemical impedance spectrum test on the to-be-tested aqueous solution sample at a frequency band of 0.05Hz to 10kHz by using a portable electrochemical workstation on site, and drawing a Bode curve on obtained data.
Comparing the Bode curve with a standard curve attached figure 1 in the attached figure, wherein the phase angle of the Bode curve of the sample to be detected is between 0.3 and 0.6mg/L of the standard curve attached figure 1, and the concentration range of phosphate ions of the sample to be detected is between 0.3 and 0.6mg/L.
The ion chromatography is used for measuring the concentration of the phosphate ions of the sample to be detected to be 0.43mg/L, and the material and the method can realize the field detection of the concentration of the phosphate ions.
Example 2:
in the embodiment, foamed nickel with the thickness of 0.3mm is cut into pieces with the thickness of 2cm multiplied by 2cm, the pieces are soaked for 15min by using 1mol/L dilute hydrochloric acid, the surface oxidation layer is removed, and finally the pieces are washed for 3 to 5 times by using deionized water and dried for 12h at the temperature of 60 ℃ in a vacuum drying oven.
3.33mmol nickel sulfate heptahydrate, 1.67mmol cobalt sulfate heptahydrate and 16.5mmol hexamethylenetetramine are weighed, dissolved in 40ml deionized water and mixed uniformly under magnetic stirring (500-600 r/min).
5mmol sodium dodecyl sulfate is added into the solution, and magnetic stirring is carried out again (500-600 r/min) until a uniform solution is obtained.
The uniformly mixed solution was transferred to a hydrothermal kettle having a volume of 200ml, and the pretreated nickel foam was placed, followed by heating to 100 ℃ in a muffle furnace and maintaining for 10 hours.
And (3) cooling the hydrothermal kettle to room temperature, ultrasonically treating the obtained material in ethanol until the surface active substances are uniformly loaded, washing the material for 3-5 times by using deionized water, and finally drying the material in a vacuum drying oven at 60 ℃ for 12 hours.
Taking a to-be-tested aqueous solution sample containing phosphate ions with unknown concentration, carrying out electrochemical impedance spectrum test on the to-be-tested aqueous solution sample at a frequency band of 0.05Hz to 10kHz by using a portable electrochemical workstation on site, and drawing a Bode curve on obtained data.
Comparing the Bode curve with the standard curve in the figure 2, as shown in the figure, the Bode amplitude curve of the sample to be detected is below the standard curve of 0.6mg/L, so that the phosphate ion concentration range of the sample to be detected is more than 0.6mg/L.
The concentration of the phosphate ions of the sample to be detected is 0.89mg/L through ion chromatography measurement, and the material and the method can realize the field detection of the concentration of the phosphate ions.
Example 3:
in the embodiment, foamed nickel with the thickness of 0.3mm is cut into pieces with the thickness of 2cm multiplied by 2cm, the pieces are soaked for 15min by using 1mol/L dilute hydrochloric acid, the surface oxidation layer is removed, and finally the pieces are washed for 3 to 5 times by using deionized water and dried for 12h at the temperature of 60 ℃ in a vacuum drying oven.
2.5mmol nickel sulfate heptahydrate, 2.5mmol cobalt sulfate heptahydrate and 16.5mmol hexamethylenetetramine are weighed, dissolved in 40ml deionized water and mixed uniformly under magnetic stirring (500-600 r/min).
7.5mmol sodium dodecyl sulfate is added into the solution, and magnetic stirring is carried out again (500-600 r/min) until a uniform solution is obtained.
The uniformly mixed solution was transferred to a hydrothermal kettle having a volume of 200ml, and the pretreated nickel foam was placed, followed by heating to 120 ℃ in a muffle furnace and maintaining for 8 hours.
And (3) cooling the hydrothermal kettle to room temperature, ultrasonically treating the obtained material in ethanol until the surface active substances are uniformly loaded, washing the material for 3-5 times by using deionized water, and finally drying the material in a vacuum drying oven at 60 ℃ for 12 hours.
Taking a to-be-tested aqueous solution sample containing phosphate ions with unknown concentration, carrying out electrochemical impedance spectrum test on the to-be-tested aqueous solution sample at a frequency band of 0.05Hz to 10kHz by using a portable electrochemical workstation on site, and drawing a Bode curve on obtained data.
Comparing the Bode curve with the standard curve in the figure 1, wherein the phase angle of the Bode curve of the sample to be detected is below 0.01mg/L of the standard curve, so that the concentration range of the phosphate ions in the sample to be detected is less than 0.01mg/L.
The concentration of the phosphate ions of the sample to be detected is 0.005mg/L through ion chromatography measurement, and the material and the method can realize the field detection of the concentration of the phosphate ions.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention. The invention belongs to the known technology.
Claims (3)
1. A detection method for distinguishing the concentration of phosphate ions in a water environment; the method is characterized in that the response of nickel-cobalt layered double hydroxides containing intercalation ions in a solution containing phosphate ions with different concentrations is tested by using an electrochemical impedance spectrum of an electrochemical workstation to obtain a Bode curve, and the Bode curve is compared with a standard curve of a sample to be tested to obtain a phosphate ion concentration range; synthesizing nickel-cobalt layered double hydroxide by adopting a one-step hydrothermal method,
1) Taking foamed nickel as a carrier;
2) Magnetically stirring and mixing mixed salt containing nickel ions and cobalt ions under the condition of hexamethylenetetramine to obtain uniform solution, then adding sodium dodecyl sulfate, magnetically stirring again to obtain uniform solution, transferring the uniform solution to a high-pressure reaction kettle, and keeping the uniform solution at the temperature of 80-120 ℃ for 8-12 hours, wherein the magnetic stirring speed is 500-600 r/min;
3) The nickel-cobalt layered double hydroxide containing the intercalation ions is obtained after washing, filtering and drying, and the interlayer spacing is 0.8-1.2 nm.
2. The method of claim 1, wherein the molar ratio of nickel ions to cobalt ions is 1 to 2:1.
3. the method of claim 1, wherein the molar ratio of nickel cobalt metal ions to sodium dodecyl sulfate is 2 to 3:3.
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