CN114226436B - Metal nanocrystalline modified composite electrode and preparation method and application thereof - Google Patents
Metal nanocrystalline modified composite electrode and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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Abstract
The invention discloses a metal nanocrystalline modified composite electrode and a preparation method thereof, comprising the following steps: (1) Adding a plurality of metal precursors into a reduction solution, adding a blocking agent and a surface stabilizer, and carrying out a constant-temperature reduction reaction to obtain metal nanocrystals; (2) Uniformly mixing the metal nanocrystalline with a catalytic carrier, and then adding a film forming solution to form a homogeneous phase modification solution; (3) And coating the homogeneous modification liquid on the flat electrode slice to form a uniform liquid film, and drying to form a modification film to obtain the metal nanocrystalline modified composite electrode. The invention also discloses application of the metal nanocrystalline modified composite electrode in restoring soil pollution by combining electrodynamic force and electrocatalysis, and the chlorine-containing organic pollutants in the soil can be removed efficiently.
Description
Technical Field
The invention relates to the technical field of nano materials and environmental protection, in particular to a metal nanocrystalline modified composite electrode, and a preparation method and application thereof.
Background
With the development of modern industry and agriculture, organic pollutants (petroleum hydrocarbons, organic pesticides, antibiotics, dyes, industrial byproduct plasticizers and the like) in soil become key problems for endangering ecological environment, especially Persistent Organic Pollutants (POPs), have long-term residue, bioaccumulation, semi-volatility and high toxicity, and the pollution control is an urgent problem.
The electrodynamic remediation technology (EKR) is a green and effective in-situ soil remediation technology, namely, direct-current electric fields are applied to two sides of polluted soil, migration of organic pollutants is realized through electromigration and electrodialysis, and the method has the advantages of small damage to soil environment, low remediation cost, short remediation period, wide application range and capability of being combined with various technologies. The research on EKR combined technology is mostly aimed at heavy metal pollution treatment in soil, only a small part aims at organic pollutants, the repair efficiency is low, the organic pollutants are often enriched near a cathode region, and effective treatment cannot be achieved.
At present, the patent literature aiming at soil electrokinetic remediation focuses on the improvement of the invention of a soil electrokinetic remediation method and a device, but the invention of an electrode combined with EKR technology has little research, and the Chinese patent literature with publication number of CN102441564A discloses a composite electrode applied to heavy metal contaminated soil remediation, namely, an active layer is wrapped on the surface of the electrode, but the adsorption effect is saturated, and the service life is not long.
The Chinese patent document with publication number of CN 103331296B discloses that the electrochemical remediation electrode for polluted soil adopts a porous electrode with good permeability and large specific surface area, so that the electrodynamic remediation efficiency is improved to a certain extent, but a large amount of oxidant is required to be thrown into an electrode cavity to realize effective removal of pollutants, and the electrode has certain application limitations.
The patent literature on modified electrodes is millions of, most of which are applied to sensors, fuel cell electrodes, and the like. Although technological researchers have great significance in the aspect of electrocatalytic organic pollutant treatment, for example, the Chinese patent document with publication No. CN 106277229A reports a modified titanium dioxide nanotube electrode applied to electrocatalytic oxidation of organic pollutant atrazine, but the invention of applying the electrocatalytic modified electrode is hardly applicable to in-situ remediation of organic pollutants in soil.
Disclosure of Invention
The invention provides a metal nanocrystalline modified composite electrode capable of realizing the combination of electrodynamic force and electrocatalysis and a preparation method thereof, and the prepared metal nanocrystalline modified composite electrode has excellent electrocatalysis activity and durability and has great application prospect in the aspect of the application of the original electrodynamic force/electrocatalysis combination technology.
The composite electrode modified by the metal nanocrystalline can be applied to in-situ remediation of chlorine-containing organic pollutants in soil, and the organic pollutants are degraded by adopting an electrocatalytic means on the premise of electrodynamic remediation and enrichment of the organic pollutants, so that the purpose of in-situ remediation of polluted soil for efficient and sustainable operation is realized.
The technical scheme of the invention is as follows:
a preparation method of a metal nanocrystalline modified composite electrode comprises the following steps:
(1) Adding a plurality of metal precursors into a reduction solution, adding a blocking agent and a surface stabilizer, and carrying out a constant-temperature reduction reaction to obtain metal nanocrystals;
(2) Uniformly mixing the metal nanocrystalline with a catalytic carrier, and then adding a film forming solution to form a homogeneous phase modification solution;
(3) And coating the homogeneous modification liquid on the flat electrode slice to form a uniform liquid film, and drying to form a modification film to obtain the metal nanocrystalline modified composite electrode.
In the step (1), the metal precursor is at least two of palladium acetylacetonate, silver nitrate, ruthenium trichloride, platinum acetylacetonate, cobalt acetylacetonate, copper nitrate and ferric nitrate.
The metal precursors may be added simultaneously or in stages.
Preferably, the metal precursor is: silver nitrate and palladium acetylacetonate; or palladium acetylacetonate and ruthenium trichloride; or platinum acetylacetonate and cobalt acetylacetonate; or silver trifluoroacetate, platinum acetylacetonate and palladium acetylacetonate.
Further preferably, the metal precursor is: the molar ratio is 1: 1-2 of silver nitrate and palladium acetylacetonate, which are added in sequence; or the molar ratio is 5-3: 1 palladium acetylacetonate and ruthenium trichloride, both of which are added simultaneously; or a molar ratio of 1: 1-2 platinum acetylacetonate and cobalt acetylacetonate, which are added simultaneously; or the molar ratio is 1-2: 1 to 3:1, silver trifluoroacetate, platinum acetylacetonate and palladium acetylacetonate are added into the reaction system for 10 to 30 minutes at the same time, and then palladium acetylacetonate is added.
The reducing solution is an aqueous solution added with a reducing agent or a polyol solution preheated at 120-150 ℃; further, the reducing agent is ascorbic acid and/or citric acid, and the polyol is glycol and/or polyethylene glycol.
The end capping agent is citrate and/or potassium bromide; the surface stabilizer is at least one of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone. The end capping agent and the surface stabilizer can be selected according to the regulation and control requirements of the metal nanocrystalline.
In the step (2) of the invention, the catalytic carrier is activated carbon and/or graphene.
Preferably, the loading concentration of the metal nanocrystals is 1 to 20wt%. The loading concentration refers to the percentage of the metal nanocrystalline to the total mass of the metal nanocrystalline and the catalytic carrier.
The film forming solution should be capable of slowly volatilizing in air and forming a uniformly loaded film, preferably, the film forming solution is a mixed solution of 0.025-0.1 wt% of Nafion polymer isopropanol water; the volume ratio of the isopropyl alcohol to the water is 1:5 to 10.
In the step (3) of the invention, the homogeneous phase modification liquid can form a uniform liquid film on the electrode plate with a flat surface.
Preferably, the electrode plate is made of graphite, stainless steel or Ti.
The invention synthesizes the metal nanocrystalline by adopting a simple liquid phase reduction method, has mild reaction conditions and controllable metal nanocrystalline components, loads the synthesized metal nanocrystalline on a catalytic carrier, and modifies the electrode to obtain the metal nanocrystalline modified composite electrode.
The invention also provides application of the metal nanocrystalline modified composite electrode in restoration and removal of chlorine-containing organic pollutants in soil by using electrodynamic force/electrocatalytic combination.
The metal nanocrystalline modified composite electrode can be used for removing chlorine-containing organic pollutants in soil by combining electrodynamic force and electrocatalytic force, namely, when the soil is repaired in situ by using electrodynamic force, the organic pollutants enriched in the electrode area can be degraded by electrocatalytic force at the same time, so that the electrodynamic force repair efficiency of the soil is improved.
The application comprises: and (3) taking the composite electrode modified by the metal nanocrystalline as a cathode, taking a common non-loaded graphite or Ti electrode plate as an anode, applying a direct-current voltage for a period of time to carry out electrodynamic repair, changing the potential to a reduction peak potential, and carrying out dechlorination reduction on chlorine-containing organic matters enriched in the cathode by taking the metal nanocrystalline on the surface of the composite electrode as an electrocatalyst.
Preferably, the chlorine-containing organic pollutant is 2-chlorophenol, 2, 4-dichlorophenol or pentachlorophenol.
The principle of the application of the metal nanocrystalline modified composite electrode in soil remediation is electrochemical reduction dechlorination, hydrogen or hydrogen anions with strong reducibility are generated through cathode electrolysis to attack chlorine-containing organic matters enriched through electrodynamic remediation, and the C-Cl bond is broken and hydrogen atom addition is realized. Noble metal Pd has excellent hydrogen storage capacity, extremely strong dechlorination reduction electrocatalytic activity, ag has high affinity to chloride ions, and Ru has strong chlorine poisoning resistance. The multi-metal nanocrystalline synthesis is an effective means for reducing noble metal consumption while improving the electrocatalytic performance by combining a multi-metal synergistic effect and an electronic effect.
Compared with the prior art, the invention has the beneficial effects that:
the metal nanocrystalline modified composite electrode has higher electrocatalytic activity and chlorine poisoning resistance, combines the advantages of electrodynamic repair and electrocatalytic dechlorination aiming at the treatment of chlorine-containing organic matters in soil, has the advantages of in-situ repair, low repair cost, short repair period, wide application range, high organic matter dechlorination efficiency, simple and convenient operation, mild condition and low secondary pollution risk, and realizes efficient and environment-friendly repair treatment.
Drawings
FIG. 1 is a transmission electron microscope image of the metal nanocrystals prepared in example 1;
FIG. 2 is a transmission electron microscope image of the metal nanocrystals prepared in example 2;
FIG. 3 is a transmission electron microscope image of the metal nanocrystals prepared in example 3 mixed with a carrier;
FIG. 4 is a schematic diagram of a simplified apparatus for performing electrodynamic/electrocatalytic combined soil remediation according to an embodiment.
Detailed Description
The following describes the preparation method and application of the metal nanocrystalline composite electrode according to the present invention with reference to specific examples, but the scope of the present invention is not limited to the scope described in the examples, which are only for the purpose of better understanding the present invention.
Example 1
Preparation of 50mmol L -1 AgNO of (A) 3 Solution, 0.1mol L -1 K of (2) 2 PdCl 4 The solution was prepared by mixing 1mL of each of the two metal precursor solutionsSequentially adding the mixture into 20mL of polyethylene glycol PEG solution (PEG average molecular weight=400) preheated at 130 ℃ for 10min, adding a proper amount of KCl end capping agent (molar ratio of metal precursor Ag: KCl=1:10) and cetyltrimethylammonium chloride CTAC (molar ratio of total metal precursor: CTAC=1:2) serving as a surface stabilizer into a reaction system in advance, performing constant temperature reaction for 3h, and then performing centrifugal washing to be redispersed in 5mL of aqueous solution. The nanocrystals were observed by high resolution transmission electron microscopy as shown in fig. 1, being metal nanocrystals smaller than 10 nm. Ultrasonically treating nanocrystalline and catalytic carrier graphene (with load of 5 wt%) in 15mL of ethanol for 8h, adding 10mL of acetic acid, stirring at 50deg.C for 24h to ensure complete uniform mixing, centrifuging, washing, collecting, oven drying at low temperature, and proportionally adding Nafion polymer isopropanol water mixed solution (0.025 wt% Nafion, V) Isopropyl alcohol ：V Water and its preparation method =1: 5) And carrying out ultrasonic treatment for 10 hours to form a homogeneous phase modification solution. And uniformly dripping 500 mu L of the electrocatalyst modification solution onto an electrode plate (graphite, stainless steel and Ti) with a flat surface at room temperature, slightly swinging left and right when the electrocatalyst modification solution can flow, so as to ensure that a uniform liquid film is formed on one surface of the electrode, and then airing at room temperature to form the electrode covered with the modification film.
Example 2
15mL of ethylene glycol solution containing a certain amount of surface stabilizer polyvinylpyrrolidone PVP (molar ratio of metal precursor: PVP monomer=1:10) and cetyltrimethylammonium bromide CTAB (molar ratio of metal precursor: CTAB=1:2) is firstly preheated at 150 ℃ for 10min, 0.15mmol of palladium acetylacetonate and 0.03mmol of ruthenium trichloride precursor are simultaneously added, stirring and constant-temperature reaction are continued for 24h, and then centrifugal washing and dispersion are carried out in 6mL of deionized water for standby. The PdRu nanocrystals were observed to be metal nanocrystals having a uniform size of 5nm or less by high resolution transmission electron microscopy as shown in fig. 2. Ultrasonically treating the nanocrystalline and catalytic carrier active carbon (loading 10 wt%) in 15mL of ethanol for 8h, adding 15mL of acetic acid, fully stirring for 24h to ensure complete uniform mixing, centrifuging, washing and collecting, drying at low temperature, and proportionally adding Nafion polymer isopropanol water mixed solution (0.05 wt% Nafion, V) Isopropyl alcohol ：V Water and its preparation method =1: 9) And performing ultrasonic treatment for 8 hours to form a homogeneous phase modification solution. Taking 500 mu L of the electrocatalyst modification liquid at room temperatureAnd uniformly dripping the mixture onto an electrode plate (graphite, stainless steel and Ti) with a flat surface, slightly swinging left and right when the liquid phase can flow, ensuring that a uniform liquid film is formed on one surface of the electrode, and then airing at room temperature to form the electrode covered with the modified film.
Example 3
A20 mL ethylene glycol solution containing 200mg polyvinylpyrrolidone PVP, 270mg potassium chloride KCl was preheated in a reaction glass flask at 125℃for 10min, followed by the addition of 0.2mmol silver trifluoroacetate and 0.3mmol platinum acetylacetonate precursor, the reaction was carried out under constant temperature stirring for 30min, followed by the continued addition of 0.1mmol palladium acetylacetonate precursor, and after a further reaction time of 6h, washing by centrifugation and redispersion were carried out. The nanocrystalline and the catalytic carrier active carbon (load 10 wt%) are fully stirred for 24 hours in 15mL of ethanol and 15mL of acetic acid to ensure complete and uniform mixing, then the mixture is centrifugally washed and collected, and after drying, nafion polymer isopropanol water mixed solution (0.1 wt% Nafion, V) is proportionally added Isopropyl alcohol ：V Water and its preparation method =1: 9) And carrying out ultrasonic treatment for 10 hours to form a homogeneous phase modification solution. Microscopic observation of this solution revealed that the synthesized multi-metal nanocrystals were already supported on a carrier, as shown in fig. 3. And (3) uniformly dripping a proper amount of the electrocatalyst modification solution onto an electrode plate (graphite, stainless steel and Ti) with a flat surface at room temperature, slightly swinging left and right when the electrocatalyst modification solution can flow in a liquid phase to ensure that a uniform liquid film is formed on one surface of the electrode, and then airing at room temperature to form the electrode covered with the modification film.
The EKR/electrocatalytic combination technique application is carried out on a self-made electrodynamic repair EKR device (the structure is shown in figure 4) by respectively using a common graphite electrode without a metal nanocrystalline modification layer and a plurality of groups of modification electrodes prepared in examples 1-3, test soil (the water content of which is 30%) added with target pollutants (2, 4-dichlorophenol, 2, 4-DCP) is filled into a soil chamber (9 cm multiplied by 6 cm), and an electrolyte (0.05 mol L) with pH of which the cathode and anode electrolysis chambers (6 cm multiplied by 6 cm) are not regulated -1 NaCl)。
EKR-electrocatalytic cycle is performed when EKR/electrocatalytic combination is performed. When the repair time is 24 hours, a DC voltage (1V cm) -1 ) After 5.5h of electrodynamic remediation, the potential was changed to the peak reduction potential measured by cyclic voltammetry to ensure maximum dechlorination efficiencyElectrocatalytic degradation is carried out for 30min; and when the repair time is 12h, the electrodynamic repair time is 2.5h, and then dechlorination is carried out for 30 min. And (3) extracting residual 2,4-DCP in the soil by adopting an accelerated solvent extraction method after 4 rounds of restoration, and measuring the average concentration by adopting an HPLC high performance liquid chromatograph. The results are shown in the following table:
from the table, the chlorine-containing organic matters (2, 4-DCP) in the soil can be repaired and treated more efficiently and thoroughly by the combination of the electrodynamic force and the electrocatalytic through the metal nanocrystalline composite electrode, wherein the removal rate of more than 90% can be achieved after the repair time of 24 hours in the embodiment 2, the removal rate of more than 80% can be achieved after the repair time of 12 hours in the embodiment 3, and the polymetallic nanocrystalline shows excellent electrocatalytic dechlorination efficiency.
The above description is only specific embodiments of the metal nanocrystalline modified electrode according to the present invention, but the scope of the present invention is not limited thereto, and any simple modification, variation and equivalent changes to the above embodiments according to the technical substance of the present invention still fall within the scope of the present invention.
Claims (1)
1. The application of the composite electrode modified by the metal nanocrystalline in removing chlorine-containing organic pollutants in soil by electro-dynamic force and electro-catalytic combined repair is characterized by comprising the steps of taking the composite electrode modified by the metal nanocrystalline as a cathode, taking common non-loaded graphite or Ti electrode plates as anodes, changing the potential to the reduction peak potential after applying direct-current voltage for electro-dynamic force repair, and dechlorination reducing the chlorine-containing organic matters enriched in the cathode by taking the metal nanocrystalline on the surface of the composite electrode as an electro-catalyst;
the preparation method of the metal nanocrystalline modified composite electrode comprises the following steps:
(1) Adding a plurality of metal precursors into a reduction solution, adding a blocking agent and a surface stabilizer, and carrying out a constant-temperature reduction reaction to obtain metal nanocrystals;
the metal precursor is as follows: silver nitrate and palladium acetylacetonate; or palladium acetylacetonate and ruthenium trichloride; or platinum acetylacetonate and cobalt acetylacetonate; or silver trifluoroacetate, platinum acetylacetonate and palladium acetylacetonate; the end capping agent is citrate and/or potassium bromide; the surface stabilizer is at least one of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone;
the reducing solution is an aqueous solution added with a reducing agent or a polyol solution preheated at 120-150 ℃;
(2) Uniformly mixing the metal nanocrystalline with a catalytic carrier, and then adding a film forming solution to form a homogeneous phase modification solution; the loading concentration of the metal nanocrystalline is 1-20wt%; the loading concentration refers to the percentage of the metal nanocrystalline in the total mass of the metal nanocrystalline and the catalytic carrier;
the catalytic carrier is activated carbon and/or graphene;
the film forming solution is 0.025-0.1wt% of Nafion polymer isopropanol water mixed solution; the volume ratio of the isopropyl alcohol to the water is 1: 5-10;
(3) And coating the homogeneous modification liquid on the flat electrode slice to form a uniform liquid film, and drying to form a modification film to obtain the metal nanocrystalline modified composite electrode.
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