CN114956267B - Supported metal palladium particle electrode taking bimetallic organic framework as intermediate layer and preparation and application thereof - Google Patents
Supported metal palladium particle electrode taking bimetallic organic framework as intermediate layer and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an electrode with a bimetal organic framework as an intermediate layer and loaded with metal palladium particles, which comprises the following steps: (1) Adding foam nickel into a precursor solution containing nickel ions, cobalt ions and organic components for reaction to obtain a NiCo-MOF/foam-Ni electrode; (2) And (3) taking the NiCo-MOF/foam-Ni electrode as a cathode, taking a solution containing palladium ions as a deposition solution, and preparing the Pd/NiCo-MOF/foam-Ni electrode by electrodeposition. The invention also relates to the Pd/NiCo-MOF/foam-Ni electrode prepared by the method and the application thereof in electrocatalytic hydrodechlorination. The electrode realizes higher catalytic performance and reaction performance of the catalytic material, more convenient operability, longer service life and higher use stability through the synergistic effect of the NiCo-MOF intermediate layer and the palladium metal particles.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a supported metal palladium particle electrode taking a bimetal organic framework as an intermediate layer, and preparation and application thereof.
Background
In recent years, medicines and personal care products have received widespread attention due to their rapid development. In various uses in modern life, these compounds may also have an impact on human and environmental health.
The U.S. environmental protection agency deems pharmaceutical and personal care products (Pharmaceuticals and Personal Care Products, PPCP) to be an emerging contaminant of interest. Because of its poor biodegradability, part of PPCP organics and their potentially harmful degradation (conversion) products remain in the wastewater after treatment, which raises concerns about the environmental system and human health. Many chlorinated PPCPs are detected in human breast milk, blood and urine. Many studies report that artificial and natural hormones in the marine environment cause endocrine disorders in marine organisms. Diclofenac sodium is bioaccumulative, induces oxidative stress, and is cytotoxic and genotoxic to aquatic organisms, and may increase the risk of poisoning when such drugs are transmitted through the food chain in different aquatic organisms. Triclosan, although not acutely toxic to mammals, has adverse effects on hormone levels, endocrine function and drug resistance in vivo, and can affect the next generation gene by inheritance.
The treatment methods of biodegradation, chemical reduction, advanced oxidation and the like of PPCP are reported in the literature, but due to the limitation of biodegradation in practical application and toxic byproducts generated in the chemical reduction and advanced oxidation processes, development of a green and economic wastewater treatment method is imperative.
The electrocatalytic hydrodechlorination (ECH) process is widely applied due to high degradation performance, mild reaction conditions and low secondary pollution. In the ECH process, noble metal catalyst modification is performed on the cathode, active atoms H are adsorbed on the surface of the catalyst, and the activity of the catalyst is improved. Palladium (Pd) is widely used because of its adsorption and storage capacity for H-x higher than other noble metals (e.g. silver, gold). However, the electrode prepared by loading Pd on the substrate has the problems of large particle size, easy aggregation and low Pd particle utilization rate. For example, the average particle diameter of Pd particles on the TiN-Pd electrode and the C-Pd electrode is 5.2nm; the average particle diameter of Pd particles on the Pd@Ni-foam electrode was 8.9nm. The aggregation of metal Pd particles on the electrode surface seriously affects the number of active sites on the electrode surface and the efficiency of the electrocatalytic reaction.
In order to control the size and dispersion of Pd nanoparticles, some research has focused on various carrier materials to support Pd catalysts. Many previous studies have used alumina, silica, activated carbon fibers and other porous materials as supports. However, the electrode prepared with these materials as a carrier has low dechlorination efficiency, and Pd nanoparticles are easily detached, which reduces the stability of the electrode to some extent.
Disclosure of Invention
In order to solve the above technical problems in the prior art, the present invention provides in a first aspect a method for preparing an electrode with a bimetal organic framework as an intermediate layer and supported with metal palladium particles, the method comprising the steps of:
(1) Adding foam nickel into a precursor solution containing nickel ions, cobalt ions and organic components for reaction to obtain a NiCo-MOF/foam-Ni electrode;
(2) And (3) taking the NiCo-MOF/foam-Ni electrode as a cathode, taking a solution containing palladium ions as a deposition solution, and preparing the Pd/NiCo-MOF/foam-Ni electrode by electrodeposition.
In the present invention, foam-Ni represents nickel foam and MOF represents a metal organic framework compound.
The present invention provides in a second aspect Pd/NiCo-MOF/foam-Ni electrodes prepared according to the preparation method of the first aspect of the invention.
In a third aspect, the invention provides the use of a Pd/NiCo-MOF/foam-Ni electrode according to the second aspect of the invention in the electrocatalytic hydrodechlorination of chlorinated PPCP compounds. Preferably, the chlorinated PPCP organic is at least one selected from the group consisting of chloramphenicol, diclofenac sodium, and triclosan.
The invention has the following advantages and positive meanings:
(1) The invention constructs a three-dimensional space network structure by taking the nickel-cobalt material which is low in cost and easy to obtain as a support body of palladium particles.
(2) The Pd/NiCo-MOF/foam-Ni electrode is synthesized by adopting a hydrothermal method and an electrodeposition method, and the preparation is simple and efficient.
(3) The invention fully utilizes the structural characteristics of the bimetal organic framework, and the structure has high porosity and rapid charge transfer capability.
(4) The Pd/NiCo-MOF/foam-Ni electrode prepared by the invention has good electrocatalytic performance to chlorinated PPCP, and the stability of the electrode is excellent.
Drawings
FIG. 1 shows scanning electron microscope images of nickel foam (a (200X)) and Pd/foam-Ni (b (10000X)).
FIG. 2 shows scanning electron micrographs of NiCo-MOF/foam-Ni electrodes at different magnifications, wherein the magnification of FIG. (a) is 2000X, the magnification of FIG. (b) is 10000X, and the magnification of FIG. (c) is 30000X.
FIG. 3 shows scanning electron microscope images of Pd/NiCo-MOF/foam-Ni electrodes at different magnifications, wherein the magnification of the image (a) is 2000X, (the magnification of the image (b) is 10000X, and the magnification of the image (c) is 30000X.
FIG. 4 is a transmission electron micrograph (a, c) of Pd/NiCo-MOF/foam-Ni electrode and a histogram (b) of particle size distribution of Pd particles.
FIG. 5 shows the electrocatalytic hydrodechlorination effect of Pd/foam-Ni, niCo-MOF/foam-Ni and Pd/NiCo-MOF/foam-Ni electrodes on chloramphenicol.
FIG. 6 shows the first order kinetics of the electrocatalytic hydrodechlorination of chloramphenicol by Pd/foam-Ni, niCo-MOF/foam-Ni and Pd/NiCo-MOF/foam-Ni electrodes.
FIG. 7 shows Pd/NiCo-MOF/foam-Ni electrodes, pd/NiCo-MOF 2 /foam-Ni、 Pd/NiCo-MOF 1 foam-Ni and Pd/NiCo-MOF 0.25 Electrocatalytic hydrodechlorination effect of foam-Ni electrode on chloramphenicol.
FIG. 8 shows the electrocatalytic hydrodechlorination effect of Pd/NiCo-MOF/foam-Ni electrodes on diclofenac sodium, triclosan, and 2, 4-dichlorophenoxyacetic acid.
FIG. 9 shows a scanning electron microscope image after 5 consecutive uses of Pd/NiCo-MOF/foam-Ni electrodes, wherein the magnification of image (a) is (2000X) and the magnification of image (b) is (5000X).
FIG. 10 shows a graph of the stability effect of Pd/NiCo-MOF/foam-Ni electrodes.
Detailed Description
The invention aims to solve the problems of large size, easy aggregation, low Pd particle utilization rate and the like of catalytic metal Pd particles loaded on the traditional electrode, and provides the preparation and application of the electrode with the bimetallic organic framework as an intermediate layer loaded with metal Pd particles.
Specifically, in order to solve the above technical problems in the prior art, the present invention provides in a first aspect a method for preparing an electrode with a bimetal organic framework as an intermediate layer and supported with metal palladium particles, the method comprising the steps of:
(1) Adding foam nickel into a precursor solution containing nickel ions, cobalt ions and organic components for reaction to obtain a NiCo-MOF/foam-Ni electrode;
(2) And (3) taking the NiCo-MOF/foam-Ni electrode as a cathode, taking a solution containing palladium ions as a deposition solution, and preparing the Pd/NiCo-MOF/foam-Ni electrode by electrodeposition.
In some preferred embodiments, the method further comprises the step of pre-treating the nickel foam to remove impurities contained in the nickel foam prior to step (1). Preferably, the pretreatment is performed by: cutting the foam nickel sheet to a target size, and then placing the foam nickel sheet into an acetone solution for ultrasonic cleaning for 10 to 20 (for example, 15) min; then, ultrasonically cleaning the foam nickel in water for 15 to 20 minutes (for example, 18 minutes); then, the nickel foam is put into a concentration of 0.4 to 0.6 (e.g. 0.5) mol.L -1 Ultrasonic cleaning in dilute sulfuric acid for 2 to 3 minutes; finally, the nickel foam is ultrasonically cleaned in water for 2 to 4 times (e.g., 3 times) for 20 to 30 minutes each time, thereby obtaining the pretreated nickel foam.
a) In some specific embodiments, the pretreatment is performed by: firstly, shearing a foam nickel sheet to a target size, and putting the foam nickel sheet into an acetone solution for ultrasonic cleaning for 15min to remove impurities attached to the surface of the foam nickel; then, the foam nickel is washed in deionized water for 15-20min, and then the foam nickel is put into the deionized water with the concentration of 0.5 mol.L -1 Ultrasonic cleaning in dilute sulfuric acid for 2-3min,to remove surface oxides thereof. Then, the foam nickel is put into deionized water for ultrasonic cleaning for 3 times (20 to 30 minutes each time), and the pretreated foam nickel matrix is put into ultrapure water for storage after cleaning is finished for later use.
In other preferred embodiments, in step (1), the target size of the nickel foam is (1-3) cm× (1-3) cm, for example 2cm×2cm.
In other preferred embodiments, the organic component is a combination of terephthalic acid and N, N-dimethylformamide; more preferably, the precursor solution comprises, in a volume of 20 mL: 0.45 to 0.55 (e.g. 0.50) mmol terephthalic acid, 0.15 to 0.25 (e.g. 0.20) mmol Co (NO) 3 ) 2 ·6H 2 O, 0.25 to 0.35 (e.g. 0.30) mmol Ni (NO) 3 ) 2 ·6H 2 O and 16 to 20 (e.g., 18) mL of N, N-dimethylformamide, 0.8 to 1.2mL (e.g., 1 mL) of ethanol, and 0.8 to 1.2mL (e.g., 1 mL) of water. It is further preferred that the precursor solution is prepared by: terephthalic acid, co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 And mixing O and N, N-dimethylformamide uniformly, then adding a mixed solution of ethanol and water, and further stirring uniformly to obtain the precursor solution. More preferably, the mixed solution of ethanol and water is an equal volume mixed solution of ethanol and water.
In other preferred embodiments, in step (1), the reaction temperature of the reaction is 140 to 160 ℃ (e.g., 150 ℃) and the reaction time is 9 to 15 hours (e.g., 12 hours). It is also preferable that in the step (1), after the completion of the reaction, the step of ultrasonically cleaning and drying the NiCo-MOF/foam-Ni electrode obtained by the reaction is further included.
In other preferred embodiments, the deposition solution comprises 0.20 to 0.30 (e.g., 0.25) mmol.L - 1 PdCl 2 And 0.70 to 0.80 (e.g., 0.75) mmol.L -1 NaCl。
In other preferred embodiments, the electrodeposition employs a platinum electrode as the anode. More preferably, the electrodeposition is performed in a constant current of 6 to 8 (e.g., 7) mA and a constant temperature water bath of 35 to 45 ℃ (e.g., 40 ℃) for 1.5 to 2.5 hours (e.g., 2 hours).
In other preferred embodiments, the sum of the moles of nickel ions and cobalt ions in the precursor solution is from 0.25 to 2.0 moles.
In some more specific embodiments, the method comprises the steps of:
(1) And preparing the NiCo-MOF on the foam nickel material by adopting a one-step hydrothermal method to obtain the NiCo-MOF/foam-Ni electrode. Specifically, first, 0.5mmol of terephthalic acid, 0.2mmol of Co (NO 3 ) 2 ·6H 2 O、0.3mmol Ni(NO 3 ) 2 ·6H 2 O and 18mL of N, N-dimethylformamide were mixed and stirred at 25℃for 15min. Then, 2mL of an ethanol-water mixed solution in equal proportion was added, and stirred to form a precursor solution. Pretreated foam nickel (2X 2 cm) 2 ) Immersed in the precursor solution and reacted in a reaction vessel at 150 ℃ for 12 hours. After the reaction, the NiCo-MOF/foam-Ni was subjected to ultrasonic washing and drying.
In this step, co (NO 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar sum of O was 0.5mmol, recorded as NiCo-MOF/foam-Ni. Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar sum of O is adjusted to 0.25, 1.0 and 2.0mmol, and Ni-Co bimetallic organic frameworks with different contents are synthesized. For descriptive purposes, these NiCo-MOF/foam-Ni electrodes may be designated as NiCo-MOF, respectively 0.25 /foam-Ni、 NiCo-MoF 1 foam-Ni and NiCo-MOF 2 /foam-Ni。
(2) Preparation of Pd/NiCo-MOF/foam-Ni electrode: the NiCo-MOF/foam-Ni electrode is used as a cathode and a platinum electrode (1X 2 cm) 2 ) As an anode, a Pd/NiCo-MOF/foam-Ni electrode was prepared by electrodeposition of a palladium chloride solution as a deposition solution in a constant current of 7mA and a constant temperature water bath of 40℃for 2 hours. The palladium chloride solution contains 0.25 mmol.L -1 PdCl 2 And 0.75 mmol.L -1 NaCl. In the deposition solution of the present invention, naCl acts as a complexing agent to aid in dissolution.
The present invention provides in a second aspect Pd/NiCo-MOF/foam-Ni electrodes prepared according to the preparation method of the first aspect of the invention.
The metal-organic framework in the electrode is a three-dimensional framework structure porous material consisting of metal ions or metal clusters and an organic complex. MOF materials have high porosity and fast charge transfer capability. The preparation of metal nanoparticles/metal-organic framework composites using MOFs as carriers can significantly reduce nanoparticle aggregation and help control nanoparticle size. In addition, MOFs can enable these complexes to exhibit properties different from their composition by providing additional active sites to act synergistically with the metal nanoparticles. Due to the synergistic effect of Ni and Co, the NiCo-based MOF electrode material not only has excellent conductivity, but also has excellent electrocatalytic performance. As a result, it was found that the NiCo-MOF and Pd particles have a synergistic effect in increasing the amount of H and in storage, and can significantly improve the performance of electrocatalytic hydrodechlorination.
In a third aspect, the invention provides the application of the Pd/NiCo-MOF/foam-Ni electrode in the electro-catalytic hydrodechlorination of chlorinated PPCP organics. Preferably, the chlorinated PPCP organic is at least one selected from the group consisting of chloramphenicol, diclofenac sodium, and triclosan.
According to the invention, a nickel-cobalt bimetal organic framework (NiCo-MOF) is introduced as an intermediate layer, so that a Pd/NiCo-MOF/foam-Ni composite electrode is synthesized, the electrode substrate has a larger specific surface area and the agglomeration of supported metal palladium particles is avoided, the electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and chlorinated PPCP organic matters in water are removed through electrocatalytic treatment. As a result, it was found that the electrode of the present invention has excellent electrocatalytic properties, and is particularly suitable for electrocatalytic hydrodechlorination (ECH) for chloro-drugs and personal care products (PPCP). Compared with the common Pd/foam-Ni electrode, the catalytic activity is obviously improved by introducing the NiCo-MOF structure. The removal efficiency of the Pd/NiCo-MOF/foam-Ni electrode to Chloramphenicol (CAP) reaches more than 95% at 40min, and the removal efficiency of the Pd/foam-Ni electrode to chloramphenicol is only about 55%.
The present invention will be illustrated by examples below, but the scope of the present invention is not limited to these examples.
Example 1
Preparation of NiCo-MOF/foam-Ni electrode
Pretreatment of foam nickel. Firstly cutting the foam nickel sheet to a required size (2X 2 cm) 2 ) Ultrasonic cleaning them in acetone solution for 15min to remove impurities adhered to the surface of foam nickel, cleaning the substrate in deionized water for 15-20min, and placing foam nickel substrate at concentration of 0.5 mol.L -1 The method comprises the steps of ultrasonically cleaning the surface of the foam nickel substrate in dilute sulfuric acid for 2-3min, then ultrasonically cleaning the foam nickel substrate in deionized water for 3 times, and after the cleaning is finished, placing the pretreated foam nickel substrate in ultrapure water for storage for later use.
Preparation of NiCo-MOF/foam-Ni electrode. The NiCo-MOF is prepared on the foam nickel material by adopting a one-step hydrothermal method. First, 0.5mmol of terephthalic acid, 0.2mmol of Co (NO 3 ) 2 ·6H 2 O，0.3mmol Ni(NO 3 ) 2 ·6H 2 O and 18mL of N, N-dimethylformamide were mixed and stirred at 25℃for 15min. Then, 2mL of an ethanol-water mixed solution in equal proportion was added, and stirred to form a precursor solution. The pretreated foam nickel (2X 2 cm) 2 ) Immersed in the precursor solution and reacted in a reaction vessel at 150 ℃ for 12 hours. After the reaction, the NiCo-MOF/foam-Ni was subjected to ultrasonic washing and drying. Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar sum of O was 0.5mmol, recorded as NiCo-MOF 0.5 foam-Ni. Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar sum of O is adjusted to 0.25, 1.0 and 2.0mmol, and Ni-Co bimetallic organic frameworks with different contents are synthesized. Thus, the present inventors named these NiCo-MOF/foam-Ni electrodes as NiCo-MOF 0.25 /foam-Ni、NiCo-MoF 1 foam-Ni and NiCo-MOF 2 /foam-Ni。
Preparation of Ni-MOF/foam-Ni electrode
Pretreatment of foam nickel. Pretreatment of the nickel foam was performed in the same manner as described above to obtain a nickel foam substrate subjected to the above pretreatment.
Ni-MOF/foam-Ni electrode preparation. The Ni-MOF is prepared on the foam nickel material by adopting a one-step hydrothermal method. First, 0.5mmol C 8 H 6 O 4 ，0.5mmol Ni(NO 3 ) 2 ·6H 2 O and 18mL DMF were mixed and stirred at 25℃for 15min. Then, 2mL of an ethanol-water mixed solution in equal proportion was added, and stirred to form a precursor solution. The pretreated foam nickel (2X 2 cm) 2 ) Immersed in the precursor solution and reacted in an autoclave at 150℃for 12 hours. After the reaction is finished, the Ni-MOF/foam-Ni is subjected to ultrasonic washing and drying to obtain the Ni-MOF/foam-Ni electrode.
Example 2
Preparation of Pd/NiCo-MOF/foam-Ni electrode
The NiCo-MOF/foam-Ni electrode is used as a cathode and a platinum electrode (1X 2 cm) 2 ) As an anode, a Pd/NiCo-MOF/foam-Ni electrode was prepared by electrodeposition of a palladium chloride solution as a deposition solution in a constant current of 7mA and a constant temperature water bath of 40℃for 2 hours. The palladium chloride solution is composed of 0.25 mmol.L -1 PdCl 2 And 0.75 mmol.L -1 And NaCl is mixed, wherein the NaCl serves as a complexing agent to assist dissolution.
Pd/Ni-MOF/foam-Ni electrode preparation
Ni-MOF/foam-Ni electrode as cathode and platinum electrode (1×2 cm) 2 ) As an anode, a Pd/Ni-MOF/foam-Ni electrode was prepared by electrodeposition of a palladium chloride solution as a deposition solution in a constant current of 7mA and a constant temperature water bath of 40℃for 2 hours. The palladium chloride solution is composed of 0.25 mmol.L -1 PdCl 2 And 0.75 mmol.L -1 And NaCl is mixed, wherein the NaCl serves as a complexing agent to assist dissolution.
Fig. 1 (a) shows a scanning electron microscope image of a foam nickel electrode after pretreatment, and as can be seen from fig. 1 (a), the foam nickel has a three-dimensional porous structure and a smoother surface. FIG. 1 (b) shows a scanning electron microscope image of Pd/foam-Ni electrode, and it can be seen from FIG. 1 (b) that metal Pd particles are uniformly supported on nickel foam.
FIG. 2 shows scanning electron microscope images of NiCo-MOF/foam-Ni electrodes at different magnifications. As can be seen from the figure, the NiCo-MOF nanocluster is composed of a plurality of layers of petal-shaped nanoplatelets, which are connected with each other on the surface of the nickel foam to form a space structure, so that the surface of the nickel foam is rough and uneven, the specific surface area of the electrode is larger, more surface active sites can be provided to improve the electron transfer efficiency, and the loading and electrocatalytic reaction of metal Pd are facilitated.
FIG. 3 shows scanning electron microscope images of the prepared Pd/NiCo-MOF/foam-Ni electrodes at different magnifications. From the figure, the metal Pd nano particles are in a cauliflower-shaped structure, are connected with each other to form clusters, uniformly grow on the NiCo-MOF nano clusters, and only a small part of Pd particles are directly supported on the foam nickel substrate, so that the catalytic performance of the electrode is greatly improved.
FIG. 4 shows a transmission electron micrograph of Pd/NiCo-MOF/foam-Ni electrodes and a histogram of particle size distribution of Pd particles. As can be seen from the figure, the average particle size of Pd particles is only 3.80nm, and the Pd/NiCo-MOF/foam-Ni electrode has clear lattice fringes, showing a clear lattice structure, and the 0.225nm lattice spacing is the (111) atomic plane of Pd with face-centered cubic (fcc).
Example 3: electrocatalytic hydrodechlorination of chloramphenicol by different electrodes
The Pd/foam-Ni electrode, the NiCo-MOF/foam-Ni electrode, the Pd/Ni-MOF/foam-Ni electrode and the Pd/NiCo-MOF/foam-Ni electrode are used as working electrodes, and the platinum sheet electrode is used as a counter electrode to perform electrocatalytic hydrodechlorination on chloramphenicol. Wherein the concentration of chloramphenicol is 35 mg.L -1 . The reaction experimental device is an H-type electrochemical reactor made of polytetrafluoroethylene, wherein two chamber channels are separated by a proton exchange membrane so as to prevent chloride ions from entering the anode. The anode solution was 50mL of 0.05 mol.L -1 Na of (2) 2 SO 4 Solution, cathode solution is target pollutant and 0.05mol.L -1 Na 2 SO 4 (i.e. comprising 0.05 mol.L) - 1 Na 2 SO 4 Target contaminant of (2). The reaction was carried out in a 40 ℃ constant temperature water bath at a constant current of 7mA and the cathode chamber was stirred using a heat collecting magnetic stirrer to ensure uniform and constant concentration and temperature of the cathode solution. The reaction time is 120min, and the extraction is carried out every 20minThe sample was taken and the contaminant concentration therein was measured by liquid chromatography. The liquid chromatography was performed by using a high performance liquid chromatography (LC-20 AT) from Shimadzu corporation and a C18 column (150X 4.6mm,5 μm) as a detector, and the detector was an LC-20A ultraviolet detector. The test conditions for chloramphenicol were as follows: the mobile phase is methanol: water, volume ratio 60:40, a step of performing a; the detection wavelength is 278nm; the flow rate is 1.0mL/min; the peak time was 11min.
FIG. 5 shows the electrocatalytic hydrodechlorination effect of Pd/foam-Ni, niCo-MOF/foam-Ni, pd/Ni-MOF/foam-Ni electrodes and Pd/NiCo-MOF/foam-Ni electrodes on chloramphenicol. As can be seen from the graph, the Pd/NiCo-MOF/foam-Ni electrode has good electro-catalytic hydrodechlorination performance on chloramphenicol, the removal rate is high, the removal rate of chloramphenicol at 40min reaches 95.08%, and the removal rates of Pd/foam-Ni and NiCo-MOF/foam-Ni and Pd/Ni-MOF/foam-Ni electrode on chloramphenicol are 54.26%, 46.47% and 70.97%, respectively. In addition, the removal rate of the Pd/Ni-MOF/foam-Ni to chloramphenicol is up to 95%, 80 minutes is needed, and the time spent by the Pd/NiCo-MOF/foam-Ni electrode is doubled; the removal rate of the Pd/NiCo-MOF/foam-Ni electrode to chloramphenicol at 60min reaches 98.01%, and the removal rates of the Pd/foam-Ni electrode and the NiCo-MOF/foam-Ni electrode to chloramphenicol at this time are 67.00%, 54.23% and 88.94% respectively; the Pd/NiCo-MOF/foam-Ni electrode can completely remove chloramphenicol within 120min (the removal rate is 100%), while the Pd/foam-Ni and NiCo-MOF/foam-Ni and Pd/Ni-MOF/foam-Ni electrodes can not completely remove chloramphenicol, and the removal rates are 94.71%, 80.52% and 97.56%, respectively.
As shown in FIG. 6, the reaction kinetic model of Pd/foam-Ni, niCo-MOF/foam-Ni, pd/Ni-MOF/foam-Ni electrode and Pd/NiCo-MOF/foam-Ni electrode for the electrocatalytic hydrodechlorination of chloramphenicol was studied, and the reaction rate constant was calculated. The reaction rate constants of the NiCo-MOF/foam-Ni, pd/Ni-MOF/foam-Ni and Pd/NiCo-MOF/foam-Ni electrodes on the electrocatalytic hydrogenation dechlorination of chloramphenicol are 0.01279min respectively -1 、0.02463min -1 、0.03414min -1 And 0.06784min -1 As can be seen, compared with Pd/foam-Ni, niCo-MOF/foam-Ni and Pd/Ni-MOF/foam-Ni electrodes,the Pd/NiCo-MOF/foam-Ni electrode had better electrocatalytic performance, and the experimental results were consistent with the removal results mentioned above.
Example 4: effect of different NiCo mole numbers on the effect of electrocatalytic hydrodechlorination of chloramphenicol
Pd/NiCo-MOF/foam-Ni electrode and Pd/NiCo-MOF 2 /foam-Ni、 Pd/NiCo-MOF 1 foam-Ni and Pd/NiCo-MOF 0.25 A foam-Ni electrode was subjected to an electrocatalytic hydrodechlorination experiment on chloramphenicol in substantially the same manner as in example 3.
FIG. 7 shows the electrocatalytic hydrodechlorination effect of four electrodes on chloramphenicol. As can be seen from FIG. 7, the optimum removal rate of chloramphenicol from Pd/NiCo-MOF/foam-Ni electrode was 100%, pd/NiCo-MOF 2 /foam-Ni、Pd/NiCo-MOF 1 foam-Ni and Pd/NiCo-MOF 0.25 The chloramphenicol removal rates of the/foam-Ni electrode were 93.27%, 97.20% and 99.87%, respectively.
Example 5: electrocatalytic hydrodechlorination effect of Pd/NiCo-MOF/foam-Ni electrode on diclofenac sodium, triclosan and 2, 4-dichlorophenoxyacetic acid
The Pd/NiCo-MOF/foam-Ni electrode was used for the electrocatalytic hydrodechlorination experiments on diclofenac sodium, triclosan and 2, 4-dichlorophenoxyacetic acid. The liquid chromatography test conditions for diclofenac sodium (DCF) were as follows: the mobile phase is methanol: glacial acetic acid (1%), volume ratio 75:25, a step of selecting a specific type of material; the detection wavelength is 276nm; the flow rate is 1.0mL/min; the peak time was 7min. Test conditions for Triclosan (TCS) are as follows: the mobile phase is methanol: water, volume ratio 90:10; the detection wavelength is 282nm; the flow rate is 1.0mL/min; the peak time was 7min. The test conditions for 2, 4-dichlorophenoxyacetic acid (2, 4-D) were as follows: the mobile phase is methanol: water, volume ratio 75:25, ph=3 with phosphoric acid; the detection wavelength is 282nm; the flow rate is 1.0mL/min; the peak time was 8min.
FIG. 8 shows the electrocatalytic hydrodechlorination effect of Pd/NiCo-MOF/foam-Ni electrodes on diclofenac sodium, triclosan, and 2, 4-dichlorophenoxyacetic acid. The removal degree of the Pd/NiCo-MOF/foam-Ni electrode on diclofenac sodium, triclosan and 2, 4-dichlorophenoxyacetic acid respectively reaches 99.81%, 94.15% and 96.94% after 120min, and further proves that the Pd/NiCo-MOF/foam-Ni electrode has good electrocatalytic performance.
Example 6: stability test of Pd/NiCo-MOF/foam-Ni electrode
Using Pd/NiCo-MOF/foam-Ni electrode as working electrode, in the same manner as in example 5, 15 times of electrocatalytic hydrodechlorination experiments were continuously conducted on chloramphenicol and diclofenac sodium.
FIG. 9 shows a scanning electron microscope image after 5 consecutive uses of Pd/NiCo-MOF/foam-Ni electrodes. The NiCo-MOF nano-sheets are still compact and uniform on the exposed foam nickel, the three-dimensional porous space network structure is not destroyed, and the Pd nano-particles are still firmly attached on the NiCo-MOF layer.
FIG. 10 shows a graph of the stability effect of Pd/NiCo-MOF/foam-Ni electrodes. As shown in FIG. (a), the removal efficiency of the Pd/NiCo-MOF/foam-Ni electrode for chloramphenicol after 4 cycles was still 100%, and after 15 cycles, it was still 95% or more (120 min per cycle). Furthermore, we also used the Pd/NiCo-MOF/foam-Ni electrode versus sodium diclofenac cycling experiments (FIG. (b)). After 10 cycles, the removal rate reaches more than 90 percent. After 15 cycles, the removal rate still reaches more than 80 percent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing an electrode with a bimetallic organic framework as an intermediate layer and supported with metal palladium particles, the method comprising the following steps:
(1) Adding foam nickel into a precursor solution containing nickel ions, cobalt ions and organic components for reaction to obtain a NiCo-MOF/foam-Ni electrode, wherein the reaction temperature of the reaction is 140-160 ℃ and the reaction time is 9-15 h;
(2) The Pd/NiCo-MOF/foam-Ni electrode is prepared by electro-deposition by taking the NiCo-MOF/foam-Ni electrode as a cathode and taking a solution containing palladium ions as a deposition solution;
the method further comprises the step of pre-treating the foam nickel to remove impurities contained in the foam nickel before the step (1), wherein the pre-treatment is carried out by the following steps: cutting the foam nickel sheet to a target size, and then putting the foam nickel sheet into an acetone solution for ultrasonic cleaning for 10 to 20 minutes; then, ultrasonically cleaning the foam nickel in water for 15 to 20 minutes; then, the foam nickel is put into the concentration of 0.4 to 0.6mol.L -1 Ultrasonic cleaning in dilute sulfuric acid for 2 to 3 minutes; finally, ultrasonically cleaning the foam nickel in water for 2 to 4 times for 20 to 30 minutes each time, thereby obtaining pretreated foam nickel;
the organic component is a combination of terephthalic acid and N, N-dimethylformamide;
the precursor solution comprises, in a volume of 20 mL: 0.45 to 0.55 mmol terephthalic acid, 0.15 to 0.25mmol Co (NO) 3 ) 2 •6H 2 O, 0.25 to 0.35 mmol Ni (NO) 3 ) 2 •6H 2 O and 16 to 20mL of n, n-dimethylformamide, 0.8 to 1.2mL ethanol and 0.8 to 1.2mL of water;
the deposition solution contains 0.20 to 0.30 mmol.L -1 PdCl 2 And 0.70 to 0.80 mmol.L -1 NaCl。
2. The method of manufacturing according to claim 1, characterized in that:
in step (1), the target size of the nickel foam is (1-3) cm× (1-3) cm.
3. The method of manufacturing according to claim 1, characterized in that:
the precursor solution is prepared by the following steps: terephthalic acid, co (NO) 3 ) 2 •6H 2 O、Ni(NO 3 ) 2 •6H 2 And mixing O and N, N-dimethylformamide uniformly, then adding a mixed solution of ethanol and water, and further stirring uniformly to obtain the precursor solution.
4. A method of preparation according to claim 3, characterized in that:
the mixed solution of ethanol and water is an equal volume mixed solution of ethanol and water.
5. The production method according to any one of claims 1 to 4, characterized in that:
in the step (1), after the reaction is finished, the method further comprises the steps of ultrasonic cleaning and drying of the NiCo-MOF/foam-Ni electrode obtained by the reaction.
6. The production method according to any one of claims 1 to 4, characterized in that:
the electrodeposition uses a platinum electrode as an anode.
7. The method of manufacturing according to claim 6, wherein:
the electrodeposition was performed in a constant current of 6 to 8 mA and a constant temperature water bath of 35 to 45 ℃ for 1.5 to 2.5 h.
8. The Pd/NiCo-MOF/foam-Ni electrode prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the Pd/NiCo-MOF/foam-Ni electrode according to claim 8 in the electro-catalytic hydrodechlorination of chlorinated PPCP organics.
10. The use according to claim 9, characterized in that:
the chlorinated PPCP organic matter is at least one selected from the group consisting of chloramphenicol, diclofenac sodium and triclosan.
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| CN109052586A (en) * | 2018-09-10 | 2018-12-21 | 南昌航空大学 | A kind of preparation method and applications of the ultra-fine Pd nano particle electrode of three-dimensional self-supporting porous foam nickel load |
| CN110794016A (en) * | 2019-10-29 | 2020-02-14 | 济南大学 | Preparation method and application of immunosensor based on nickel-cobalt MOFs loaded molybdenum disulfide doped palladium nanoparticles |
| CN110911174A (en) * | 2019-12-23 | 2020-03-24 | 中国矿业大学 | Preparation method and application of NiCo-LDH nano material |
| CN111250106A (en) * | 2020-01-20 | 2020-06-09 | 浙江工业大学 | Preparation method of flower-like nano palladium/foamed nickel catalytic material and application of flower-like nano palladium/foamed nickel catalytic material in electro-catalytic reduction dechlorination reaction |
| CN111285446A (en) * | 2020-02-24 | 2020-06-16 | 浙江工业大学 | Pd/NiCo2O4/Ni foam composite electrode and preparation method and application thereof |
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| CN109052586A (en) * | 2018-09-10 | 2018-12-21 | 南昌航空大学 | A kind of preparation method and applications of the ultra-fine Pd nano particle electrode of three-dimensional self-supporting porous foam nickel load |
| CN110794016A (en) * | 2019-10-29 | 2020-02-14 | 济南大学 | Preparation method and application of immunosensor based on nickel-cobalt MOFs loaded molybdenum disulfide doped palladium nanoparticles |
| CN110911174A (en) * | 2019-12-23 | 2020-03-24 | 中国矿业大学 | Preparation method and application of NiCo-LDH nano material |
| CN111250106A (en) * | 2020-01-20 | 2020-06-09 | 浙江工业大学 | Preparation method of flower-like nano palladium/foamed nickel catalytic material and application of flower-like nano palladium/foamed nickel catalytic material in electro-catalytic reduction dechlorination reaction |
| CN111285446A (en) * | 2020-02-24 | 2020-06-16 | 浙江工业大学 | Pd/NiCo2O4/Ni foam composite electrode and preparation method and application thereof |
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