CN116282393A - Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof - Google Patents

Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof Download PDF

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CN116282393A
CN116282393A CN202310218075.6A CN202310218075A CN116282393A CN 116282393 A CN116282393 A CN 116282393A CN 202310218075 A CN202310218075 A CN 202310218075A CN 116282393 A CN116282393 A CN 116282393A
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electrode
nickel
palladium
composite electrode
foam
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王鑫宏
王明钰
于洪斌
苏婷
秦伟超
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Jilin Agricultural University
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2201/46—Apparatus for electrochemical processes
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/08—Nanoparticles or nanotubes

Abstract

The invention discloses a palladium-nickel phosphide copper-foam nickel composite electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, preprocessing an NF substrate; preparing an intermediate layer by a constant current deposition method to obtain Ni-Cu-P/NF; step three, preparing a catalytic layer by a pulse electrodeposition method to obtain Pd/Ni-Cu-P/NF; the Pd/Ni-Cu-P/NF electrode designed by the invention improves the deposition environment of the Pd catalytic layer from three-dimensional scale through the Ni-Cu-P interlayer, and improves the dispersion of Pd nano particlesThe activity is increased, the Pd consumption is reduced; in addition, under the action of Ni-Cu-P, the generation of active hydrogen can be accelerated, and Pd in the Pd catalytic layer is increased 2+ The content of C-Cl bond is promoted, so that the dechlorination efficiency is further improved, and the problems of poor dispersity, low activity, large consumption and high electrode preparation cost of the conventional dechlorination electrode Pd can be solved.

Description

Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a palladium-nickel phosphide copper-foam nickel composite electrode and a preparation method and application thereof.
Background
Chlorophenols are widely used as intermediates for synthesis of industrial products such as dyes and pesticides, and frequently occur in water environments along with discharge of chemical wastewater and use of chlorinated products. Chlorophenol is a typical global chlorinated organic pollutant, has extremely strong biotoxicity, cannot be completely degraded in natural environment, and the characteristic of durability and easy bioaccumulation increases the environmental risk after exposure of the chlorophenol, and causes serious threat to human health and ecological environment, so that the chlorophenol pollution is concerned in the global scope. Therefore, the research on the efficient and green degradation technology of chlorophenols has important significance for guaranteeing human health and water environment safety. At present, the main treatment methods of chlorophenols in water bodies include biological methods, physical methods, chemical oxidation reduction methods and the like. The biological method has low cost and large operation scale, but the method has strict requirements on water quality and environmental conditions, can only treat low-concentration chlorophenol wastewater, has long period and slow degradation rate, and has larger practical application limit. The physical method is mainly to carry out phase transfer on chlorophenols in water bodies, and the purpose of removal is generally difficult to achieve, and the physical method is often used as a pretreatment method of other methods. In the chemical oxidation-reduction method, substances with strong oxidability or reducibility are added to realize chlorophenol degradation in the treatment process, so that the treatment cost is increased, the cost is high, and the general reaction conditions are relatively harsh.
Compared with the method, the Electrocatalytic Hydrodechlorination (EHDC) technology is more and more considered as a more promising chloridizing treatment method for chlorinated organic matters due to the advantages of high efficiency, mild reaction conditions, simple and convenient operation, no secondary pollution and the like. Among them, the development of high dechlorination performance electrodes is the research focus in this field. Among common electrode materials, foam Nickel (NF) is widely used as an electrode base material because of its advantages of large specific surface area, porous structure, good conductivity, and the like. Noble metal palladium (Pd) shows better EHDC activity due to its good catalytic generation and storage capacity of active hydrogen, and is the most frequently used catalytic layer material for dechlorination electrodes. However, in the prior art, pd is directly supported on a substrate, such as a Pd/NF electrode, and the Pd particles have large size and less exposure of active sites, so that the EHDC activity of the electrode is limited, the dechlorination efficiency is low, and the Pd particles are easy to aggregate, so that the Pd consumption is large, and the electrode preparation cost is increased. Studies show that the Pd catalytic layer is deposited on the intermediate layer and then supported on the substrate, so that the electrode catalytic activity, such as Pd/polypyrrole/NF, pd/graphene-polypyrrole/NF and the like, can be improved, but the Pd particles still have aggregation phenomenon, and the dechlorination performance is also required to be improved.
Disclosure of Invention
The invention aims to provide a palladium-nickel phosphide-nickel foam composite electrode and a preparation method and application thereof, so as to solve the problems of poor Pd dispersibility, low activity, large consumption and high electrode preparation cost of the conventional dechlorination electrode in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the palladium-nickel phosphide-nickel foam composite electrode comprises an NF substrate, a Ni-Cu-P intermediate layer and a Pd catalytic layer, wherein the Ni-Cu-P intermediate layer is arranged on the outer wall of the NF substrate, and the Pd catalytic layer is arranged on the outer wall of the Ni-Cu-P intermediate layer.
The preparation method of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, preprocessing an NF substrate; preparing an intermediate layer by a constant current deposition method to obtain Ni-Cu-P/NF; step three, preparing a catalytic layer by a pulse electrodeposition method to obtain Pd/Ni-Cu-P/NF;
in the first step, the foam nickel is placed in a 3M hydrochloric acid solution for ultrasonic cleaning for 10-20 minutes, a surface oxide layer is removed, then deionized water is used for cleaning, ultrasonic cleaning is performed in an absolute ethyl alcohol solution for 5-10 minutes, deionized water is used for cleaning, and then high-purity nitrogen is used for drying for standby, so that an NF substrate is obtained;
in the second step, the NF substrate obtained in the first step is used as a cathode, a platinum sheet is used as an anode, and a constant current deposition method is adopted to prepare a Ni-Cu-P interlayer, so as to obtain Ni-Cu-P/NF;
in the third step, the Ni-Cu-P/NF obtained in the second step is used as a working electrode, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a Pd catalytic layer is loaded on the Ni-Cu-P/NF by adopting a pulse electrodeposition method to obtain the Pd/Ni-Cu-P/NF composite electrode.
Preferably, in the first step, the size of the nickel foam is 25mm×25mm×0.5mm.
Preferably, in the second step, the conditions for preparing the Ni-Cu-P interlayer by adopting the constant current deposition method are as follows: the current density is 8-12mA/cm 2 The electrowinning time is 10-20 minutes, the electrolyte is 40mL, and the composition comprises NH 4 Cl(0.2-0.3M)、CuCl 2 ·2H 2 O(0.01-0.04M)、NiCl 2 ·6H 2 O(0.15-0.25M)、NaH 2 PO 2 ·H 2 O (0.15-0.25M), hold NiCl 2 ·6H 2 O and NaH 2 PO 2 ·H 2 The O molar ratio was 1:1.
Preferably, in the third step, the conditions for preparing the Pd catalyst layer by using the pulse electrodeposition method are as follows: double potential step 7500 times (high potential 0Vvs. SCE, pulse width 0.2s; low potential-1.4-1.6 Vvs. SCE, pulse width 0.2 s), electrolyte 100mL, composition including 0.2-1.0mM PdCl 2 12-60mM NaCl, hold PdCl 2 Molar ratio to NaCl is 1:60.
The application of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, constructing an electrode system; step two, electrolytic dechlorination; detecting dechlorination effect;
in the first step, an anode chamber and a cathode chamber of an H-type electrolytic cell are separated by a Nafion-117 proton exchange membrane, and a Pd/Ni-Cu-P/NF electrode is used as a working electrode and is arranged in the cathode chamber; platinum sheets are used as counter electrodes and are arranged in an anode chamber; injecting cathode liquid into the cathode chamber, and injecting anode liquid into the anode chamber; completing construction of an electrode system;
in the second step, high-purity nitrogen is introduced into the cathode and anode chambers for 10 minutes, then constant current electrolysis dechlorination is carried out, and during the period, the cathode chambers are kept magnetically stirred to eliminate concentration polarization effects;
in the third step, 0.8mL of the cathode solution is sampled at a set time, and the dechlorination performance of the Pd/Ni-Cu-P/NF electrode is detected by detecting the changes of the concentrations of 2, 4-dichlorophenol, 2-chlorophenol, 4-chlorophenol and phenol with time by utilizing high performance liquid chromatography.
Preferably, in the first step, the platinum sheet has a specification of 25mm×25mm.
Preferably, in the first step, the volume of the catholyte is 80mL, the concentration of 2, 4-dichlorophenol is 25-150mg/L, na 2 SO 4 The concentration is 0.01-0.1M, and the pH value is 1.5-6.2; volume of anolyte 80mL, na 2 SO 4 The concentration was 0.05M.
Preferably, in the second step, the current density is 0.24-0.64mA/cm 2 。
Compared with the prior art, the invention has the beneficial effects that: the Pd/Ni-Cu-P/NF electrode designed by the invention improves the deposition environment of the Pd catalytic layer from a three-dimensional scale through the Ni-Cu-P interlayer, improves the dispersity of Pd nano particles, increases active sites and reduces the Pd consumption; in addition, under the action of Ni-Cu-P, the generation of active hydrogen can be accelerated, and Pd in the Pd catalytic layer is increased 2+ The content of C-Cl bond is promoted, so that the dechlorination efficiency is further improved, and the problems of poor dispersity, low activity, large consumption and high electrode preparation cost of the conventional dechlorination electrode Pd can be solved.
Drawings
FIG. 1 is a front cut-away view of a composite electrode of the present invention;
FIG. 2 is a flow chart of a preparation method of the invention;
FIG. 3 is a flow chart of an application of the present invention;
FIG. 4 is a diagram of a Ni-Cu-P/NF scanning electron microscope;
FIG. 5 is a Pd/Ni-Cu-P/NF scanning electron microscope image;
FIG. 6 is Pd/NF, pd 4.0 Graph of EHDC performance contrast for/NF, pd/Ni-Cu-P/NF electrode versus 2, 4-dichlorophenol;
FIG. 7 is a graph of product selectivity and material balance during 2, 4-dichlorophenol EHDC;
FIG. 8 is a graph of the effect of Pd/Ni-Cu-P/NF electrode on 2, 4-dichlorophenol five consecutive times EHDC;
in the figure: 1. an NF substrate; 2. a Ni-Cu-P interlayer; 3. pd catalytic layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, an embodiment of the present invention is provided: the palladium-nickel phosphide-nickel foam composite electrode comprises an NF substrate 1, a Ni-Cu-P intermediate layer 2 and a Pd catalytic layer 3, wherein the Ni-Cu-P intermediate layer 2 is arranged on the outer wall of the NF substrate 1, and the Pd catalytic layer 3 is arranged on the outer wall of the Ni-Cu-P intermediate layer 2.
Referring to fig. 2,4 and 5, an embodiment of the present invention is provided: the preparation method of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, preprocessing an NF substrate; preparing an intermediate layer by a constant current deposition method to obtain Ni-Cu-P/NF; step three, preparing a catalytic layer by a pulse electrodeposition method to obtain Pd/Ni-Cu-P/NF;
in the first step, foam nickel with the size of 25mm multiplied by 0.5mm is placed in a 3M hydrochloric acid solution for ultrasonic cleaning for 15 minutes, a surface oxide layer is removed, then deionized water is used for cleaning, ultrasonic cleaning is performed in an absolute ethyl alcohol solution for 5 minutes, deionized water is used for cleaning, and then high-purity nitrogen is used for drying for standby, so that an NF substrate 1 is obtained;
in the second step, the NF substrate 1 obtained in the first step is used as a cathode, a platinum sheet is used as an anode, and a constant current deposition method is adopted to prepare a Ni-Cu-P interlayer 2, so as to obtain Ni-Cu-P/NF; the conditions are as follows: the current density was 10mA/cm 2 The electrowinning time was 10 minutes, the electrolyte 40mL, the composition included NiCl 2 ·6H 2 O(0.2M)、CuCl 2 ·2H 2 O(0.03M)、NaH 2 PO 2 ·H 2 O(0.2M)、NH 4 Cl(0.25M)；
In the third step, the Ni-Cu-P/NF obtained in the second step is used as a working electrode, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a Pd catalytic layer 3 is loaded on the Ni-Cu-P/NF by adopting a pulse electrodeposition method to obtain a Pd/Ni-Cu-P/NF composite electrode; the conditions are as follows: double potential step 7500 times (high potential 0Vvs. SCE, pulse width 0.2s; low potential-1.5 Vvs. SCE, pulse width 0.2 s), electrolyte 100mL, composition including 0.5mM PdCl 2 、30mMNaCl。
Referring to fig. 3, an embodiment of the present invention is provided: the application of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, constructing an electrode system; step two, electrolytic dechlorination; detecting dechlorination effect;
in the first step, an anode chamber and a cathode chamber of an H-type electrolytic cell are separated by a Nafion-117 proton exchange membrane, and a Pd/Ni-Cu-P/NF electrode is used as a working electrode and is arranged in the cathode chamber; a platinum sheet with the specification of 25mm multiplied by 25mm is taken as a counter electrode and is arranged in an anode chamber; injecting cathode liquid into the cathode chamber, and injecting anode liquid into the anode chamber; completing construction of an electrode system; wherein, the volume of the catholyte is 80mL, the concentration of 2, 4-dichlorophenol is 50mg/L, na 2 SO 4 Concentration 0.05M, pH 2.3; volume of anolyte 80mL, na 2 SO 4 Concentration 0.05M;
in the second step, high-purity nitrogen is introduced into the cathode and anode chambers for 10 minutes, and then constant current electrolysis dechlorination is carried out, wherein the current density is 0.40mA/cm 2 During this period, the cathode chamber remains magnetically agitated to eliminate concentration polarization effects;
in the third step, 0.8mL of the cathode solution is sampled at a set time, and the dechlorination performance of the Pd/Ni-Cu-P/NF electrode is detected by detecting the changes of the concentrations of 2, 4-dichlorophenol, 2-chlorophenol, 4-chlorophenol and phenol with time by utilizing high performance liquid chromatography.
Comparative example 1:
the preparation method of the palladium-nickel phosphide-nickel foam composite electrode is the same as the embodiment, and the preparation method of the palladium-nickel phosphide-nickel foam composite electrode is characterized in that the Ni-Cu-P/NF serving as a working electrode in the third step is changed into the NF serving as a working electrode, and other preparation conditions are unchanged, so that the Pd/NF electrode with the same Pd loading capacity can be prepared.
Comparative example 2:
the preparation method of the palladium-nickel phosphide-nickel foam composite electrode comprises the steps of first and second, wherein the same as the embodiment, only the Ni-Cu-P/NF serving as a working electrode in the third step is changed into the NF serving as the working electrode, and the electrolyte composition is changed into 2.0mM PdCl 2 120mM NaCl, other preparation conditions are unchanged, and Pd with 4 times Pd loading capacity can be prepared 4.0 A NF electrode.
Based on the above, as shown in fig. 4, the Ni-Cu-P micro-morphology presents micro-nano dendrite structure, which can provide abundant pores and huge specific surface area for depositing Pd catalytic layer; as shown in fig. 5, on the Pd/Ni-Cu-P/NF electrode, pd nanoparticles are uniformly supported on the Ni-Cu-P interlayer, and from the appearance, the micro-nano dendrite structure is still maintained, so that more reactive sites can be provided; as shown in FIG. 6, the dechlorination efficiency of the Pd/NF electrode is only 52.7% in 150 minutes, and the dechlorination performance of the Pd/Ni-Cu-P/NF electrode is greatly enhanced, the reaction is carried out for 150 minutes, and the dechlorination efficiency reaches 100%; the introduction of the Ni-Cu-P interlayer is shown to significantly improve the EHDC activity of the composite electrode; when Pd load is increased to 4 times, dechlorination performance is also obviously improved, and dechlorination efficiency after 150 minutes reaches 90 percent and is close to that of Pd/Ni-Cu-P/NF electrodes; but with Pd 4.0 Compared with the NF electrode, the Pd consumption of the Pd/Ni-Cu-P/NF electrode is reduced by 75 percent, and the higher EHDC performance is shown; FIG. 7 shows the trend of 2, 4-dichlorophenol, 2-chlorophenol, 4-chlorophenol and phenol over the course of the reaction and the sum of all products, showing that as the concentration of 2, 4-dichlorophenol decreases, the concentration of phenol increases rapidly, only trace amounts of 2-chlorophenol being detected within 80 minutes prior to the course of the reaction, while 4-chlorophenol is not detected during the course of the reaction; after 150 minutes of reaction, the dechlorination efficiency of the 2, 4-dichlorophenol is 100%, no 2-chlorophenol and 4-chlorophenol are detected, and the conversion rate of the phenol reaches 96.5%, which indicates that the Pd/Ni-Cu-P/NF electrode prepared by the method has better dechlorination performance and higher selectivity; as shown in FIG. 8, after five times of recycling, the dechlorination efficiency of the Pd/Ni-Cu-P/NF electrode still reaches 95.1%, which shows that the electrode has good stability; the high stability can be attributed to the conductive properties of the Pd and Ni-Cu-P catalytic layersThe in-situ growth on the substrate ensures that the surface layer and the middle layer have good contact and higher mechanical strength; the composite electrode designed by the invention takes NF as a substrate, dendrite-shaped Ni-Cu-P as an intermediate layer and Pd nano-particles as a catalytic layer, and the Ni-Cu-P can crack H-OH bonds, provide rich hydrogen sources for Pd catalysts, accelerate the generation of active hydrogen and increase Pd in the Pd catalytic layer 2+ The activation of C-Cl bond is promoted, so that the dechlorination performance of the composite electrode is improved; in addition, the dendritic micro-nano structure of Ni-Cu-P can provide huge specific surface area for palladium loading, and is beneficial to increasing the dispersibility and active sites of Pd particles, so that the Pd consumption is reduced; the preparation method of each step of the invention is an electrochemical method, and has simple process, mild synthesis condition and easy operation; the Pd/Ni-Cu-P/NF electrode has high dechlorination efficiency on chlorophenol compounds (specifically 2, 4-dichlorophenol), good selectivity and few byproducts, and is convenient for the subsequent treatment of chlorophenol wastewater; the Pd particles of the Pd/Ni-Cu-P/NF electrode catalytic layer have good dispersibility and low Pd consumption, and compared with the Pd/NF electrode without the Ni-Cu-P intermediate layer, the Pd consumption can be reduced by 75 percent on the premise of the same dechlorination efficiency, and the preparation cost of the electrode is greatly reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (9)

1. The palladium-nickel phosphide-foam nickel composite electrode comprises an NF substrate (1), a Ni-Cu-P intermediate layer (2) and a Pd catalytic layer (3), and is characterized in that: the NF substrate is characterized in that a Ni-Cu-P middle layer (2) is arranged on the outer wall of the NF substrate (1), and a Pd catalytic layer (3) is arranged on the outer wall of the Ni-Cu-P middle layer (2).
2. The preparation method of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, preprocessing an NF substrate; preparing an intermediate layer by a constant current deposition method to obtain Ni-Cu-P/NF; step three, preparing a catalytic layer by a pulse electrodeposition method to obtain Pd/Ni-Cu-P/NF; the method is characterized in that:
in the first step, foam nickel is placed in a 3M hydrochloric acid solution for ultrasonic cleaning for 10-20 minutes, a surface oxide layer is removed, then deionized water is used for cleaning, ultrasonic cleaning is performed in an absolute ethyl alcohol solution for 5-10 minutes, deionized water is used for cleaning, and then high-purity nitrogen is used for drying for standby, so that an NF substrate (1) is obtained;
in the second step, the NF substrate (1) obtained in the first step is used as a cathode, a platinum sheet is used as an anode, and a constant current deposition method is adopted to prepare a Ni-Cu-P interlayer (2) so as to obtain Ni-Cu-P/NF;
in the third step, the Ni-Cu-P/NF obtained in the second step is used as a working electrode, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a Pd catalytic layer (3) is loaded on the Ni-Cu-P/NF by adopting a pulse electrodeposition method to obtain the Pd/Ni-Cu-P/NF composite electrode.
3. The method for preparing the palladium-nickel phosphide-foam nickel composite electrode according to claim 2, wherein the method comprises the following steps: in the first step, the size of the foam nickel is 25mm multiplied by 0.5mm.
4. The method for preparing the palladium-nickel phosphide-foam nickel composite electrode according to claim 2, wherein the method comprises the following steps: in the second step, the conditions for preparing the Ni-Cu-P interlayer (2) by adopting a constant current deposition method are as follows: the current density is 8-12mA/cm 2 The electrowinning time is 10-20 minutes, the electrolyte is 40mL, and the composition comprises NH 4 Cl(0.2-0.3M)、CuCl 2 ·2H 2 O(0.01-0.04M)、NiCl 2 ·6H 2 O(0.15-0.25M)、NaH 2 PO 2 ·H 2 O (0.15-0.25M), hold NiCl 2 ·6H 2 O and NaH 2 PO 2 ·H 2 The O molar ratio was 1:1.
5. The method for preparing the palladium-nickel phosphide-foam nickel composite electrode according to claim 2, wherein the method comprises the following steps: in the third step, the conditions for preparing the Pd catalytic layer (3) by adopting a pulse electrodeposition method are as follows: double potential step 7500 times (high potential 0Vvs. SCE, pulse width 0.2s; low potential-1.4-1.6 Vvs. SCE, pulse width 0.2 s), electrolyte 100mL, composition including 0.2-1.0mM PdCl 2 12-60mM NaCl, holding PdCl 2 Molar ratio to NaCl is 1:60.
6. The application of the palladium-nickel phosphide-foam nickel composite electrode comprises the steps of firstly, constructing an electrode system; step two, electrolytic dechlorination; detecting dechlorination effect; the method is characterized in that:
in the first step, an anode chamber and a cathode chamber of an H-type electrolytic cell are separated by a Nafion-117 proton exchange membrane, and a Pd/Ni-Cu-P/NF electrode is used as a working electrode and is arranged in the cathode chamber; platinum sheets are used as counter electrodes and are arranged in an anode chamber; injecting cathode liquid into the cathode chamber, and injecting anode liquid into the anode chamber; completing construction of an electrode system;
in the second step, high-purity nitrogen is introduced into the cathode and anode chambers for 10 minutes, then constant current electrolysis dechlorination is carried out, and during the period, the cathode chambers are kept magnetically stirred to eliminate concentration polarization effects;
in the third step, 0.8mL of the cathode solution is sampled at a set time, and the dechlorination performance of the Pd/Ni-Cu-P/NF electrode is detected by detecting the changes of the concentrations of 2, 4-dichlorophenol, 2-chlorophenol, 4-chlorophenol and phenol with time by utilizing high performance liquid chromatography.
7. The use of a palladium-nickel phosphide-nickel foam composite electrode according to claim 6, characterized in that: in the first step, the specification of the platinum sheet is 25mm multiplied by 25mm.
8. The use of a palladium-nickel phosphide-nickel foam composite electrode according to claim 6, characterized in that: in the first step, the volume of the catholyte is 80mL, the concentration of 2, 4-dichlorophenol is 25-150mg/L, and Na is 2 SO 4 The concentration is 0.01-0.1M, and the pH value is 1.5-6.2;volume of anolyte 80mL, na 2 SO 4 The concentration was 0.05M.
9. The use of a palladium-nickel phosphide-nickel foam composite electrode according to claim 6, characterized in that: in the second step, the current density is 0.24-0.64mA/cm 2 。
CN202310218075.6A 2023-03-08 2023-03-08 Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof Pending CN116282393A (en)

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CN117265529A (en) * 2023-11-23 2023-12-22 天津工业大学 Pd/NiFeP-MXene/NF electrode and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117265529A (en) * 2023-11-23 2023-12-22 天津工业大学 Pd/NiFeP-MXene/NF electrode and preparation method and application thereof
CN117265529B (en) * 2023-11-23 2024-01-30 天津工业大学 Pd/NiFeP-MXene/NF electrode and preparation method and application thereof

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