CN115646503A - Foamed nickel loaded Ni-WC composite material and preparation method and application thereof - Google Patents

Foamed nickel loaded Ni-WC composite material and preparation method and application thereof Download PDF

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CN115646503A
CN115646503A CN202211229693.2A CN202211229693A CN115646503A CN 115646503 A CN115646503 A CN 115646503A CN 202211229693 A CN202211229693 A CN 202211229693A CN 115646503 A CN115646503 A CN 115646503A
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composite material
nickel
loaded
catalyst
heteropolyphosphotungstate
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韩占刚
马媛媛
王琪
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Hebei Normal University
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Abstract

The invention relates to the technical field of electrocatalysis, and particularly discloses a foamed nickel loaded Ni-WC composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: adding Keggin type triple-vacancy heteropolyphosphotungstate and tris (hydroxymethyl) aminomethane into an acetic acid buffer solution, mixing, adding soluble nickel salt, ethylenediamine and trimesic acid, reacting at 150-180 ℃ for 20-26 h, and carbonizing at 690-710 ℃ in a nitrogen atmosphere to obtain the foamed nickel loaded Ni-WC composite material. The foam nickel loaded Ni-WC composite material provided by the invention has a three-dimensional nano structure and rich heterogeneous interfaces, enhances the catalytic activity of the composite material on chlorine-containing organic matters, enables a non-noble metal catalyst Ni-WC/NF to show the catalytic activity of a noble metal-like Pd catalyst, provides a novel and simple way for research and exploration of the non-noble metal catalyst for treating waste water containing chlorine-containing organic matters, and has high potential application value.

Description

Foamed nickel loaded Ni-WC composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a foamed nickel loaded Ni-WC composite material and a preparation method and application thereof.
Background
chlorine-Containing Organic Compounds (COC) are widely applied to chemical production, pesticide production and papermaking industry as important chemical raw materials. Chlorine-containing organic matters enter the environment through approaches such as wastewater discharge, pesticide use, burning of chlorine-containing organic matter products and the like, and soil, underground water, surface water and atmosphere are seriously polluted. The organic matters contained in the industrial wastewater have high teratogenicity and high carcinogenicity, and the enrichment of the residual chlorine-containing organic matters in the industrial wastewater through a food chain poses serious threats to plant and human health. Therefore, the development of a practical and effective treatment technique for chlorinated organics has become a focus of attention for many researchers.
At present, the method for treating chlorine-containing organic matters mainly comprises a physical method, a chemical method and a biological method, and the methods have the defects of high treatment cost, long period, possibility of causing secondary pollution and the like. The electro-catalytic dechlorination technology is to provide electrons through an external power supply and electrolyze water in situ to generate H * ，H * And the chlorine is removed by replacing Cl with a reducing agent. Compared with other technologies, the electrocatalytic dechlorination technology has the following advantages: (1) Continuously providing electrons through an external power supply to ensure that the reaction is continuously carried out; (2) Reaction kinetics and paths are adjusted through voltage, so that the applicability is wider; (3) No additional chemical substance is needed, the device is simple, and the mobile wastewater treatment can be realized; and (4) no secondary pollution and mild reaction conditions. The above advantages make electrocatalytic dechlorination considered as the most promising dechlorination technology. Most of the electrocatalytic dechlorination catalysts reported at present are Pd-based noble metals, but the application of the electrocatalytic dechlorination catalyst in the field of electrocatalytic dechlorination is greatly limited by expensive preparation cost and scarce Pd reserves. Therefore, the design of a cheap and efficient non-noble metal catalyst is of great significance for promoting the development of the electrocatalytic dechlorination technology.
Disclosure of Invention
Aiming at the problems of high preparation cost and low electrocatalytic performance of the conventional electrocatalytic dechlorination catalyst, the invention provides a foamed nickel loaded Ni-WC composite material and a preparation method and application thereof.
In order to solve the technical problem, the embodiment of the invention provides the following technical scheme:
a preparation method of a foam nickel loaded Ni-WC composite material comprises the following steps:
step a, adding Keggin type triple-vacancy heteropolyphosphotungstate and tris (hydroxymethyl) aminomethane into an acetic acid buffer solution, uniformly mixing, adding soluble nickel salt, ethylenediamine and trimesic acid, and uniformly mixing to obtain a precursor solution;
and b, adding the precursor solution and the foamed nickel into a hydrothermal kettle, reacting for 20-26 h at 150-180 ℃, then placing the foamed nickel after reaction in a protective atmosphere, and carbonizing at 690-710 ℃ to obtain the foamed nickel loaded Ni-WC composite material.
Compared with the prior art, the preparation method of the foamed nickel loaded Ni-WC composite material provided by the invention has the advantages that Keggin type triple-vacancy heteropolyphosphotungstate is used as a precursor for preparing Ni-WC, on one hand, the Ni/W interface can be regulated and controlled at the molecular level, and the uniform mixing of Ni atoms and W atoms on the molecular scale is realized, so that the problem of easy phase separation of a bimetallic catalyst is effectively avoided, and the interaction of the Ni/W interface is improved; on the other hand, keggin type three-vacancy heteropolyphosphotungstate is used as a precursor, in-situ complexation is formed between the Keggin type three-vacancy heteropolyphosphotungstate and a trihydroxymethyl aminomethane ligand, and in-situ ligand decomposition is carried out in a carbonization process, so that the prepared Ni-WC composite material has a three-dimensional nano structure and is more beneficial to exposure of active sites, and the Ni-WC composite material with a three-dimensional hierarchical structure has rich heterogeneous interfaces, which are beneficial to modification of an electronic structure of Ni, enhancement of adsorption of the Ni-WC composite material on a substrate, and reduction of desorption energy of a product on the surface of the composite material, so that the active sites can be exposed in time after reaction is finished, and the catalytic activity of the Ni-WC composite material is remarkably improved, so that the Ni-WC composite material shows the catalytic activity of noble metal like Pd.
In step b of the invention, the chemical formula of the green crystal loaded on the surface of the foamed nickel after the hydrothermal reaction is finished is [ Ni (en) 2 (H 2 O) 2 ] 6 {Ni 6 (Tris)(en) 3 (BTC) 1.5 (B-α-PW 9 O 34 )} 8 ·12en·54H 2 O (hereinafter abbreviated as { Ni) 54 W 72 }) wherein en represents ethylenediamine, BTC represents trimesic acid, tris represents Tris (hydroxymethyl) aminomethane, and the hydrothermal reaction product is hereinafter abbreviated as { Ni } 54 W 72 }/NF。
The foamed nickel-loaded Ni-WC composite material prepared by the invention is abbreviated as Ni-WC/NF below.
Preferably, the Keggin type three-vacancy heteropolyphosphotungstate is Na 9 [A-α-PW 9 O 34 ]。
Illustratively, the soluble nickel salt is nickel chloride, nickel nitrate, or nickel sulfate.
Preferably, the mass ratio of the Keggin type three-vacancy heteropolyphosphotungstate to the tris-hydroxymethyl aminomethane is 0.6-0.8.
Preferably, the pH of the acetic acid buffer solution is 4.5-5.0, and the volume-to-mass ratio of the acetic acid buffer solution to the Keggin type triple-vacancy heteropolyphosphotungstate is 1000-23, wherein the volume unit is milliliter, and the mass unit is gram.
Preferably, the mass ratio of the soluble nickel salt to the Keggin type three-vacancy heteropolyphosphotungstate is 1.3-0.4.
Preferably, the volume-mass ratio of the ethylenediamine to the Keggin type three-vacancy heteropolyphosphotungstate is 1.9-1.1, wherein the volume unit is milliliter, and the mass unit is gram.
Preferably, the mass ratio of the trimesic acid to the Keggin type three-vacancy heteropolyphosphotungstate is 1-1.2.
Illustratively, the dimensions of the nickel foam are 2cm by 2.5cm.
Preferably, the carbonization time is 2h-4h.
The optimized reaction conditions are favorable for fully reacting the raw materials to prepare the uniform Ni-WC/NF composite material with the three-dimensional hierarchical structure, thereby being favorable for improving the catalytic activity and the stability of the Ni-WC/NF composite material.
The invention also provides a foamed nickel loaded Ni-WC composite material which is prepared by the preparation method of any one of the above foamed nickel loaded Ni-WC composite materials.
The Ni-WC/NF composite material prepared by the invention has the advantages of excellent electrocatalysis performance, high stability, simple preparation process, wide raw material source and low cost, can efficiently catalyze the decomposition of chlorine-containing organic matters, and has wide application prospect in the treatment of the chlorine-containing organic matters in wastewater.
The invention also provides application of the foamed nickel loaded Ni-WC composite material in electrocatalysis treatment of chlorine-containing organic matters in wastewater.
The invention also provides a method for removing chlorine-containing organic matters in wastewater through electrocatalysis, which comprises the following steps:
the foam nickel loaded Ni-WC composite material is used as a working electrode, a Pt net is used as a counter electrode, ag/AgCl is used as a reference electrode, chlorine-containing organic matter wastewater is introduced, and constant-current electro-catalysis dechlorination is carried out.
Preferably, the electrocatalysis adopts an H-type electrolytic cell, the current is controlled to be 10mA, and the electrolysis time is not less than 3H.
Illustratively, the anolyte is a 0.05M sodium sulfate solution and the catholyte is a 0.05M sodium sulfate solution.
When the wastewater containing chlorine organic matter is subjected to electrocatalysis treatment, the wastewater containing chlorine organic matter is introduced into the catholyte to be subjected to electrocatalysis dechlorination.
Illustratively, the electrode spacing of the working electrode and the counter electrode is 6cm.
The foam nickel loaded Ni-WC composite material provided by the invention has a three-dimensional nano structure, can realize uniform mixing of Ni and W atoms on a molecular scale, has rich heterogeneous interfaces, enhances the catalytic activity of the composite material on chlorine-containing organic matters, enables a non-noble metal catalyst Ni-WC/NF to show the catalytic activity of a noble metal-like Pd catalyst, has a simple preparation process and cheap and easily available raw materials, provides a novel and simple way for research and exploration of the non-noble metal catalyst for treating the chlorine-containing organic matter wastewater, and has a high potential application value.
Drawings
FIG. 1 is a schematic diagram of the process for preparing Ni-WC/NF catalyst of example 1;
FIG. 2 is a morphology characterization graph of Ni-WC/NF catalyst prepared in example 1, wherein FIGS. 2 a-2 c are SEM images at different magnifications, and the inset in FIG. 2c is a particle size distribution graph of the Ni-WC/NF catalyst; FIGS. 2 d-2 g are TEM images at different magnifications, and FIGS. 2 h-2 k are TEM elemental maps;
FIG. 3 is an XRD pattern of the Ni-WC/NF catalyst prepared in example 1;
FIG. 4 is a chart of EDX spectroscopy analysis of the Ni-WC/NF catalyst prepared in example 1;
FIG. 5 is a XPS analysis of Ni-WC/NF catalysts prepared in example 1, wherein FIG. 5a is a XPS survey, FIG. 5b is C1s, FIG. 5C is Ni-WC/NF prepared in example 1 and Ni 2p in Ni-C/NF prepared in comparative example 1, and FIG. 5d is Ni-WC/NF prepared in example 1 and W4 f in WC/NF prepared in comparative example 2;
FIG. 6 is a graph comparing the performance of the catalysts prepared in example 1 and comparative examples 1-4 for electrocatalysis of p-chlorophenol; FIG. 6a is a graph comparing the removal rate of electrocatalytic p-chlorophenol, wherein, a, comparative example 2WC/NF; b, comparative example 1Ni-C/NF; c, comparative example 4Ni + WC/NF; d, comparative example 3Pd/C/NF; e, example 1Ni-WC/NF; FIG. 6b is a pseudo first order kinetic fit of the electrocatalytic dechlorination reaction versus electrolysis time for example 1 and comparative examples 1, comparative examples 3-4; FIG. 6c is a graph comparing TOF values of example 1 and comparative examples 1 and 3-4; FIG. 6d is a graph comparing current efficiencies of example 1 and comparative example 3;
FIG. 7 is a scanning electron micrograph of a Ni-WC/C catalyst prepared in comparative example 5 and a graph of the properties of electrocatalytic p-chlorophenol, wherein FIGS. 7a to 7b are SEM images at different magnifications, and FIG. 7C is a graph of the properties of electrocatalytic p-chlorophenol;
FIG. 8 is a scanning electron micrograph of a different catalyst prepared according to comparative example 6; wherein, FIGS. 8a to 8e are electron microscope scanning images of Ni-WC/NF-500, ni-WC/NF-600, ni-WC/NF-650, ni-WC/NF-750 and Ni-WC/NF-800 in sequence;
FIG. 9 is a graph comparing the electrocatalytic performance of p-chlorophenol with different catalysts, 9a, ni-WC/NF-500 prepared in comparative example 6; 9b, ni-WC/NF-600;9c, ni-WC/NF-800;9d, ni-WC/NF-750;9e, ni-WC/NF-650;9f, ni-WC/NF prepared in example 1;
FIG. 10 is a graph of the performance of the Ni-WC/NF catalyst prepared in example 1 in an electrocatalytic 2-chlorophenol test; wherein, the inset in the upper right corner is a pseudo first order kinetic fitting curve of the electrocatalytic dechlorination reaction and the electrolysis time of the Ni-WC/NF catalyst prepared in example 1;
FIG. 11 is a graph comparing the effect of Ni-WC/NF catalyst prepared in example 1 on the removal rate of chlorophenol after 5 cycles;
FIG. 12 is a comparative XRD plot before and after 5 cycles of use of the Ni-WC/NF catalyst prepared in example 1;
FIG. 13 is an SEM image of the Ni-WC/NF catalyst prepared in example 1 after 5 cycles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment provides a preparation method of a Ni-WC/NF catalyst, which comprises the following steps:
step one, weighing 0.9g of Na 9 [A-α-PW 9 O 34 ]·nH 2 Dissolving O and 1.2g of Tris (hydroxymethyl) aminomethane (Tris) in 40mL of acetic acid-sodium acetate buffer solution (pH4.8), stirring until the solution is clear, adding 2.4g of nickel chloride, 0.75g of trimesic acid (BTC) and 0.9mL of ethylenediamine (en), and stirring for 30min to obtain a precursor solution;
step two, transferring the precursor solution and foamed nickel (2 cm multiplied by 2.5 cm) into a hydrothermal kettle, heating at the constant temperature of 160 ℃ for 25h, cooling to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and drying to obtain { Ni } 54 W 72 }/NF；
Step three, obtaining the { Ni 54 W 72 And (4) placing the Ni/NF in a tube furnace, and calcining for 3h at 700 ℃ in nitrogen atmosphere to obtain the Ni-WC/NF. The Ni-WC is on foamed nickelThe supported amount of (B) was 26 mg. Cm -2 。
This example shows a schematic of the process for preparing Ni-WC/NF catalyst as shown in FIG. 1.
SEM images of Ni-WC/NF catalysts prepared in this example are shown in FIGS. 2 (a) to 2 (c), and it can be seen that the catalysts are composed of particles having an average particle size of 74.3 nm. TEM images of Ni-WC/NF catalysts are shown in FIGS. 2 (d) -2 (g), in which the lattice spacing and the angles of the different crystal planes demonstrate that the elements constituting the nanoparticles are Ni and WC. The TEM element maps of the Ni-WC/NF catalyst are shown in FIGS. 2 (h) -2 (K), which prove that the Ni and W elements are uniformly distributed in the catalyst, and no phase separation phenomenon is generated.
The XRD characterization pattern of the Ni-WC/NF catalyst prepared in the example is shown in 3, and the composition of the catalyst is Ni and WC, and no other components are contained in the pattern.
The EDX spectrum of the Ni-WC/NF catalyst prepared in this example is shown in FIG. 4, from which it can be seen that the atomic ratio of Ni to W in the catalyst is 3.
The XPS analysis of Ni-WC/NF catalyst prepared in this example is shown in FIG. 5, and the XPS survey of FIG. 5 (a) further demonstrates the presence of C, O, ni and W in the catalyst. Fig. 5 (b) shows the presence of element C in the catalyst. In FIG. 5 (C), the binding energy of zero-valent Ni in Ni-WC/NF was shifted by 0.53eV toward the direction of low binding energy, as compared with Ni-C prepared in comparative example 1. In FIG. 5 (d), the binding energy of tetravalent tungsten in Ni-WC/NF was shifted by 0.69eV toward the direction of high binding energy, as compared with WC prepared in comparative example 2, and this result demonstrates that the phenomenon of transferring electrons to Ni by WC exists at the interface of Ni-WC heterojunction, which is important for the action of reactants, reaction intermediates and reaction products on the surface of catalyst during the electrocatalytic dechlorination process.
Example 2
The embodiment provides a preparation method of a Ni-WC/NF catalyst, which comprises the following steps:
step one, weighing 0.9g of Na 9 [A-α-PW 9 O 34 ]·nH 2 O and 1.5g Tris are dissolved in 45mL acetic acid-sodium acetate buffer (pH 4.5), stirred until the solution is clear, and added with chlorineNickel dissolving 3.0g, trimesic acid (BTC) 0.9g and ethylenediamine (en) 0.9mL, stirring for 30min to obtain precursor solution;
step two, transferring the precursor solution and foamed nickel (2 cm multiplied by 2.5 cm) into a hydrothermal kettle, heating at the constant temperature of 150 ℃ for 26h, cooling to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and drying to obtain { Ni } 54 W 72 }/NF；
Step three, obtaining the { Ni 54 W 72 The Ni-WC/NF is placed in a tubular furnace and calcined for 4 hours at 690 ℃ in nitrogen atmosphere to obtain Ni-WC/NF.
Example 3
The embodiment provides a preparation method of a Ni-WC/NF catalyst, which comprises the following steps:
step one, weighing 0.9g of Na 9 [A-α-PW 9 O 34 ]·nH 2 Dissolving O and 1.1g of Tris (hydroxymethyl) aminomethane (Tris) in 42mL of acetic acid-sodium acetate buffer solution (pH5.0), stirring until the solution is clear, adding 2.3g of nickel chloride, 0.8g of trimesic acid (BTC) and 1.0mL of ethylenediamine (en), and stirring for 30min to obtain a precursor solution;
step two, transferring the precursor solution and foamed nickel (2 cm multiplied by 2.5 cm) into a hydrothermal kettle, heating at the constant temperature of 180 ℃ for 20h, cooling to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and drying to obtain { Ni } 54 W 72 }/NF；
Step three, obtaining the { Ni } 54 W 72 The Ni-WC/NF is placed in a tube furnace and calcined for 2h at 710 ℃ in nitrogen atmosphere to obtain the Ni-WC/NF.
Application example 1
The application example provides a method for removing chlorine-containing organic matters in wastewater through electrocatalysis, which comprises the following steps:
an H-type electrolytic cell is adopted, the Ni-WC/NF catalyst prepared in example 1 is used as a working electrode, a Pt net is used as a counter electrode, ag/AgCl is used as a reference electrode, an anolyte is 40mL of 0.05M sodium sulfate solution, a catholyte is 40mL of 0.05M sodium sulfate solution containing 80mg/L of p-chlorophenol (4-CP), constant-current (10 mA) electrocatalytic dechlorination is carried out, 200 mu L of electrolyte is taken at intervals of 30min to dilute, and then the conversion rate of p-chlorophenol is tested.
Adopting high performance liquid chromatography, and analyzing the content of p-chlorophenol in the electrolyte by using a C18 reverse chromatographic column, wherein the mobile phase is methanol-water with a volume ratio of 60.
The calculation method of the TOF value comprises the following steps:
Figure BDA0003881066500000091
in the formula, n phenol Amount (mol) of substance which is 4-CP, n catalyst The amount of species (mol) which is the active species Ni, and t the reaction time (h).
The current efficiency CE% is calculated by the following method:
Figure BDA0003881066500000092
in the formula, n is the number of transferred electrons in the electrocatalytic dechlorination process (n = 2), C phenol The mass concentration (mg. L) of the phenol product is -1 ) F is the Faraday constant (96500℃ Mol) -1 ) V volume of electrolyte (L), Q is the total number of transferred electrons in the reaction process.
Comparative example 1
The comparative example provides a preparation method of a Ni-C/NF catalyst, which comprises the following steps:
weighing 0.24g of nickel chloride and 0.75g of urea, uniformly mixing, placing in a tubular furnace, and calcining for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain Ni-C;
step two, adding 130mg of the prepared Ni-C sample into 1mL of mixed solution of ethanol and naphthol with the volume ratio of 9.
Comparative example 2
The comparative example provides a preparation method of a WC/NF catalyst, which comprises the following steps:
step one, weighing 0.3g of sodium tungstate and 0.75g of urea, uniformly mixing, placing in a tubular furnace, and calcining for 3 hours at 700 ℃ in nitrogen atmosphere to obtain WC;
step two, adding 130mg of the prepared WC sample into 1mL of a mixed solution of ethanol and naphthol with the volume ratio of 9, uniformly mixing, dripping all the mixed solution on the surface of foam nickel with the thickness of 2cm multiplied by 2.5cm, and drying to obtain the WC/NF catalyst.
Comparative example 3
The comparative example provides a preparation method of a Pd/C/NF catalyst, which comprises the following steps:
a commercial Pd/C catalyst (10 wt% Pd) of 130mg was added to a 1mL mixed solution of ethanol and naphthol in a volume ratio of 9.
Comparative example 4
The comparative example provides a preparation method of a Ni + WC/NF catalyst, which comprises the following steps:
weighing 0.24g of nickel chloride, 0.3g of sodium tungstate and 1.5g of urea, uniformly mixing, placing in a tube furnace, and calcining for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain Ni + WC;
and step two, adding the prepared Ni + WC into 1mL of mixed solution of ethanol and naphthol with the volume ratio of 9, uniformly mixing, dropwise coating the mixture on the surface of foam nickel with the thickness of 2cm multiplied by 2.5cm, and drying to obtain the Ni + WC/NF catalyst.
The catalysts prepared in example 1 and comparative examples 1 to 4 were electrocatalyzed for p-chlorophenol according to the method of application example 1 above, and the results are shown in FIG. 6 a. As can be seen from the figure, the Ni-WC/NF catalyst prepared in example 1 can completely convert p-chlorophenol into phenol within 3h, and the catalytic activity is obviously superior to that of the commercial Pd/C/NF catalyst (the conversion rate within 4h is 63%), ni-C/NF (8.9% within 4 h), WC/NF (0%) and Ni + WC/NF (9.6% within 4 h).
By C/C 0 Log-ln (C/C) of log value of (2) 0 ) Plotted as an ordinate versus an abscissa for electrolysis time, as shown in FIG. 6b, it can be seen that the Ni-WC/NF catalyst prepared in example 1 has the fastest reaction rate (2.2X 10) -2 ) Is obviously superior to the commercial Pd/C/NF catalyst (4.1 multiplied by 10) -3 ) Wherein, the reaction rates of the Ni + WC/NF catalyst and the Ni-C/NF catalyst are respectivelyIs 3.9 multiplied by 10 -4 And 3.6X 10 -4 The two lines are substantially coincident due to the proximity of the reaction rates.
In order to further compare the intrinsic activity of the catalysts, the TOF values of the catalysts were compared by the present invention, and the results are shown in FIG. 6c, from which it can be seen that the Ni-WC/NF catalyst prepared in example 1 has the highest TOF value of 0.04h -1 Is 2 times of that of commercial Pd/C/NF (0.02 h) -1 ) 46.5 times (8.6X 10) of Ni-C/NF -4 h -1 ) 40 times (1X 10) of Ni + WC/NF -3 h -1 ). And by comparing the current efficiency with the Pd/C/NF catalyst (fig. 6 d), the current efficiency of the Ni-WC/NF catalyst prepared in example 1 is much higher than that of the noble metal Pd/C catalyst, which fully demonstrates the high catalytic activity of the Ni-WC/NF catalyst.
Comparative example 5
The present comparative example provides a method for preparing a Ni-WC/C catalyst, comprising the steps of:
step one, weighing 0.9g of Na 9 [A-α-PW 9 O 34 ]·nH 2 Dissolving O and 1.2g of Tris (hydroxymethyl) aminomethane (Tris) in 40mL of acetic acid-sodium acetate buffer (pH = 4.8), stirring until the solution is clear, adding 2.4g of nickel chloride, 0.75g of trimesic acid (BTC) and 0.9mL of ethylenediamine (en), and stirring for 30min to obtain a precursor solution;
step two, transferring the precursor solution into a hydrothermal kettle, heating at the constant temperature of 160 ℃ for 25h, cooling to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and drying to obtain { Ni 54 W 72 }；
Step three, obtaining the { Ni 54 W 72 Putting the mixture into a tubular furnace, and calcining the mixture for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain Ni-WC/C;
step four, adding 130mg of the prepared Ni-WC/C into 1mL of mixed solution of ethanol and naphthol with the volume ratio of 9.
Scanning electron micrographs of the Ni-WC/C catalyst prepared in this comparative example are shown in FIGS. 7a-7b, from which it can be seen that the catalyst prepared in this comparative example does not have a three-dimensional hierarchical structure and does not give uniform nanoparticles. The material was applied to electrocatalytic p-chlorophenol in exactly the same manner as in application example 1 above, and as a result, as shown in fig. 7C, it can be seen from the graph that the Ni-WC/C electrode prepared in this comparative example converted 45.4% of p-chlorophenol within 3h, while the Ni-WC/NF with a hierarchical structure prepared in example 1 could completely remove the same amount of p-chlorophenol within 3h.
Comparative example 6
This comparative example provides a method of preparing a Ni-WC/NF catalyst, which is exactly the same as example 1, except that { Ni } prepared in step two is used 54 W 72 The catalyst obtained by carbonizing the catalyst at 500 ℃, 600 ℃, 650 ℃, 750 ℃ and 800 ℃ respectively is marked as Ni-WC/NF-500, ni-WC/NF-600, ni-WC/NF-650, ni-WC/NF-750 and Ni-WC/NF-800.
The scanning electron microscope images of the catalyst are shown in fig. 8a-8e, and it can be seen from fig. 8a-8e that the particle size of the Ni-WC nanoparticles gradually increases with the increase of the annealing temperature, and when the carbonization temperature is higher than 700 ℃, the nanoparticles agglomerate and the morphology of the nanoparticles disappears.
The different catalyst samples were used to electrocatalyze p-chlorophenol according to the method of application example 1, and the results are shown in FIG. 9. As can be seen from the figure, ni-WC/NF prepared in example 1 showed the best dechlorination effect, converting p-chlorophenol completely into phenol within 3h. Under the same conditions, the conversion rate of the Ni-WC/NF-500 to the parachlorophenol is 12%, the conversion rate of the Ni-WC/NF-600 to the parachlorophenol is 40%, the conversion rate of the Ni-WC/NF-650 to the parachlorophenol is 58%, the conversion rate of the Ni-WC/NF-750 to the parachlorophenol is 45% and the conversion rate of the Ni-WC/NF-800 to the parachlorophenol is 24%.
Application example 2
In order to prove that the Ni-WC/NF catalyst provided by the embodiment of the invention has universality on chlorine-containing organic matters, the Ni-WC/NF catalyst prepared in the embodiment 1 is subjected to an electrocatalytic 2-chlorophenol test:
an H-type electrolytic cell is adopted, the Ni-WC/NF catalyst prepared in example 1 is used as a working electrode, a Pt net is used as a counter electrode, ag/AgCl is used as a reference electrode, an anolyte is 40mL of 0.05M sodium sulfate solution, a catholyte is 40mL of 0.05M sodium sulfate solution containing 80mg/L of-2 chlorophenol (2-CP), constant-current (10 mA) electrocatalytic dechlorination is carried out, 200 mu L of electrolyte is taken at intervals of 30min for dilution, and then the conversion rate of chlorophenol is tested. The results are shown in FIG. 10.
As shown in FIG. 10, the Ni-WC/NF catalyst prepared in example 1 has universality for chlorine-containing substrates (containing monochloro), can completely remove 2-CP in the same time, and has a faster reaction rate.
In order to demonstrate the recycling stability of the catalyst, the Ni — WC/NF catalyst was reused 5 times according to the above method, and the results are shown in fig. 11, which demonstrates that the catalytic activity was not significantly decreased after 5 consecutive uses.
As shown in fig. 12 and 13, XRD and SEM of the Ni-WC/NF catalyst after 5 cycles of recycling showed no significant changes in structure and morphology of the catalyst during recycling, demonstrating that the Ni-WC/NF catalyst prepared by the examples of the present invention has good stability.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Claims (10)

1. A preparation method of a foam nickel loaded Ni-WC composite material is characterized by comprising the following steps:
step a, adding Keggin type three-vacancy heteropolyphosphotungstate and trihydroxymethyl aminomethane into an acetic acid buffer solution, uniformly mixing, adding soluble nickel salt, ethylenediamine and trimesic acid, and uniformly mixing to obtain a precursor solution;
and b, adding the precursor solution and the foamed nickel into a hydrothermal kettle, reacting for 20-26 h at 150-180 ℃, then placing the foamed nickel after reaction in a protective atmosphere, and carbonizing at 690-710 ℃ to obtain the foamed nickel loaded Ni-WC composite material.
2. The method of preparing a nickel foam loaded Ni-WC composite material according to claim 1,the Keggin type three-vacancy heteropolyphosphotungstate is Na 9 [A-α-PW 9 O 34 ](ii) a And/or
The soluble nickel salt is nickel chloride, nickel nitrate or nickel sulfate.
3. The preparation method of the foamed nickel-loaded Ni-WC composite material as claimed in claim 1 or 2, wherein the mass ratio of the Keggin type triple-vacancy heteropolyphosphotungstate to the tris (hydroxymethyl) aminomethane is 0.6-0.8; and/or
The pH value of the acetic acid buffer solution is 4.5-5.0, the volume-mass ratio of the acetic acid buffer solution to Keggin type three-vacancy heteropolyphosphotungstate is 1000-23, wherein the volume unit is milliliter, and the mass unit is gram.
4. The method for preparing the nickel foam-loaded Ni-WC composite material according to claim 1, wherein the mass ratio of the soluble nickel salt to the Keggin type triple-vacancy heteropolyphosphotungstate is 1; and/or
The volume-mass ratio of the ethylenediamine to the Keggin type three-vacancy heteropolyphosphotungstate is 1.9-1.1, wherein the volume unit is milliliter, and the mass unit is gram.
5. The method for preparing the foamed nickel-loaded Ni-WC composite material according to claim 1, wherein the mass ratio of the trimesic acid to the Keggin type triple-vacancy heteropolyphosphotungstate is 1-1.2.
6. The method of preparing a foamed nickel loaded Ni-WC composite according to claim 1, wherein the carbonization time is between 2h and 4h.
7. A nickel foam-loaded Ni-WC composite material produced by the method of any one of claims 1-6 for producing a nickel foam-loaded Ni-WC composite material.
8. The use of the foamed nickel loaded Ni-WC composite of claim 7 in the electrocatalytic treatment of chlorine-containing organics in wastewater.
9. A method for removing chlorine-containing organic matters in wastewater through electrocatalysis is characterized by comprising the following steps:
the foamed nickel loaded Ni-WC composite material as claimed in claim 7 is used as a working electrode, a Pt net is used as a counter electrode, ag/AgCl is used as a reference electrode, and chlorine-containing organic matter wastewater is introduced for constant-current electro-catalytic dechlorination.
10. The method for removing chlorinated organic compounds in wastewater through electrocatalysis as claimed in claim 9, characterized in that the electrocatalysis is carried out by using an H-type electrolytic cell, the current is controlled to be 10mA, and the electrolysis time is not less than 3H.
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