CN113005478A - Porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material and preparation method and application thereof - Google Patents
Porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material and preparation method and application thereof Download PDFInfo
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- CN113005478A CN113005478A CN202110214901.0A CN202110214901A CN113005478A CN 113005478 A CN113005478 A CN 113005478A CN 202110214901 A CN202110214901 A CN 202110214901A CN 113005478 A CN113005478 A CN 113005478A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention relates to a porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material and a preparation method and application thereof, belonging to the technical field of electrochemical water treatment. The composite material consists of porous nitrogen-doped carbon and copper-nickel alloy nanoparticles uniformly loaded on the porous nitrogen-doped carbon. The specific surface area of the composite material is 100-300m2When the catalyst is used as a catalyst for electrocatalytic reduction of nitrate, nitrate can be efficiently removed, and the catalyst has good cycle stability. The composite material has no noble metal load, low cost and preparation method thereofThe method is simple and easy to operate, has low requirement on equipment, greatly reduces energy consumption and can realize industrial production.
Description
Technical Field
The invention belongs to the technical field of electrochemical water treatment, and particularly relates to a porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material and a preparation method and application thereof.
Background
With the rapid development of industry and agriculture, especially the overproof discharge of nitrogen-containing waste water of chemical enterprises and the overuse of agricultural chemical fertilizers, the nitrate content in surface water and underground water is rapidly increased. Nitrate is converted into nitrite in human body by nitrate reducing bacteria, which causes a series of health problems, such as cancer, blue infant disease, etc. Therefore, the world health organization has limited the concentration of nitrate nitrogen in drinking water to 10 mg/L.
Converting nitrate into environment-friendly nitrogen or ammonia which is a value-added product is an ideal way. Ammonia is an important raw material for producing chemical fertilizers and is a green hydrogen-rich fuel. The electrochemical cathode reduces nitrate without adding chemical reagent, which gets rid of the limitation of traditional biological denitrification process to carbon nitrogen ratio. Electrochemical reduction of nitrate to ammonia is an eight-electron process with slow reaction kinetics, often requiring electrocatalysts to increase reaction rates. However, obtaining electrocatalysts of high activity and stability remains challenging. The copper-nickel alloy catalyst proved to have better activity than pure copper or pure nickel, even comparable to noble metals. At present, the synthesis of the copper-nickel alloy catalyst mainly adopts an electrochemical deposition method, namely copper and nickel ions in a solution are deposited by high cathodic current, but because the generation and growth speed of crystal nuclei on the surface of a substrate are difficult to control, the agglomeration of metal particles is inevitable. In another common method, inorganic salts containing copper and nickel are prepared into a solution, a gel is prepared through a sol-gel process, and a desired phase is obtained through calcination and decomposition.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material; the second purpose is to provide a preparation method of the porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material; the third purpose is to provide the application of the porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material as an electrochemical water treatment catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material is composed of porous nitrogen-doped carbon and copper-nickel alloy nanoparticles uniformly loaded on the porous nitrogen-doped carbon.
Preferably, the specific surface area of the composite material is 100-300m2The atomic ratio of copper to nickel in the composite material is 1-5:1-3, and the particle size of the copper-nickel alloy nano particles is 10-100 nm.
2. The preparation method of the porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material comprises the following steps:
dissolving soluble copper salt and soluble nickel salt in water, adding an organic carbon nitrogen source, stirring until copper ions and nickel ions in the solution are fully adsorbed on the organic carbon nitrogen source, adding nano silicon dioxide, continuously stirring until the nano silicon dioxide is uniformly dispersed, drying, grinding to obtain a precursor, roasting, pickling, washing, and drying.
Preferably, the molar ratio of the soluble copper salt to the soluble nickel salt to the organic carbon nitrogen source to the nano-silica is 1-3:1-3:3-30: 3-60.
Preferably, stirring is carried out for 15-60min to ensure that copper ions and nickel ions in the solution are fully adsorbed on the organic carbon nitrogen source, and stirring is continued for 3-10h to ensure that the nano silicon dioxide is uniformly dispersed.
Preferably, the drying specifically comprises: drying at 80-110 deg.C to constant weight; the drying specifically comprises the following steps: drying at 30-50 deg.C to constant weight.
Preferably, the roasting specifically comprises: raising the temperature to 700-800 ℃ at the temperature rise speed of 2-5 ℃/min under the protective atmosphere, and then preserving the heat for 3-4 h.
Preferably, the acid washing is specifically as follows: dispersing the roasted precursor in hydrofluoric acid with the mass fraction of 5-10%, and stirring for 3-6 h.
Preferably, the washing is specifically: washing with water for 3-5 times, and washing with anhydrous ethanol for 1-2 times.
Preferably, the soluble copper salt is copper chloride dihydrate, copper sulfate pentahydrate or copper nitrate trihydrate; the soluble nickel salt is nickel chloride hexahydrate, nickel sulfate hexahydrate or nickel nitrate hexahydrate; the organic carbon nitrogen source is melamine, dicyanodiamine or urea.
3. The porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material is applied as an electrochemical water treatment catalyst.
The invention has the beneficial effects that: the invention provides a porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material and a preparation method and application thereof, wherein the specific surface area of the composite material is 100-300m2When the catalyst is used as a catalyst for electrocatalytic reduction of nitrate, nitrate can be efficiently removed, and the catalyst has good cycle stability. When the composite material is prepared, the molar ratio of the soluble copper salt, the soluble nickel salt and the organic carbon-nitrogen source is controlled, so that the molar quantity of copper and nickel in the composite material is controlled, the electrocatalytic activity of the composite material is improved, and in addition, the nano silicon dioxide is added, so that the finally prepared composite material is ensured to have a porous structure and is beneficial to the exposure of active sites and the transmission of reaction substances, and on the other hand, the organic carbon-nitrogen source can be dispersed, the organic carbon-nitrogen source is prevented from forming blocks in the high-temperature sintering process, the growth of copper-nickel alloy nanoparticles is limited to large-size particles, the particle size of the copper-nickel alloy nanoparticles is controlled to be 10-100nm, the defect that the copper-nickel alloy nanoparticles fall off from porous nitrogen-doped carbon due to overlarge particles is effectively avoided, and the copper-. The composite material has no noble metal load, low cost, simple and easy operation of the preparation method, low requirement on equipment, greatly reduced energy consumption and realization of industrial production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite prepared in example 1;
fig. 2 is a TEM image of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite prepared in example 1;
fig. 3 is an XRD pattern of the porous nitrogen-doped carbon-supported cupronickel alloy nanoparticle composite material prepared in examples 1 to 3;
fig. 4 is a nitrogen adsorption and desorption graph of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1;
fig. 5 is a graph showing the results of the electrocatalytic reduction nitrate removal rate test on the porous nitrogen-doped carbon-supported cupronickel alloy nanoparticle composites prepared in examples 1 to 3;
fig. 6 is a graph of the results of the stability test of the electrocatalytic reduction of nitrate by the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material (Cu)0.43Ni0.57/NC)
Dissolving copper chloride dihydrate and nickel chloride hexahydrate in 20mL of deionized water, adding melamine, stirring for 15min to make copper ions and nickel ions in the solution fully adsorbed on the melamine, adding nano-silica, continuing stirring for 5h to uniformly disperse the nano-silica, drying at 100 ℃ to constant weight, grinding to obtain a precursor, wherein the molar ratio of copper chloride dihydrate to nickel chloride hexahydrate to melamine to nano silicon dioxide is 1:1:7:13, placing the precursor in a tube furnace, heating to 750 ℃ at a heating rate of 3 ℃/min under Ar atmosphere, preserving heat for 3h, dispersing in 5% hydrofluoric acid, stirring for 4h, washing with water for 4 times, washing with anhydrous ethanol for 1 time, and drying at 40 ℃ to constant weight to prepare the porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material.
Example 2
Preparation of porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material (Cu)0.26Ni0.74/NC)
Dissolving copper nitrate trihydrate and nickel nitrate hexahydrate in 20mL of deionized water, adding dicyanodiamide, stirring for 40min to enable copper ions and nickel ions in the solution to be fully adsorbed on the dicyanodiamide, adding nano-silicon dioxide, continuing stirring for 8h to enable the nano-silicon dioxide to be uniformly dispersed, drying at 110 ℃ to constant weight, grinding to obtain a precursor, wherein the molar ratio of the copper nitrate trihydrate, the nickel nitrate hexahydrate, the dicyandiamide to the nano silicon dioxide is 1:3:20:30, the precursor is placed in a tube furnace, heating to 700 ℃ at a heating rate of 2 ℃/min under Ar atmosphere, preserving heat for 4h, dispersing in 8% hydrofluoric acid, stirring for 6h, washing with water for 3 times, washing with anhydrous ethanol for 2 times, and drying at 50 ℃ to constant weight to prepare the porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material.
Example 3
Preparation of porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material (Cu)0.79Ni0.21/NC)
Dissolving copper chloride dihydrate and nickel chloride hexahydrate in 20mL of deionized water, adding urea, stirring for 60min to enable copper ions and nickel ions in the solution to be fully adsorbed to the urea, adding nano-silica, continuing stirring for 10h to enable the nano-silica to be uniformly dispersed, drying at 80 ℃ to constant weight, grinding to obtain a precursor, wherein the molar ratio of the copper chloride dihydrate to the nickel chloride hexahydrate to the urea to the nano-silica is 3:1:30:60, placing the precursor in a tubular furnace, raising the temperature to 800 ℃ at the temperature raising speed of 5 ℃/min under the Ar atmosphere, keeping the temperature for 3h, dispersing in hydrofluoric acid with the mass fraction of 10%, stirring for 3h, finally washing with water for 5 times, then washing with absolute ethyl alcohol for 2 times, and drying at 30 ℃ to constant weight to obtain the porous nitrogen-carbon-doped copper-nickel alloy nanoparticle composite material.
Fig. 1 is an SEM image of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1, and fig. 2 is a TEM image of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1, and it can be seen from fig. 1 and fig. 2 that the copper-nickel alloy nanoparticles are successfully supported on the porous nitrogen-doped carbon, and the particle size of the copper-nickel alloy nanoparticles is 20-50 nm.
Fig. 3 is an XRD chart of the porous nitrogen-doped carbon-supported cupronickel alloy nanoparticle composite materials prepared in examples 1 to 3, which shows that alloy structures with different copper-nickel atomic ratios can be prepared by changing the molar ratio of the soluble copper salt to the soluble nickel salt in the raw materials.
Fig. 4 is a nitrogen adsorption and desorption graph of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1, and it can be seen that the specific surface area of the composite material is 142m2/g。
The composite materials prepared in the above examples 1 to 3 were respectively coated on carbon cloth as a working electrode, Ir-Ru/Ti as a counter electrode, and a saturated calomel electrode as a reference electrode. 100mL of nitrate solution with the concentration of 50mg-N/L is prepared by using sodium nitrate, 50mM sodium sulfate is added to improve the conductivity of the solution, a nitrate reduction experiment is carried out for 5h under the potential of-1.3V, 2.0mL of samples are taken out every 1h for testing, and the removal rate of electrocatalytic reduction nitrate of each composite material is calculated. As shown in fig. 5, it can be seen from fig. 5 that the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material of the present invention can remove 90% of nitrate within 5 hours.
The stability of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1 in the electrocatalytic reduction of nitrate was tested, and 12 repeated tests were performed at-1.3V using the above-mentioned nitrate removal rate as an index, and the test results are shown in fig. 6, and it can be seen from fig. 6 that when the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material prepared in example 1 was used as a catalyst in the electrocatalytic reduction of nitrate, the removal rates of 12 cycles were all maintained at 80% or more, and good cycle stability was exhibited.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The porous nitrogen-doped carbon-loaded copper-nickel alloy nanoparticle composite material is characterized by consisting of porous nitrogen-doped carbon and copper-nickel alloy nanoparticles uniformly loaded on the porous nitrogen-doped carbon.
2. The porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material as claimed in claim 1, wherein the specific surface area of the composite material is 100-300m2The atomic ratio of copper to nickel in the composite material is 1-5:1-3, and the particle size of the copper-nickel alloy nano particles is 10-100 nm.
3. The preparation method of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material as claimed in claim 1 or 2, wherein the method comprises the following steps:
dissolving soluble copper salt and soluble nickel salt in water, adding an organic carbon nitrogen source, stirring until copper ions and nickel ions in the solution are fully adsorbed on the organic carbon nitrogen source, adding nano silicon dioxide, continuously stirring until the nano silicon dioxide is uniformly dispersed, drying, grinding to obtain a precursor, roasting, pickling, washing, and drying.
4. The method of claim 3, wherein the molar ratio of the soluble copper salt, the soluble nickel salt, the organic carbon nitrogen source and the nano-silica is 1-3:1-3:3-30: 3-60.
5. The method of claim 4, wherein the stirring is carried out for 15-60min to ensure that copper ions and nickel ions in the solution are fully adsorbed on the organic carbon nitrogen source, and the stirring is continued for 3-10h to ensure that the nano silicon dioxide is uniformly dispersed.
6. The method according to claim 3, wherein the drying is specifically: drying at 80-110 deg.C to constant weight; the drying specifically comprises the following steps: drying at 30-50 deg.C to constant weight.
7. The method of claim 3, wherein the firing is specifically: raising the temperature to 700-800 ℃ at the temperature rise speed of 2-5 ℃/min under the protective atmosphere, and then preserving the heat for 3-4 h.
8. The method according to claim 3, characterized in that the pickling is in particular: dispersing the roasted precursor in hydrofluoric acid with the mass fraction of 5-10%, and stirring for 3-6 h.
9. The method of any one of claims 3 to 8, wherein the soluble copper salt is copper chloride dihydrate, copper sulfate pentahydrate or copper nitrate trihydrate; the soluble nickel salt is nickel chloride hexahydrate, nickel sulfate hexahydrate or nickel nitrate hexahydrate; the organic carbon nitrogen source is melamine, dicyanodiamine or urea.
10. Use of the porous nitrogen-doped carbon-supported copper-nickel alloy nanoparticle composite material of claim 1 or 2 as an electrochemical water treatment catalyst.
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