CN112007651A - Method for preparing two-dimensional alloy/carbon composite nano material by electroplating and organic sludge - Google Patents
Method for preparing two-dimensional alloy/carbon composite nano material by electroplating and organic sludge Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 56
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- 238000009713 electroplating Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 55
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
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- 229910052802 copper Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
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- 239000007789 gas Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
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- 150000002736 metal compounds Chemical class 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- B01J35/33—
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- B01J35/39—
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- B01J35/40—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
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- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
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- C02F2101/40—Organic compounds containing sulfur
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of solid waste recycling treatment, and discloses a method for preparing a two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge. Mixing electroplating sludge, organic sludge and inorganic salt, heating and stirring until the water is evaporated to dryness, depositing to obtain a precursor containing a metal component/an organic carbon component/the inorganic salt, grinding, roasting in a protective atmosphere to obtain an alloy nanoparticle/carbon @ inorganic salt compound, adding the alloy nanoparticle/carbon @ inorganic salt compound into water to dissolve an inorganic salt template, and separating and recovering a black substance floating on the surface of the solution to obtain conductive graphite carbon; and centrifuging the residual mixture to obtain the two-dimensional alloy/carbon composite nano material, and concentrating the residual inorganic salt solution for recycling. The method not only improves the utilization rate of resources, but also provides a scheme with economic benefit for solving the two solid waste pollutions.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling treatment, and particularly relates to a method for preparing a two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge.
Background
The problem of environmental pollution caused by waste water and sludge generated in the current electroplating process is serious, mainly because the waste water generated in the electroplating process contains heavy metal ions (Cu) with high concentration2+、Ni2+、Cr6+、Zn2+、Fe3+Etc.), a large amount of electroplating sludge is generated in the electroplating wastewater treatment process, and secondary pollution is caused to the environment if the electroplating sludge cannot be scientifically and reasonably treated.
The grade of metal contained in the electroplating sludge is higher than that of common metal-rich ores, taking nickel as an example, common nickel ore has commercial exploitation value when the nickel content reaches 2%, and the nickel content in the electroplating sludge is generally 2% -4%, so that considerable commercial value can be generated by resource utilization of metal elements in the electroplating sludge.
The prior recycling treatment method for the electroplating sludge mainly comprises wet extraction, a roasting and leaching method, a carbon-thermal smelting method and the like; however, when these methods are used for treating electroplating sludge containing a plurality of metal components, the problems of complicated operation, difficult element separation and further treatment of the product for use are inevitably encountered. Therefore, the development of a process which is simple to operate and can synthesize the electroplating sludge into an industrial product which can be directly applied is of great significance.
The industrial organic sludge is a precipitation substance which is generated by precipitation equipment and takes organic matters as main components, and is a product for treating organic wastewater (including domestic sewage). The water content of the industrial organic sludge is generally more than 90 percent, the dehydration is difficult, and the storage and the disposal of the industrial organic sludge are easy to cause environmental pollution due to the fact that the industrial organic sludge is rotten and consumes high oxygen. Organic sludges are generally treated by converting organic matter into gas by microbial digestion or chemical oxidation. However, the microbial digestion method requires additional supply of oxygen, and energy consumption is also large; the chemical agent oxidation method is difficult to thoroughly destroy organic matters in the sludge and is easy to form new pollution. Therefore, the development of a method with lower cost, higher degradation efficiency and more environmental protection is still needed for the treatment of industrial organic sludge.
Patent CN103028412A discloses a method for preparing carbon black-metal oxide composite catalyst by using electroplating wastewater or sludge. The method comprises the steps of mixing and precipitating electroplating wastewater or dried electroplating sludge containing iron, zinc, chromium, nickel, copper and cobalt and organic wastewater with the organic matter content of more than 1000ppm, and cracking the obtained mixed precipitate at the temperature of 800-; the carbon black-metal oxide composite catalyst can be used for high-temperature catalytic decomposition of organic pollutants. The principle of utilization is that the electroplating sludge powder has larger specific surface area and larger adsorption capacity to organic matters in the organic wastewater; when the pH value of the organic wastewater is controlled to be within the range of 9-12, a part of metals in the electroplating wastewater and the sludge and organic matters in the organic wastewater form a complex structure and are precipitated on the surface of the electroplating sludge. However, the method has limited effect of mixing and precipitation, and partial metal components and organic components are difficult to realize solid-liquid separation and are effectively utilized.
The phase transfer-fused salt-carbothermic method is a method capable of preparing two-dimensional nano catalyst on a large scale, firstly, a surfactant is complexed with metal cations in a liquid phase, and the liquid phase moves to an oil phase, and then the liquid separation is carried out to remove the water phase; then heating and evaporating the organic solvent in the oil phase, mixing the residual surfactant-metal ion complex with a certain proportion of inorganic salt, and then grinding; and reducing the ground solid mixed powder at high temperature in a tube furnace in an inert atmosphere, and reducing the metal ions/oxides into simple substances or alloys by using a surfactant as a carbon source. The FeNi @ C series of catalysts synthesized by the carbothermic method by the Hazeg project group of university of major continental engineering show excellent catalytic performance in both electrocatalytic ORR and OER due to the bimetallic catalytic sites (DOI: 10.1002/chem.201904685). Research of the Huanglian topic group of Huazhong university of science and technology shows that a thinner two-dimensional nanomaterial can be prepared by uniformly mixing a salt template used in a molten salt method with a precursor in a liquid phase and then roasting the mixture, and the catalytic performance of the two-dimensional nanomaterial can be further improved (DOI:10.1039/c7ta05821 g). Therefore, if the technology can be used for the treatment of solid wastes as resources, the technology is a measure with significant innovation in the environmental protection industry and the resource recycling industry.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a method for preparing a two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge. The method takes electroplating sludge, industrial organic sludge and cheap industrial inorganic salt as raw materials, and prepares the two-dimensional alloy/carbon composite nano catalyst with low cost and excellent catalytic performance in a large scale by a chemical method.
The invention also aims to provide the two-dimensional alloy/carbon composite nano material prepared by the method.
The invention further aims to provide the application of the two-dimensional alloy/carbon composite nano material as a catalyst in chemical reactions such as photocatalytic water oxidation, photocatalytic degradation or electrocatalytic Oxygen Evolution (OER).
The purpose of the invention is realized by the following technical scheme:
a method for preparing a two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge comprises the following preparation steps:
(1) deposition: mixing electroplating sludge, organic sludge and inorganic salt, heating and stirring until the water is evaporated to dryness, and depositing to obtain a precursor containing a metal component/an organic carbon component/inorganic salt;
(2) roasting: grinding the precursor obtained in the step (1), and then roasting in a protective atmosphere to obtain an alloy nanoparticle/carbon @ inorganic salt compound;
(3) separation: adding the alloy nanoparticle/carbon @ inorganic salt compound obtained in the step (2) into water to dissolve an inorganic salt template, and separating and recovering black substances floating on the surface of the solution to obtain conductive graphite carbon; and (3) centrifugally separating the residual mixture, wherein the obtained black solid is the target product two-dimensional alloy/carbon composite nano material, and the residual inorganic salt solution is recycled in the step (1) after being concentrated.
The electroplating sludge is mainly electroplating sludge containing heavy metal compounds such as chromium, iron, nickel, copper, zinc and the like and soluble salts thereof generated in the electroplating wastewater treatment process; the organic sludge is a sediment substance which is generated by treating organic wastewater and takes organic matters as main components. The invention mainly realizes the purposes of recycling heavy metals in electroplating sludge and organic carbon components in organic sludge and realizing harmless treatment of solid waste.
Further, the inorganic salt in the step (1) includes at least one of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium carbonate and potassium carbonate.
Further, the particle size of the inorganic salt in the step (1) is preferably 200 mesh or less.
Further, the weight ratio of the mixture of the electroplating sludge, the organic sludge and the inorganic salt in the step (1) is 100 (20-200) to 20-500.
Further, the temperature of the heating and stirring in the step (1) is 40-90 ℃, and the rotation speed is 500-2000 rpm.
Further, the protective atmosphere in the step (2) refers to a hydrogen/argon mixed atmosphere with a hydrogen volume fraction of 5% -20%.
Further, the temperature of the roasting treatment in the step (2) is 300-.
Further, the inorganic salt dissolving template in the step (3) is stirred for 10-60min by hot water with the temperature of 40-90 ℃.
A two-dimensional alloy/carbon composite nano material is prepared by the method.
The two-dimensional alloy/carbon composite nano material is applied as a catalyst in chemical reactions such as photocatalytic water oxidation, photocatalytic degradation or electrocatalytic Oxygen Evolution (OER).
The principle of the invention is as follows: through the deposition step, metal components in the electroplating sludge and carbon-containing components in the organic sludge are deposited on the surface of the inorganic salt in the process of evaporating water to dryness, and a precursor containing metal components/organic carbon components/inorganic salt is formed. Then through a roasting step, the multi-element metal oxide in the electroplating sludge is reduced by carbon and/or hydrogen in the organic sludge to form alloy nano particles (containing two or more of Cr, Cu, Ni, Fe and Zn), and meanwhile, due to the action of an inorganic salt template, a part of carbon forms a two-dimensional nano film in a pyrolysis process to wrap the surface of inorganic salt, so that an alloy nano particle/carbon @ inorganic salt compound is formed. Then through a separation step, dissolving the inorganic salt template by hot water, wherein black substances floating on the surface of the solution are parts with higher carbon content, and can be recovered and used as conductive graphite carbon after being filtered by upper-layer liquid; and (3) centrifugally separating the residual mixture, wherein the separated black solid is a target product two-dimensional alloy/carbon nano composite, and the separated inorganic salt solution is recycled after being concentrated.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method for preparing the two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge saves the cost for treating solid waste of two industries, and can fully utilize metal elements in the electroplating sludge and carbon elements in the organic sludge to prepare the two-dimensional alloy/carbon composite nano catalyst with high catalytic activity and economic benefit. Not only improves the utilization rate of resources, but also provides a scheme with economic benefits for solving the two solid waste pollutions.
(2) According to the method for preparing the two-dimensional alloy/carbon composite nanomaterial by using electroplating sludge and organic sludge, substances such as strong acid, strong alkali, toxic and volatile solvents are not used in the process of treating the electroplating sludge and the organic sludge, and excrement harmful to the environment is not generated, so that the requirements of environmental protection and high atom utilization rate can be met.
(3) The method can almost realize the full utilization of recoverable resources in the electroplating sludge and the organic sludge.
(4) The two-dimensional alloy/carbon composite material prepared by the invention can be used as an efficient catalyst for catalyzing chemical reactions such as photocatalytic water oxidation, photocatalytic degradation, electro-catalytic Oxygen Evolution (OER) and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing a two-dimensional alloy/carbon composite nanomaterial by electroplating and organic sludge in example 1.
FIG. 2 is a TEM image of the morphology of the two-dimensional alloy/carbon composite obtained in example 1.
FIG. 3 is a graph showing the results of the photocatalytic water oxidation performance tests on samples of the two-dimensional alloy/carbon composite material obtained under different calcination conditions in example 1.
FIG. 4 is a TEM image of the morphology of the two-dimensional alloy/carbon composite obtained in example 2.
Fig. 5 is a graph of the performance results of the two-dimensional alloy/carbon composite sample obtained in example 2 in degrading methylene blue under visible light.
FIG. 6 is the LSV polarization curve of the electrocatalytic oxygen evolution reaction of the composite nanomaterial obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Mixing 100 parts by weight of untreated electroplating sludge (containing heavy metals of 5.66% of chromium, 7.15% of iron, 3.71% of nickel, 1.99% of copper and 0.06% of cobalt in mass fraction), 100 parts by weight of industrial organic sludge which is not dried and 300 parts by weight of NaCl with the particle size of less than 200 meshes, mechanically stirring at the rotating speed of 1000rpm under the constant temperature condition of 80 ℃ until the water is evaporated to dryness, and depositing to obtain a precursor containing a metal component/an organic carbon component/NaCl.
(2) And (2) grinding the precursor obtained in the step (1) into powder, placing the powder into a tubular furnace, and roasting for 2 hours at 700 ℃ in the atmosphere of hydrogen/argon mixed gas (the volume fraction of hydrogen is 10%), so as to obtain alloy nano particle/carbon @ NaCl compound powder.
(3) And (3) cooling the composite powder obtained in the step (2), adding the cooled composite powder into 300 parts by weight of hot water (80 ℃) and stirring for 20min to dissolve the NaCl template. After stirring, standing, wherein the black substance floating on the surface of the solution is graphite carbon roasted by organic sludge, and can be recovered and used as conductive graphite carbon after being filtered by supernatant liquor; and centrifuging the residual suspension, wherein the separated black solid is a target product two-dimensional alloy/carbon composite material, and the separated NaCl solution can be recycled after concentration.
The process flow diagram of the present example is shown in fig. 1; the morphology of the product of the obtained two-dimensional alloy/carbon composite material is shown in figure 2, so that the carbon-based film is formed after the organic sludge is roasted, and the particle size of the nano particles formed after the electroplating sludge is roasted is about 15nm and is uniformly loaded on the carbon-based film.
Different roasting conditions are set, and two-dimensional alloy/carbon composite material samples are obtained under the conditions of 600 ℃ argon atmosphere, 700 ℃ argon atmosphere, 600 ℃ hydrogen/argon mixed atmosphere (the volume fraction of hydrogen is 10%), 700 ℃ hydrogen/argon mixed atmosphere and 800 ℃ hydrogen/argon mixed atmosphere respectively. The samples obtained under different calcination conditions were tested for photocatalytic water oxidation performance (test conditions: visible light, 1mg of photocatalyst, 1mM of photosensitizer, 10mM of potassium persulfate, and 10mL of boric acid buffer), and the test results are shown in FIG. 3. As can be seen from the results in FIG. 3, the two-dimensional alloy/carbon composite nanomaterial prepared by roasting under the atmosphere of hydrogen/argon gas mixture with the hydrogen volume fraction of 10% at 700 ℃ has the oxygen yield of 49.7 mu mol within 10 min. And the catalytic performance of the two-dimensional alloy/carbon composite material obtained by roasting under the condition of hydrogen/argon mixed atmosphere is obviously higher than that of the composite material obtained under the condition of pure argon protective atmosphere.
Example 2
(1) 100 parts by weight of untreated plating sludge (containing heavy metals: 5.34% by mass of chromium, 6.25% by mass of iron, 4.56% by mass of zinc, 3.35% by mass of nickel, and 1.37% by mass of copper), 50 parts by weight of undried industrial organic sludge, and 400 parts by weight of Na having a particle size of 200 mesh or less2CO3Mixing, mechanically stirring at 60 deg.C and constant temperature at 1500rpm until water content is evaporated, and depositing to obtain metal-containing component/organic carbon component/Na2CO3The precursor of (1).
(2) Grinding the precursor obtained in the step (1) into powder, placing the powder into a tube furnace, and roasting for 1h at the temperature of 750 ℃ in the atmosphere of hydrogen/argon mixed gas (the volume fraction of hydrogen is 15%), so as to obtain alloy nanoparticles/carbon @ Na2CO3And (3) composite powder.
(3) Cooling the composite powder obtained in the step (2), adding the cooled composite powder into 300 parts by weight of hot water (60 ℃) and stirring for 20min to dissolve Na2CO3And (5) template. After stirring, standing, wherein the black substance floating on the surface of the solution is graphite carbon roasted by organic sludge, and can be recovered and used as conductive graphite carbon after filtering supernatant liquor; centrifuging the rest suspension to obtain black solid as target product, and separating Na2CO3The solution can be recycled after being concentrated.
In the electroplating sludge of this example, the morphology of the target product obtained under the condition that the organic sludge is 2:1 is shown in fig. 4, and it can be seen that alloy nanoparticles are densely stacked together after the amount of the organic sludge is reduced, but the roasted sample still has a two-dimensional structure due to the action of the inorganic salt. The performance of the sample in degrading methylene blue under visible light (reaction conditions: 10mg/L of catalyst, 10mg/L of methylene blue and 19.65mM of hydrogen peroxide) is shown in FIG. 5, and under the optimized reaction conditions, the concentration of the methylene blue is reduced by 96.3% within 110 min.
Example 3
(1) 100 parts by weight of untreated electroplating sludge (containing heavy metals of 5.19% chromium, 3.96% zinc, 3.28% nickel, 1.76% copper, and 0.13% cobalt), 150 parts by weight of undried industrial organic sludge, and 200 parts by weight of K with a particle size of 200 mesh or less2SO4Mixing, mechanically stirring at constant temperature of 70 deg.C at 800rpm until water content is evaporated, and depositing to obtain metal-containing component/organic carbon component/K2SO4The precursor of (1).
(2) Grinding the precursor obtained in the step (1) into powder, placing the powder into a tube furnace, and roasting for 2 hours at 900 ℃ in the atmosphere of hydrogen/argon mixed gas (the volume fraction of hydrogen is 5%) to obtain alloy nanoparticles/carbon @ K2SO4And (3) composite powder.
(3) Cooling the composite powder obtained in the step (2), adding the cooled composite powder into 300 parts by weight of hot water (70 ℃) and stirring for 40min to dissolve K2SO4And (5) template. After stirring, standing, wherein the black substance floating on the surface of the solution is graphite carbon roasted by organic sludge, and can be recovered and used as conductive graphite carbon after filtering supernatant liquor; centrifuging the rest suspension mixture, separating black solid as target product two-dimensional alloy/carbon composite nanometer material, and separating K2SO4The solution can be recycled after being concentrated.
The LSV polarization curve of the electrocatalytic oxygen evolution reaction of the composite nano material obtained in the example is shown in FIG. 6, and the LSV polarization curve is obtained when the composite nano material contains saturated O2In KOH solution with the concentration of 1M, the overpotential for electrolyzing water to generate oxygen by the composite material is only 301 mV.
From the implementation results, the invention can prepare the two-dimensional alloy/carbon composite nano material by using the electroplating sludge and the industrial organic sludge as raw materials through a deposition-roasting-separation method. The method not only realizes the aim of treating the electroplating sludge by using industrial organic sludge to treat wastes with processes of wastes against one another, but also can prepare the two-dimensional alloy/carbon composite nano-catalyst with high catalytic activity, and provides a high-benefit strategy for recycling solid wastes.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing a two-dimensional alloy/carbon composite nano material by using electroplating and organic sludge is characterized by comprising the following preparation steps:
(1) deposition: mixing electroplating sludge, organic sludge and inorganic salt, heating and stirring until the water is evaporated to dryness, and depositing to obtain a precursor containing a metal component/an organic carbon component/inorganic salt;
(2) roasting: grinding the precursor obtained in the step (1), and then roasting in a protective atmosphere to obtain an alloy nanoparticle/carbon @ inorganic salt compound;
(3) separation: adding the alloy nanoparticle/carbon @ inorganic salt compound obtained in the step (2) into water to dissolve an inorganic salt template, and separating and recovering black substances floating on the surface of the solution to obtain conductive graphite carbon; and (3) centrifugally separating the residual mixture, wherein the obtained black solid is the target product two-dimensional alloy/carbon composite nano material, and the residual inorganic salt solution is recycled in the step (1) after being concentrated.
2. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: the inorganic salt in the step (1) comprises at least one of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium carbonate and potassium carbonate.
3. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: the particle size of the inorganic salt in the step (1) is 200 meshes or less.
4. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the weight ratio of the mixture of the electroplating sludge, the organic sludge and the inorganic salt is 100 (20-200) to 20-500.
5. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: the heating and stirring temperature in the step (1) is 40-90 ℃, and the rotating speed is 500-2000 rpm.
6. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: the protective atmosphere in the step (2) is a hydrogen/argon mixed atmosphere with the hydrogen volume fraction of 5-20%.
7. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: the temperature of the roasting treatment in the step (2) is 300-900 ℃, and the time of the roasting treatment is 0.5-4 h.
8. The method for preparing the two-dimensional alloy/carbon composite nano material by using the electroplating and the organic sludge as claimed in claim 1, wherein the method comprises the following steps: and (3) stirring the inorganic salt dissolving template in hot water at the temperature of 40-90 ℃ for 10-60 min.
9. A two-dimensional alloy/carbon composite nanomaterial, characterized in that: prepared by the method of any one of claims 1 to 8.
10. Use of a two-dimensional alloy/carbon composite nanomaterial as defined in claim 9 as a catalyst in photocatalytic water oxidation, photocatalytic degradation, or electrocatalytic oxygen evolution chemical reactions.
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