CN111900415A - Method for preparing metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge - Google Patents
Method for preparing metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge Download PDFInfo
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- CN111900415A CN111900415A CN202010663359.2A CN202010663359A CN111900415A CN 111900415 A CN111900415 A CN 111900415A CN 202010663359 A CN202010663359 A CN 202010663359A CN 111900415 A CN111900415 A CN 111900415A
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/90—Selection of catalytic material
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- 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
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge, which comprises the steps of mixing the electroplating sludge, melamine and corn straw biomass powder according to a certain proportion, dissolving the mixture in ultrapure water, magnetically stirring the mixture for 4 hours at room temperature, drying the mixture at 50-70 ℃ after stirring, and grinding the mixture into powder after drying; then taking appropriate amount of powder, and heating at 950 deg.C and N2Pyrolyzing for 2h under protection, cooling to below 100 ℃, and taking out; and placing the obtained product in 1mol/L hydrochloric acid for soaking, shaking, washing and drying to obtain the metal-nitrogen co-doped oxygen reduction catalyst based on the electroplating sludge. The catalyst has oxygen reduction catalytic activity comparable to that of commercial Pt/C in test, has excellent stability, good methanol resistance and simple preparation, is a good measure for changing waste into valuable, and provides a choice for a cathode catalyst of a fuel cell.
Description
Technical Field
The invention relates to a method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge, belonging to the technical field of electrocatalysis and waste recycling.
Background
The fuel cell is an environment-friendly energy device with high efficiency and low noise, but the cathode oxygen reduction reaction has high overpotential and poor methanol resistance, and the fuel cell can have good performance only by needing a proper catalyst, thereby playing the advantages of the fuel cell. The current commercialized Pt catalyst is expensive and has a limited Pt storage, and a non-noble metal catalyst with good catalytic performance, low price and large storage needs to be developed to replace the Pt catalyst. Non-noble metal based oxygen reduction catalysts have created new promise for fuel cells, especially metal-nitrogen/carbon based catalysts.
The metal source is an important component in the metal-nitrogen/carbon type catalyst. The electroplating sludge as a final state substance for wastewater treatment in the electroplating industry contains a large amount of important metals such as copper, nickel, chromium, iron, zinc and the like with different contents, and if the electroplating sludge is not properly treated, the electroplating sludge can cause pollution and damage to the environment, but has the potential of becoming a metal source. The electroplating sludge is taken as a metal source of a metal-nitrogen/carbon catalyst, which is a two-step measure of waste utilization and environmental protection, but the electroplating sludge is not reported in documents until now.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge, the operation is simple and convenient, the preparation time is short, the used metal source is electroplating industrial waste, the prepared catalyst has good oxygen reduction catalytic performance which can be comparable to the current commercial Pt/C, and the prepared catalyst also has good methanol resistance and durability.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge comprises the following steps:
a. drying and grinding corn straws, and then sieving the ground straw powder with a 100-mesh sieve and collecting to obtain straw powder;
b. mixing electroplating sludge, melamine and the straw powder sieved in the step a, dissolving the mixture in ultrapure water, magnetically stirring the mixture at room temperature for at least 4 hours, filtering and separating the mixture after stirring to obtain solid matters, drying the solid matters at 50-70 ℃, and grinding the dried solid matters into mixture powder;
c. putting the mixture powder obtained in the step b into a quartz boat, and carrying out reaction at the temperature of not less than 950 ℃ and in N2Pyrolyzing the mixture for at least 2 hours under protection, then cooling a pyrolysis production area to be not higher than 100 ℃, and taking out a pyrolysis product to obtain pyrolytic metal-nitrogen modified biochar;
d. and c, placing the biochar obtained in the step c in hydrochloric acid with the concentration not lower than 1mol/L, soaking, shaking and washing for at least 12 hours, then performing suction filtration and washing with ultrapure water until the pH value is 7, separating and collecting washed products, and then drying at 50-70 ℃ to obtain the metal-nitrogen co-doped oxygen reduction catalyst.
In the step b, the electroplating sludge, the melamine and the straw powder sieved in the step a are mixed according to the mass ratio of 1:20: 4.
As a preferred technical scheme of the invention, in the step c, the mixture powder obtained in the step b is placed in a quartz boat, a non-redox protection gas is introduced into a vacuum tube furnace, the flow rate is not lower than 200mL/min, the temperature is programmed to be not lower than 100 ℃ from room temperature, the temperature rise rate is not lower than 10 ℃/min, the temperature is kept for at least 20min at a constant temperature, so that the oxygen in the tube furnace is completely discharged, and the biomass is in a dry state; then heating to be not less than 950 ℃ at the heating rate of not less than 10 ℃/min, and carrying out constant-temperature carbonization treatment for at least 2 h; and then cooling the pyrolysis product obtained after the constant-temperature carbonization treatment to be not higher than 100 ℃, and taking out the pyrolysis product to obtain the pyrolytic metal-nitrogen modified biochar.
As a preferred technical solution of the present invention, in the step d, the mass percent of the metal contained in the prepared metal-nitrogen co-doped oxygen reduction catalyst is not less than 0.65 wt.%, and the mass percent of the nitrogen contained in the prepared metal-nitrogen co-doped oxygen reduction catalyst is not less than 4.76 wt.%.
As a further preferable technical solution of the present invention, in the step d, the prepared metal-nitrogen co-doped oxygen reduction catalyst contains not less than 0.65 wt.% of metal, not less than 4.76 wt.% of nitrogen, not less than 2.13 wt.% of silicon, not less than 14.35 wt.% of oxygen, and the balance of carbon and impurities.
The invention relates to a metal-nitrogen co-doped oxygen reduction catalyst, which is prepared by a method for preparing the metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method can prepare a metal-nitrogen co-doped oxygen reduction catalyst based on the electroplating sludge, the catalyst has oxygen reduction catalytic activity comparable to that of commercial Pt/C during testing, and has excellent stability, good methanol resistance and simple preparation, thereby being a good measure for changing waste into valuable and providing a choice for a cathode catalyst of a fuel cell;
2. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is SEM and TEM test images of the preparation method of the preferred embodiment of the invention.
FIG. 2 is a LSV graph comparing the metal-nitrogen co-doped oxygen reduction catalyst prepared by the preferred embodiment of the present invention and commercial Pt/C.
FIG. 3 is a methanol resistance test plot for a commercial Pt/C oxygen reduction catalyst of the prior art.
Fig. 4 is a methanol resistance test chart of the metal-nitrogen co-doped oxygen reduction catalyst prepared in the preferred embodiment of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
in this embodiment, a method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge comprises the following steps:
a. drying and grinding corn straws, and then sieving the ground straw powder with a 100-mesh sieve and collecting to obtain straw powder;
b. mixing electroplating sludge, melamine and the straw powder sieved in the step a according to the mass ratio of 1:20:4, dissolving in ultrapure water, magnetically stirring at room temperature for 4 hours, filtering and separating after stirring to obtain a solid matter, drying at 50-70 ℃, and grinding the dried solid matter into mixture powder;
c. b, placing the mixture powder obtained in the step b in a quartz boat, introducing non-redox protective gas into the vacuum tube furnace, wherein the flow rate of the non-redox protective gas is 200mL/min, carrying out programmed temperature rise from room temperature to 100 ℃, the temperature rise rate is 10 ℃/min, and keeping the constant temperature for 20min, so that the oxygen in the tube furnace is completely discharged, and the biomass is in a dry state; then heating to 950 ℃ at the heating rate of 10 ℃/min, and carrying out constant-temperature carbonization treatment for 2 h; then cooling the pyrolysis product obtained after the constant-temperature carbonization treatment to 100 ℃, and taking out the pyrolysis product to obtain pyrolytic metal-nitrogen modified biochar;
d. and c, placing the biochar obtained in the step c in hydrochloric acid with the concentration of 1mol/L, soaking, shaking and washing for 12 hours, then performing suction filtration and washing with ultrapure water until the pH value is 7, separating and collecting washed products, and then drying at 50-70 ℃ to obtain the metal-nitrogen co-doped oxygen reduction catalyst.
Experimental test analysis:
the metal-nitrogen co-doped oxygen reduction catalyst prepared in this example was used as a test sample to conduct property examination.
In this example, the composition of the electroplating sludge is shown in Table 1.
TABLE 1 electroplating sludge ingredient Table
The results of the composition analysis of the plating sludge used in this example show that the plating sludge is mainly Fe and contains a small amount of a mixture of other metals.
In this example, the ingredients of the prepared metal-nitrogen co-doped oxygen reduction catalyst are shown in table 2.
TABLE 2 XPS analysis of ES-N/BC samples
Table 2 shows XPS composition analysis of the catalyst prepared in this example, and both metal and nitrogen have been successfully doped into the material.
Fig. 1 is an SEM and TEM test chart of the preparation method of the present embodiment, wherein fig. 1(a) is an SEM and fig. 1(b) is a TEM test chart. As can be seen from fig. 1, the material prepared in this example has a porous flocculent structure and has a rich edge structure. FIG. 2 is a LSV graph comparing the metal-nitrogen co-doped oxygen reduction catalyst prepared in this example with commercial Pt/C. at-0.80V, the absolute value of the limiting current density of ES-N/BC reaches 5.094mA cm-2Reaching and exceeding 5.048mAcm of commercial Pt/C-2The catalytic activity of the catalysts prepared in the examples was comparable to commercial Pt/C. FIG. 3 is a methanol resistance test plot for a commercial Pt/C oxygen reduction catalyst of the prior art. Fig. 4 is a methanol resistance test chart of a metal-nitrogen co-doped oxygen reduction catalyst prepared according to an example of the present invention. As can be seen from FIGS. 3 and 4, the commercial Pt/C showed a clear methanol reaction peak after adding methanol, and its methanol resistance was poor. The material prepared in the embodiment has no change of curve after adding methanol, and has good methanol resistance.
In the embodiment, the method for preparing the metal-nitrogen co-doped oxygen reduction catalyst by using the electroplating sludge comprises the steps of mixing the electroplating sludge, melamine and corn straw biomass powder according to a certain proportion, dissolving the mixture in ultrapure water, magnetically stirring the mixture at room temperature for 4 hours, drying the mixture at 50-70 ℃ after stirring, and grinding the mixture into powder after drying; then taking appropriate amount of powder, and heating at 950 deg.C and N2Pyrolyzing for 2h under protection, cooling to below 100 ℃, and taking out; and placing the obtained product in 1mol/L hydrochloric acid for soaking, shaking, washing and drying to obtain the metal-nitrogen co-doped oxygen reduction catalyst based on the electroplating sludge. The catalyst has oxygen reduction catalytic activity comparable to that of commercial Pt/C in test, has excellent stability, good methanol resistance and simple preparation, is a good measure for changing waste into valuableThe cathode catalyst of the fuel cell provides one option.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (6)
1. A method for preparing a metal-nitrogen codoped oxygen reduction catalyst by using electroplating sludge is characterized by comprising the following steps:
a. drying and grinding corn straws, and then sieving the ground straw powder with a 100-mesh sieve and collecting to obtain straw powder;
b. mixing electroplating sludge, melamine and the straw powder sieved in the step a, dissolving the mixture in ultrapure water, magnetically stirring the mixture at room temperature for at least 4 hours, filtering and separating the mixture after stirring to obtain solid matters, drying the solid matters at 50-70 ℃, and grinding the dried solid matters into mixture powder;
c. putting the mixture powder obtained in the step b into a quartz boat, and carrying out reaction at the temperature of not less than 950 ℃ and in N2Pyrolyzing the mixture for at least 2 hours under protection, then cooling the pyrolysis product to be not higher than 100 ℃, and taking out the pyrolysis product to obtain pyrolytic metal-nitrogen modified biochar;
d. and c, placing the biochar obtained in the step c in hydrochloric acid with the concentration not lower than 1mol/L, soaking, shaking and washing for at least 12 hours, then performing suction filtration and washing with ultrapure water until the pH value is 7, separating and collecting washed products, and then drying at 50-70 ℃ to obtain the metal-nitrogen co-doped oxygen reduction catalyst.
2. The method for preparing the metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge according to claim 1, wherein in the step b, the electroplating sludge, the melamine and the straw powder sieved in the step a are mixed according to a raw material mass ratio of 1:20: 4.
3. The method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge according to claim 1, wherein in the step c, the mixture powder obtained in the step b is taken and placed in a quartz boat, a non-redox protection gas is introduced into a vacuum tube furnace, the flow rate is not lower than 200mL/min, the temperature is programmed to be not lower than 100 ℃ from room temperature, the heating rate is not lower than 10 ℃/min, the temperature is kept for at least 20min at constant temperature, so that the oxygen in the tube furnace is exhausted, and the biomass is in a dry state; then heating to be not less than 950 ℃ at the heating rate of not less than 10 ℃/min, and carrying out constant-temperature carbonization treatment for at least 2 h; and then cooling the pyrolysis product obtained after the constant-temperature carbonization treatment to be not higher than 100 ℃, and taking out the pyrolysis product to obtain the pyrolytic metal-nitrogen modified biochar.
4. The method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge as claimed in claim 1, wherein in the step d, the prepared metal-nitrogen co-doped oxygen reduction catalyst contains not less than 0.65 wt.% of metal and not less than 4.76 wt.% of nitrogen.
5. The method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge as claimed in claim 4, wherein in the step d, the prepared metal-nitrogen co-doped oxygen reduction catalyst contains not less than 0.65 wt.% of metal, not less than 4.76 wt.% of nitrogen, not less than 2.13 wt.% of silicon, not less than 14.35 wt.% of oxygen, and the balance of carbon and impurities.
6. A metal-nitrogen co-doped oxygen reduction catalyst, which is prepared by the method for preparing a metal-nitrogen co-doped oxygen reduction catalyst by using electroplating sludge according to claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769190A (en) * | 2014-01-27 | 2014-05-07 | 华南理工大学 | Method for preparing auto-doping carbon catalytic material of fuel cell by using excess sludge |
| CN105601074A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院广州能源研究所 | Novel efficient resource utilization method of electroplating sludge and carbon dioxide co-processing |
| CN106311224A (en) * | 2016-09-10 | 2017-01-11 | 上海大学 | Preparation method of charcoal-based oxygen reduction catalyst |
| CN109103468A (en) * | 2018-08-22 | 2018-12-28 | 北京化工大学 | A kind of Fe-Mn cycle and transference charcoal oxygen reduction catalyst and its preparation method and application |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
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2020
- 2020-07-10 CN CN202010663359.2A patent/CN111900415A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769190A (en) * | 2014-01-27 | 2014-05-07 | 华南理工大学 | Method for preparing auto-doping carbon catalytic material of fuel cell by using excess sludge |
| CN105601074A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院广州能源研究所 | Novel efficient resource utilization method of electroplating sludge and carbon dioxide co-processing |
| CN106311224A (en) * | 2016-09-10 | 2017-01-11 | 上海大学 | Preparation method of charcoal-based oxygen reduction catalyst |
| CN109103468A (en) * | 2018-08-22 | 2018-12-28 | 北京化工大学 | A kind of Fe-Mn cycle and transference charcoal oxygen reduction catalyst and its preparation method and application |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
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