CN111647907A - Preparation method of self-supporting heteroatom-doped sludge carbon electrode material - Google Patents
Preparation method of self-supporting heteroatom-doped sludge carbon electrode material Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- 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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
Compared with the prior art, the self-supporting heteroatom-doped sludge carbon electrode material prepared by the invention can simultaneously meet the requirements of serving as a hydrogen production catalyst and a working electrode, combines the hydrogen production catalyst and the working electrode into a whole, effectively avoids the problems of the traditional powder catalyst, effectively increases the active sites of hydrogen evolution reaction due to a unique porous self-supporting structure, and solves the problems of high consumption and low efficiency of the existing electrochemical hydrogen evolution technology. In addition, the preparation method provided by the invention is simple and rapid, does not need a loading step, does not need to add various chemical additives such as a doping agent, a modifying agent, a pore-forming agent and the like, reduces the preparation cost, embodies the effects of recycling wastes and generating high added value, and simultaneously provides a new electrode material for the electrolytic water hydrogen evolution technology.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a preparation method of a self-supporting heteroatom-doped sludge carbon electrode material.
Background
Hydrogen energy is recognized as a clean, high calorific value and environmentally friendly energy source. Hydrogen energy can also be used as a medium for storing, transporting, and converting other clean energy sources (solar, wind, biological, etc.). The electrolytic water is an important hydrogen preparation method, most of catalysts for the electrolytic water Hydrogen Evolution Reaction (HER) are precious metal-based (such as Pt) materials, the reserves are rare, the cost is high, and in contrast, the development of low-cost and high-activity non-precious metal catalysts is an important challenge in the field of hydrogen production.
Carbon materials have gradually entered the human vision due to low cost, abundant resources, and good stability. Conventional hydrogen evolution catalytic materials require doping by complex chemical methods to improve the hydrogen evolution performance of the catalyst. However, in the synthesis process of the carbon-doped catalytic material, a chemical agent is required to be added as a dopant, and sometimes a carbon-doped precursor, a pore-forming agent, a template agent and the like are also required to improve the content of doped atoms in the carbon material, the catalytic activity of the catalytic material and active sites of the reaction. The cost of preparing the catalytic material is increased due to the complicated reaction involved, and byproducts are easily generated.
At present, most of the forms of the catalysts for hydrogen evolution from electrolyzed water are powder. When preparing a working electrode, a polymer binder and a conductive additive are needed to load a catalyst on the electrode, but the following problems exist:
(1) the morphology and structure of the catalyst cannot be effectively controlled, so that the dead volume on the catalyst is large, the electrochemical active sites are reduced, an interference interface which is not beneficial to reaction is formed on the surface of the electrode, and the electronic conduction between the electrode and electrolyte in the electrochemical process and the mass transfer of reactants/products in the multiphase reaction process are limited.
(2) Because the gas separated out on the surface of the electrode in the electrocatalytic hydrogen evolution reaction continuously escapes, the catalyst coated on the electrode is easy to separate, and the activity and the service life of the catalyst are damaged.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
The invention aims to: the preparation method of the self-supporting heteroatom-doped sludge carbon electrode material is provided, and the problems of high consumption and low efficiency of the traditional electrochemical hydrogen evolution technology are solved; the electrode material is low in manufacturing cost, chemical agents do not need to be added in the preparation process to serve as doping agents, modifying agents, pore-forming agents and the like, and the effect of recycling wastes to generate high added value is fully reflected.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a self-supporting heteroatom-doped sludge carbon electrode material comprises the following steps:
1) putting the sludge dry powder in an atmosphere furnace, introducing inert gas, heating and pre-carbonizing to obtain first sludge carbon powder, washing and drying the first sludge carbon powder to obtain second sludge carbon powder;
2) placing phenolic resin into a container, adding deionized water for first ultrasonic dispersion, and then adding the second sludge carbon powder for second ultrasonic dispersion to obtain uniform mixed liquor; transferring the mixed solution into an evaporator, and heating and drying the mixed solution in a vacuum state to obtain a sludge-like mixture of the sludge autodoped phenolic resin;
3) pressing and forming the sludge-shaped mixture of the sludge autodoped phenolic resin, and solidifying to obtain a sheet-shaped mixture of the sludge autodoped phenolic resin; then placing the sheet-shaped mixture of the sludge self-doping phenolic resin in an atmosphere furnace, introducing inert gas, keeping the temperature rise and carbonization under anaerobic condition until the sheet-shaped mixture of the sludge self-doping phenolic resin has a porous self-supporting structure; and after carbonization, washing to be neutral, and drying to obtain the self-supporting heteroatom-doped sludge carbon electrode material.
The self-supporting heteroatom-doped sludge carbon electrode material prepared by the invention has an independent supporting structure, can be directly applied to a working electrode of electrochemical reaction, does not need to coat a catalyst on the electrode, does not need to coat an organic adhesive and a conductive additive, and fully utilizes the characteristic of heteroatom doping contained in sludge to improve the electro-catalytic hydrogen evolution performance. The preparation method ensures the integrity and mechanical strength of the self-supporting electrode catalyst, and is beneficial to the electron transfer and gas conduction between the electrode and the electrolyte; the preparation process is simple, the raw materials are easy to obtain, and the electrode has good activity and stability and wide application value. In addition, compared with the powder catalyst, the self-supporting sludge carbon electrode material has rich porous structures, so that on one hand, the self-supporting sludge carbon electrode material is beneficial to the permeation of electrolyte, the diffusion of ions and reaction products and the improvement of the electro-catalytic reaction kinetics in the electrochemical process; on the other hand, the active surface area is increased, and the electrochemical active sites are increased.
The phenolic resin adopted by the invention is the earliest artificially synthesized resin, has the advantages of mature production process, low price, high carbonization yield, single component, low impurity content, easiness in activation and pore formation and the like, and has wide application prospect when being used as an electrode material. The sludge has the characteristic of heteroatom autodoping, and the heteroatoms can not only improve the catalytic performance of the carbon material, but also enhance the stability of the carbon material. The sludge and the phenolic resin are dispersed and mixed uniformly by ultrasound, and are carbonized at high temperature under anaerobic conditions, so that the obtained novel electrode material with the self-supporting structure fully exerts the characteristic of sludge heteroatom autodoping, realizes resource treatment of the sludge on the one hand, and provides a new practical application mode for a sludge resource utilization technology by combining the application of the field of electrocatalysis hydrogen production on the other hand, and has good innovation and research value.
Preferably, the preparation process of the sludge dry powder comprises the following steps: drying sludge to obtain blocky dry sludge, crushing the blocky dry sludge, screening by using a screen to obtain sludge fine powder, carrying out magnetic stirring and cleaning on the sludge fine powder, and drying to obtain the sludge dry powder. The sludge in the digestion tank is subjected to anaerobic biological treatment, most of impurities are removed, organic matters in the sludge are degraded into organic matters mainly comprising methane by bacteria under an anaerobic condition, so that the organic matters are decomposed more quickly and easily in the subsequent pre-carbonization and carbonization processes, and uniform and continuous formation of holes is facilitated.
Preferably, the drying temperature of the sludge is 80-105 ℃; the mesh opening of the mesh screen is 60-80 meshes; the magnetic stirring time of the sludge fine powder is 0.5-1 h, and the drying temperature of the sludge fine powder is 60-80 ℃.
Preferably, in the step 1), the sludge dry powder is placed in an atmosphere furnace, inert gas is introduced, and heating and pre-carbonization are carried out to obtain first sludge carbon powder; and washing the first sludge carbon powder by using deionized water and absolute ethyl alcohol under the condition of magnetic stirring, and drying to obtain second sludge carbon powder. The contact area of the small-particle sludge carbon powder is large, the mixing reaction with the phenolic resin is more uniform, and the mixture formed by the small-particle sludge carbon powder and the phenolic resin is more uniform and consistent in the subsequent processes of press forming, self-supporting structure building and the like due to smaller particles on the whole; in addition, the small particulate matters have small interaction force with each other, and gas generated by the decomposition of the organic matters is more easily discharged.
Preferably, in the step 1), the pre-carbonization temperature is 400-500 ℃, the pre-carbonization time is 1-2 hours, and the flow rate of the inert gas is 200-300 mL/min; the magnetic stirring time of the first sludge carbon powder is 1-2 h; the drying temperature of the first sludge carbon powder is 60-80 ℃. The method is characterized in that the pre-carbonization is carried out at the temperature of 400-500 ℃, a part of substances in the sludge are decomposed and gas is generated to be discharged, holes are formed in advance, a foundation is provided for subsequent carbonization at high temperature by uniformly mixing with phenolic resin, the mixing is more uniform, a certain supporting structure is formed, the formation of a subsequent self-supporting structure is facilitated, and the self-supporting heteroatom-doped sludge carbon electrode material is obtained.
Preferably, in the step 2), the weight ratio of the phenolic resin to the second sludge carbon powder is 1: 2-1: 4. The deionized water can be mixed with the phenolic resin in the ratio of (80-100) to (1-2). The phenolic resin and the second sludge carbon powder can be uniformly mixed by mixing according to the proportion. The higher the proportion of the second sludge carbon powder is, the higher the heteroatom of the sludge is, the more holes are formed in and on the surface of the obtained sludge carbon electrode material, the more active sites of the corresponding electrocatalytic hydrogen evolution reaction are, and the higher the stability of the electrode material is. However, if the proportion of the second sludge carbon powder is too high and the proportion of the phenolic resin is insufficient, the carbonization rate is low, which adversely affects the formation of pores in the second sludge carbon powder and the hydrogen evolution effect of the electrode material. Thus, the weight ratio of the phenolic resin to the second sludge carbon powder is preferably kept to be 1: 2-1: 4, specifically, the weight of the phenolic resin is 5-10 g, the weight of the deionized water is 400-500 mL, and the weight of the second sludge carbon powder is 15-20 g.
Preferably, in the step 2), the time of the first ultrasonic dispersion and the time of the second ultrasonic dispersion are both 1-2 hours; the drying temperature of the mixed liquid is 60-80 ℃, and the drying time of the mixed liquid is 6-8 h. The specific ultrasonic time can be changed along with the different carbonization contents of the added phenolic resin and the second sludge, so that the phenolic resin and the second sludge can be ensured to be finally uniformly mixed.
Preferably, in the step 3), the pressing degree of the mud-like mixture of the sludge self-doping phenolic resin is 20-30 Mpa; the curing is constant temperature curing at the temperature of 180-220 ℃; the curing time is 5-6 h. The mixture is cured under a constant temperature state, so that each surface of the mixture can be uniformly cured, the property of the mixture cannot be influenced due to different temperatures in the mixture and the surface of the mixture, the preheating effect can be achieved when the mixture is cured at 180-220 ℃, a solid foundation is laid for subsequent high-temperature carbonization, and preferably, the constant-temperature curing temperature is 200 ℃.
Preferably, in the step 3), the flow rate of the inert gas is 200-400 mL/min; the temperature rise rate of the carbonization is 5-10 ℃/min, and the temperature of the carbonization is 800-1000 ℃; the carbonization time is 2-2.5 h. The uniform heating rate is helpful for fully exciting the early reaction of the organic components in the sludge, and provides a foundation for the subsequent rapid decomposition of the organic components under the high-temperature anaerobic carbonization condition, and decomposed gas can be continuously discharged, so that abundant holes are formed inside and on the surface of the sludge carbon electrode, and a porous self-supporting structure can be uniformly formed under the condition.
Preferably, in the step 3), after carbonization, acid washing is performed firstly, then water washing is performed to be neutral, and the self-supporting heteroatom-doped sludge carbon electrode material is obtained after drying; wherein the acid concentration of the acid washing is 0.1-0.2M, and the drying temperature is 60-80 ℃. The acid used for acid washing may be HNO3、HCl、H2SO4At least one of (1).
The invention has the beneficial effects that:
1) compared with the prior art, the self-supporting heteroatom-doped sludge carbon electrode material prepared by the invention can simultaneously meet the requirements of serving as a hydrogen production catalyst and a working electrode, combines the hydrogen production catalyst and the working electrode into a whole, not only effectively avoids the problems of the traditional powder catalyst, but also effectively increases the active sites of hydrogen evolution reaction due to the unique porous self-supporting structure, and solves the problems of high consumption and low efficiency of the existing electrochemical hydrogen evolution technology. In addition, the preparation method provided by the invention is simple and rapid, does not need a loading step, does not need to add various chemical additives such as a doping agent, a modifying agent, a pore-forming agent and the like, reduces the preparation cost, embodies the effects of recycling wastes and generating high added value, and simultaneously provides a new electrode material for the electrolytic water hydrogen evolution technology.
2) The preparation method comprises the steps of ultrasonically dispersing and uniformly mixing the sludge and the phenolic resin, then performing press forming on the mixture, performing anaerobic high-temperature carbonization on the mixture, and finally converting the mixture into the electrode material.
3) Under the condition of high-temperature anaerobic carbonization, the organic components of the sludge are quickly decomposed and generate gas to be discharged, and because the gas is continuously discharged, rich holes are formed in the interior and the surface of the sludge carbon electrode material, so that the active surface area of the sludge carbon electrode material is increased, and further, active sites of the sludge carbon electrode material for electrocatalytic hydrogen evolution reaction are increased, hydrogen production reaction and hydrogen gas precipitation are facilitated, the blockage and inactivation of the sludge carbon electrode material are prevented, and the stability of the sludge carbon electrode material is improved.
4) The sludge contains heteroatom catalytic components such as Fe, S, P and the like, has the advantage of heteroatom self-doping, and the doped heteroatom is beneficial to the catalytic hydrogen evolution reaction, so that the electrocatalytic hydrogen evolution effect of the sludge carbon electrode material is further improved, and if the sludge carbon electrode material is taken as a catalyst, the activity and the service life of the catalyst are prolonged.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
FIG. 2 is a scanning electron micrograph of an electrode material according to example 3.
FIG. 3 is a second SEM image of the electrode material of example 3.
FIG. 4 is an elemental analysis chart of the electrode material of example 3.
FIG. 5 is a linear voltammogram of hydrogen evolution for the electrode materials of examples 1, 2, and 3 made at different temperatures.
FIG. 6 is a graph of current versus time at 1000 ℃ for the electrode material of example 3.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
As shown in fig. 1, a preparation method of a self-supporting heteroatom-doped sludge carbon electrode material comprises the following steps:
1) naturally airing sludge in a digestion tank under outdoor conditions, and then putting the sludge into an oven to dry the sludge to obtain blocky dry sludge, wherein the drying temperature is 105 ℃; taking out the blocky dry sludge, putting the blocky dry sludge into a grinder for grinding and polishing, and then screening the blocky dry sludge by a 60-mesh screen to obtain sludge fine powder; and then placing the sludge fine powder into a container, adding deionized water, carrying out magnetic stirring and cleaning for 1h, filtering through a filter membrane of 0.45 mu m, and then placing into a drying oven to dry for 6h at 60 ℃ to obtain sludge dry powder.
2) Placing the sludge dry powder in a tubular atmosphere furnace, and introducing inert gas N with the flow rate of 250mL/min2Pre-carbonizing at 450 ℃ for 1h to obtain first sludge carbon powder, stirring with deionized water and absolute ethyl alcohol under magnetic stirring for 1h to wash the first sludge carbon powder, and drying to obtain second sludge carbon powder at 60 ℃.
3) 10g of phenolic resin is placed in a container, 500mL of deionized water is added for the first ultrasonic dispersion, and the dispersion time is 2 h; then adding 20g of second sludge carbon powder for second ultrasonic dispersion for 2 h; obtaining uniform mixed liquor; transferring the mixed solution to a rotary evaporator, heating to 70 ℃ in a vacuum state, and drying for 6h to obtain a sludge-like mixture of the sludge autodoped phenolic resin.
4) Shaping the sludge-shaped mixture of the sludge autodoping phenolic resin by using a cylindrical mold with the diameter of 20.20.3 mm for 30min, pressing the shaped mixture into a plate with the diameter of 20.20 mm and the thickness of 3mm by using a tablet press under the force of 30Mpa, and curing the plate for 6h in a vacuum constant-temperature drying box with the temperature of 200 ℃ to obtain a plate-shaped mixture of the sludge autodoping phenolic resin; then placing the sheet mixture of the sludge self-doped phenolic resin in a tubular atmosphere furnace, heating and carbonizing under the protection of 300mL/min nitrogen atmosphere, respectively heating to 800 ℃ at the heating rate of 5 ℃/min, carbonizing at high temperature for 2h, cooling to room temperature, and taking out to finish carbonization; then firstly passes through 0.1M HNO3And (3) pickling for 6h, washing with water to be neutral, and drying in an oven at 60 ℃ to obtain the self-supporting heteroatom-doped sludge carbon electrode material.
Example 2
As shown in fig. 1, a preparation method of a self-supporting heteroatom-doped sludge carbon electrode material comprises the following steps:
1) naturally airing sludge in a digestion tank under outdoor conditions, and then putting the sludge into an oven to dry the sludge to obtain blocky dry sludge, wherein the drying temperature is 80 ℃; taking out the blocky dry sludge, putting the blocky dry sludge into a grinder for grinding and polishing, and then screening the blocky dry sludge by a 60-mesh screen to obtain sludge fine powder; and then placing the sludge fine powder into a container, adding deionized water, carrying out magnetic stirring and cleaning for 1h, filtering through a filter membrane of 0.45 mu m, and then placing into a drying oven to dry for 5.5h at 80 ℃ to obtain sludge dry powder.
2) Placing the sludge dry powder in a tubular atmosphere furnace, and introducing inert gas N with the flow rate of 300mL/min2Pre-carbonizing at 500 deg.C for 1h to obtain first sludge charcoal powder, stirring with deionized water and anhydrous ethanol under magnetic stirring for 1.5h to wash the first sludge charcoal powder, and drying to obtain second sludge charcoal powder at 70 deg.C.
3) Putting 7.5g of phenolic resin into a container, and adding 450mL of deionized water for first ultrasonic dispersion, wherein the dispersion time is 1.5 h; then adding 17.5g of second sludge carbon powder for second ultrasonic dispersion, wherein the dispersion time is 1.5 h; obtaining uniform mixed liquor; transferring the mixed solution to a rotary evaporator, heating to 70 ℃ in a vacuum state, and drying for 6h to obtain a sludge-like mixture of the sludge autodoped phenolic resin.
4) Shaping the sludge-shaped mixture of the sludge autodoping phenolic resin by using a cylindrical mold with the diameter of 20.20.3 mm for 30min, pressing the shaped mixture into a sheet with the diameter of 20.20 mm and the thickness of 3mm by using a tablet press under the force of 30Mpa, and curing the sheet for 5h in a vacuum constant-temperature drying box with the temperature of 200 ℃ to obtain a sheet-shaped mixture of the sludge autodoping phenolic resin; then placing the sheet mixture of the sludge self-doped phenolic resin in a tubular atmosphere furnace, heating and carbonizing under the protection of 300mL/min nitrogen atmosphere, respectively heating to 900 ℃ at the heating rate of 7.5 ℃/min, carbonizing at high temperature for 2h, cooling to room temperature, and taking out to finish carbonization; then firstly passes through 0.1M HNO3And (3) pickling for 6h, washing with water to be neutral, and drying in an oven at 60 ℃ to obtain the self-supporting heteroatom-doped sludge carbon electrode material.
Example 3
As shown in fig. 1, a preparation method of a self-supporting heteroatom-doped sludge carbon electrode material comprises the following steps:
1) naturally airing sludge in a digestion tank under outdoor conditions, and then putting the sludge into an oven to dry the sludge to obtain blocky dry sludge, wherein the drying temperature is 105 ℃; taking out the blocky dry sludge, putting the blocky dry sludge into a grinder for grinding and polishing, and then screening the blocky dry sludge by a 60-mesh screen to obtain sludge fine powder; and then placing the sludge fine powder into a container, adding deionized water, carrying out magnetic stirring and cleaning for 1h, filtering through a filter membrane of 0.45 mu m, and then placing into a drying oven to dry for 6h at 60 ℃ to obtain sludge dry powder.
2) Placing the sludge dry powder in a tubular atmosphere furnace, and introducing inert gas N with the flow rate of 200mL/min2Pre-carbonizing at 400 ℃ for 2h to obtain first sludge carbon powder, stirring with deionized water and absolute ethyl alcohol under magnetic stirring for 2h to wash the first sludge carbon powder, and drying to obtain second sludge carbon powder at 80 ℃.
3) Putting 5g of phenolic resin into a container, and adding 400mL of deionized water for first ultrasonic dispersion, wherein the dispersion time is 1 h; then adding 15g of second sludge carbon powder for second ultrasonic dispersion, wherein the dispersion time is 1.5 h; obtaining uniform mixed liquor; transferring the mixed solution to a rotary evaporator, heating to 60 ℃ in a vacuum state, and drying for 6h to obtain a sludge-like mixture of the sludge autodoped phenolic resin.
4) Shaping the sludge-shaped mixture of the sludge autodoping phenolic resin by using a cylindrical mold with the diameter of 20.20.3 mm for 30min, pressing the shaped mixture into a plate with the diameter of 20.20 mm and the thickness of 3mm by using a tablet press under the force of 30Mpa, and curing the plate for 6h in a vacuum constant-temperature drying box with the temperature of 180 ℃ to obtain a plate-shaped mixture of the sludge autodoping phenolic resin; then placing the sheet mixture of the sludge self-doped phenolic resin in a tubular atmosphere furnace, heating and carbonizing under the protection of 200mL/min nitrogen atmosphere, respectively heating to 1000 ℃ at the heating rate of 10 ℃/min, carbonizing at high temperature for 2h, cooling to room temperature, and taking out to finish carbonization; then firstly passes through 0.1M HNO3And (3) pickling for 6h, washing with water to be neutral, and drying in an oven at 60 ℃ to obtain the self-supporting heteroatom-doped sludge carbon electrode material.
The self-supporting heteroatom-doped sludge carbon electrode material obtained in the example 3 is characterized and directly applied to a hydrogen evolution electrochemical experiment as a working electrode, and the characterization and experiment results are shown in fig. 2-6.
As can be seen from fig. 2 to 4, the electrode material has a porous structure, contains heteroatoms such as S, P, Fe, has the characteristic of heteroatom autodoping, and the heteroatom-doped carbon material is beneficial to the hydrogen evolution reaction.
In the hydrogen evolution electrochemical experiment, a three-electrode electrochemical reaction is used for carrying out an experiment, wherein a working electrode is the self-supporting heteroatom-doped sludge carbon electrode, a counter electrode is a graphite rod, a reference electrode is a saturated calomel electrode, and an electrolyte is 0.5MH2SO4. As can be seen from FIG. 5, the overpotential of the sludge carbon electrode material at different temperatures is-173 mV, -314mV, -385mV when the hydrogen evolution reaction reaches 10mA, and the hydrogen evolution current efficiency of the sludge carbon electrode material is superior to that of the conventional carbon-based electrode materials such as graphite plates, graphite felts and the like. From fig. 6, it can be seen that the prepared self-supporting heteroatom-doped sludge carbon electrode material has excellent stability after long-term current stability analysis. The self-supporting heteroatom-doped sludge carbon electrode material can be used as an independent working electrode to perform a hydrogen evolution experiment and is a novel electrocatalytic carbon electrode material.
From the data results, the self-supporting heteroatom-doped sludge carbon electrode material simultaneously meets the requirements of a hydrogen production catalyst and a working electrode, combines the hydrogen production catalyst and the working electrode into a whole, not only omits the catalyst loading arrangement, but also omits the addition of various chemical additives such as a doping agent, a modifying agent, a pore-forming agent and the like, reduces the production cost and simultaneously improves the efficiency of the electrochemical hydrogen evolution technology.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a self-supporting heteroatom-doped sludge carbon electrode material is characterized by comprising the following steps:
1) putting the sludge dry powder in an atmosphere furnace, introducing inert gas, heating and pre-carbonizing to obtain first sludge carbon powder, washing and drying the first sludge carbon powder to obtain second sludge carbon powder;
2) placing phenolic resin into a container, adding deionized water for first ultrasonic dispersion, and then adding the second sludge carbon powder for second ultrasonic dispersion to obtain uniform mixed liquor; transferring the mixed solution into an evaporator, and heating and drying the mixed solution in a vacuum state to obtain a sludge-like mixture of the sludge autodoped phenolic resin;
3) pressing and forming the sludge-shaped mixture of the sludge autodoped phenolic resin, and solidifying to obtain a sheet-shaped mixture of the sludge autodoped phenolic resin; then placing the sheet-shaped mixture of the sludge self-doping phenolic resin in an atmosphere furnace, introducing inert gas, keeping the temperature rise and carbonization under anaerobic condition until the sheet-shaped mixture of the sludge self-doping phenolic resin has a porous self-supporting structure; and after carbonization, washing to be neutral, and drying to obtain the self-supporting heteroatom-doped sludge carbon electrode material.
2. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein the preparation process of the sludge dry powder is as follows: drying sludge to obtain blocky dry sludge, crushing the blocky dry sludge, screening by using a screen to obtain sludge fine powder, carrying out magnetic stirring and cleaning on the sludge fine powder, and drying to obtain the sludge dry powder.
3. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 2, wherein the drying temperature of the sludge is 80-105 ℃; the mesh opening of the mesh screen is 60-80 meshes; the magnetic stirring time of the sludge fine powder is 0.5-1 h, and the drying temperature of the sludge fine powder is 60-80 ℃.
4. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 1), sludge dry powder is placed in an atmosphere furnace, inert gas is introduced, and heating and pre-carbonization are performed to obtain first sludge carbon powder; and washing the first sludge carbon powder by using deionized water and absolute ethyl alcohol under the condition of magnetic stirring, and drying to obtain second sludge carbon powder.
5. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 4, wherein in the step 1), the pre-carbonization temperature is 400-500 ℃, the pre-carbonization time is 1-2 h, and the flow rate of the inert gas is 200-300 mL/min; the magnetic stirring time of the first sludge carbon powder is 1-2 h; the drying temperature of the first sludge carbon powder is 60-80 ℃.
6. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 2), the weight ratio of the phenolic resin to the second sludge carbon powder is 1: 2-1: 4.
7. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 2), the time of the first ultrasonic dispersion and the time of the second ultrasonic dispersion are both 1-2 h; the drying temperature of the mixed liquid is 60-80 ℃, and the drying time of the mixed liquid is 6-8 h.
8. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 3), the pressing forming pressure of the sludge-like mixture of the sludge self-doped phenolic resin is 20-30 Mpa; the curing is constant temperature curing at the temperature of 180-220 ℃; the curing time is 5-6 h.
9. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 3), the flow rate of the inert gas is 200-400 mL/min; the temperature rise rate of the carbonization is 5-10 ℃/min, and the temperature of the carbonization is 800-1000 ℃; the carbonization time is 2-2.5 h.
10. The preparation method of the self-supporting heteroatom-doped sludge carbon electrode material as claimed in claim 1, wherein in the step 3), after carbonization is completed, acid washing is performed firstly, then water washing is performed to neutrality, and drying is performed to obtain the self-supporting heteroatom-doped sludge carbon electrode material; wherein the acid concentration of the acid washing is 0.1-0.2M, and the drying temperature is 60-80 ℃.
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| CN109500062A (en) * | 2018-12-13 | 2019-03-22 | 南京工业大学 | A kind of preparation method of the waste tire recycling material of excess sludge improvement |
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| WO2018033161A1 (en) * | 2016-08-19 | 2018-02-22 | 山东圣泉新材料股份有限公司 | Modified phenolic-resin fiber and method for fabricating same and use of same, and composite material made of said modified phenolic-resin fiber and used for electrode |
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