CN112591728A - Waste paper aerogel, aerogel derivative and preparation method thereof - Google Patents
Waste paper aerogel, aerogel derivative and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a waste paper aerogel, an aerogel derivative and a preparation method thereof, belonging to the technical field of aerogel materials. The method for preparing aerogel by using the waste paper comprises the following steps: soaking, deinking and surface functionalization treatment of waste paper, filtering, molding and drying to obtain waste paper aerogel, and calcining at 400-1000 ℃ to obtain waste paper carbon aerogel; the surface functionalization treatment comprises the following steps: and (2) treating the waste paper by using a compound A solution, wherein the pH value of the treatment is 4-4.5, the treatment temperature is 70-80 ℃, the treatment time is 2-6 h, and the compound A is one of hydrogen peroxide, sodium hypochlorite, sodium chlorite and sodium periodate. The method for preparing aerogel by using waste paper has the advantages of simple preparation process, short period, small secondary pollution and the like. The prepared aerogel is more stable. The metal organic framework derivative @ waste paper based composite carbon aerogel can load a large amount of electrocatalytic active substances, is light and has high conductivity, and can be widely used for commercial electrocatalytic materials.
Description
Technical Field
The invention relates to a waste paper aerogel, an aerogel derivative and a preparation method thereof, belonging to the technical field of aerogel materials.
Background
The recycling of waste printing paper, corrugated paper, paper towels and the like in daily life has become one of the focuses of urgent attention of people. The realization of the recycling of waste paper is of great significance in solving the aspects of resource consumption and environmental pollution, and three major applications of waste paper recycling currently include the manufacture of recycled paper, the manufacture of household appliances and the production of solid fuels for power generation.
Currently, realizing the recycling of waste paper with high added value is one of the major challenges facing currently. The waste paper contains a large amount of cellulose, and the waste paper is used as a source of cellulose raw materials to prepare the cellulose carbon aerogel, so that high-added-value recycling of the waste paper can be realized, the problems of environment and resources are relieved, and sustainable development is realized. The cellulose carbon aerogel has the advantages of large specific surface area, rich pore structure, high mechanical property, chemical stability, thermal stability and electrical conductivity, and has good performances in the fields of catalyst carriers, supercapacitor electrodes, adsorbents and sensors. The carbon aerogel prepared by using the waste paper as the raw material by a relatively simple, convenient, economic and safe method has great value potential.
The process for preparing the aerogel by using the waste paper in the prior art is complex, high in cost and large in environmental pollution, for example, the method for preparing the aerogel by using the waste paper disclosed in CN2016112074128, CN2019100559969, CN2017104470419 and the like needs to use alkali, and cellulose in the waste paper is dissolved, gelatinized and then freeze-dried. Aerogels prepared from these prior art broke are prone to damage the metal organic framework structure, and severely affect the crosslinking of the cellulose and inhibit gelation. In addition, in the process of phosphorization or phosphorylation treatment, the aerogel prepared from the existing waste paper cannot resist high temperature calcination and hydrothermal treatment, and the cellular porous structure of the aerogel cannot be effectively maintained.
Patent application CN2020100850482 discloses a metal organic framework composite aerogel material, a preparation method and use thereof; it is used in the field of electromagnetic shielding. Patent application CN2015100986180 discloses a method for synthesizing ZIF-8 aerogel based on cellulose hard template; the aerogel disclosed therein is used in combination with a metal organic framework for gas storage. It is not disclosed how to prepare a material with good electrocatalytic properties.
Disclosure of Invention
The first problem to be solved by the invention is to provide a novel method for preparing aerogel from waste paper.
In order to solve the first technical problem of the present invention, the method for preparing aerogel by using waste paper comprises the following steps:
soaking, deinking and surface functionalization treatment of waste paper, filtering, molding and drying to obtain waste paper aerogel, and calcining at 400-1000 ℃ to obtain waste paper carbon aerogel;
the surface functionalization treatment comprises the following steps: treating waste paper by using a compound A solution, wherein the pH value of the treatment is 4-4.5, the treatment temperature is 70-80 ℃, the treatment time is 2-6 h, and the compound A is one of hydrogen peroxide, sodium hypochlorite, sodium chlorite and sodium periodate;
the pH is preferably adjusted with glacial acetic acid, dilute hydrochloric acid or dilute sulfuric acid.
The soaking and deinking can adopt water.
Before the waste paper is soaked, the waste paper can be cut into pieces. The solution can also be washed before the suction filtration.
In one embodiment, compound a is sodium hypochlorite; the concentration of the sodium hypochlorite solution is preferably 0.1-0.3 mol/L; the preferable mass ratio of the sodium hypochlorite dosage to the waste paper is 0.7-3: 1.
in one embodiment, the method comprisesThe calcination is in N2Or Ar gas atmosphere, wherein the temperature rise rate of the calcination is preferably 2-5 ℃/min, and the calcination time is preferably kept at 400-1000 ℃ for 2-3 h.
The second technical problem to be solved by the invention is to provide a waste paper aerogel.
In order to solve the second technical problem of the invention, the waste paper aerogel is prepared by adopting the method for preparing aerogel from waste paper.
The aerogel manufactured by the invention is fiber aerogel formed by stacking carbon fibers formed by carbonizing waste paper fibers, and obvious hole structures are formed among the fibers, so that the aerogel has obvious structural difference from the aerogel prepared by the existing waste paper.
The third technical problem to be solved by the invention is to provide a preparation method of the metal organic framework derivative @ composite carbon aerogel.
In order to solve the third technical problem of the invention, the preparation method of the metal organic framework derivative @ composite carbon aerogel comprises the following steps:
a. mixing the aerogel with a metal organic framework precursor solution to obtain a mixed solution, and aging or hydro-thermal treating to obtain metal organic framework @ carbon aerogel;
preferably, the mass ratio of the aerogel to the metal organic framework precursor is 3-5: 50 to 100
b. Phosphating or phosphorylating a metal organic framework @ carbon aerogel, and obtaining a metal organic framework derivative @ composite carbon aerogel by using a high-temperature carbonization or hydrothermal treatment method;
the metal organic framework precursor solution is a mixed solution of at least one of cobalt nitrate, ferric nitrate, zinc nitrate, cerium nitrate and zirconium nitrate and an organic ligand, wherein the organic ligand is at least one of isophthalic acid, terephthalic acid and 2-methylimidazole;
the metal organic framework is preferably at least one of ZIF-67, ZIF-8, MIL-88 and UiO-66;
the aerogel in the step a is preferably prepared by adopting the method for preparing the aerogel from the waste paper.
In a specific embodiment, the aging treatment in the step a is aging at 20-30 ℃ for 3-24 h, and the hydrothermal treatment in the step a is hydrothermal treatment at 120-160 ℃ for 2-5 h.
In one embodiment, the phosphating treatment in step b uses at least one of sodium hypophosphite and sodium phosphite as the phosphorus source, and the phosphating treatment in step b uses at least one of sodium phosphate and potassium phosphate as the phosphorus source.
In a specific embodiment, when the high-temperature carbonization is adopted in the step b, the mass ratio of the phosphorus source to the metal organic framework @ aerogel is 2-10: 1;
preferably, the high-temperature carbonization in the step b is kept for 2-3 h at 300-350 ℃ in Ar atmosphere, and preferably, the heating rate of the high-temperature carbonization is 2-5 ℃/min.
In a specific embodiment, when the hydrothermal treatment is adopted in the step b, the concentration of the phosphorus source is 0.5-1.5 g/L;
b, preferably carrying out hydrothermal treatment at 100-150 ℃ for 10-24 h;
preferably, before hydrothermal treatment, the metal organic framework @ carbon aerogel and at least one of nickel nitrate or nickel sulfate solution are subjected to ultrasonic or water bath heating treatment to obtain layered double hydroxide @ composite carbon aerogel, and then the layered double hydroxide @ composite carbon aerogel is mixed with a phosphorus source and subjected to hydrothermal treatment; more preferably, the ultrasonic time is 10-120 min or the water bath heating temperature is 30-80 ℃, the heating time is 60-180 min, and the concentration of the nickel nitrate or nickel sulfate solution is preferably 1-5 g/L.
The fourth technical problem to be solved by the invention is to provide a metal organic framework derivative @ composite carbon aerogel.
In order to solve the fourth technical problem, the metal organic framework derivative @ composite carbon aerogel is prepared by adopting the preparation method of the metal organic framework derivative @ composite carbon aerogel;
preferably, the density of the metal organic framework derivative @ composite carbon aerogel is 30-80 mg/cm3；
More preferably, the metal-organic framework is derivatizedThe composite carbon aerogel is prepared at 10mA/cm2The OER overpotential under the current density is 300-410 mV.
Has the advantages that:
1. the method for manufacturing the aerogel by using the waste paper directly adopts a suction filtration method for cellulose in the waste paper, and the aerogel can be obtained by collecting and drying.
2. The aerogel prepared by the waste paper is fiber aerogel formed by stacking carbon fibers formed by carbonizing waste paper fibers, obvious hole structures are formed among the fibers, and the aerogel is obviously different from the aerogel prepared by the existing waste paper in structure, and is more stable in compounding with a metal frame and subsequent phosphating treatment.
3. The metal organic framework derivative @ waste paper-based composite carbon aerogel prepared by using waste paper has the characteristics of high production efficiency, simple process and easiness in large-scale production, and solves the problem of environmental pollution caused by the waste paper.
4. The metal organic framework derivative @ waste paper-based composite carbon aerogel prepared by the method is of an internal loose porous structure and has the characteristic of high specific surface area. A large amount of electrocatalytically active material may be supported.
5. The metal organic framework derivative @ waste paper based composite carbon aerogel prepared by the method is light and high in conductivity, and the density is 30-80 mg/cm3The conductivity is 0.5 to 10S/m.
6. The metal organic framework derivative @ waste paper based composite carbon aerogel prepared by the invention is 10mA/cm2The overpotential of the electrocatalytic oxygen evolution reaction under the current density is 300-410 mV, which reaches the commercial standard and can be widely used for commercial electrocatalytic materials.
7. The invention does not need alkali to treat the waste paper, does not need a cross-linking agent and has low cost.
Drawings
FIG. 1 is a flow chart of a method for preparing a metal-organic framework derivative @ waste paper-based composite carbon aerogel in example 2 of the present invention.
FIG. 2 is a schematic representation of a metal-organic framework derivative @ waste paper-based composite carbon aerogel in example 2 of the present invention.
FIG. 3 is a scanning electron microscope image of the metal-organic framework derivative @ waste paper-based composite carbon aerogel in example 2 of the present invention.
Detailed Description
In order to solve the first technical problem of the present invention, the method for preparing aerogel by using waste paper comprises the following steps:
soaking, deinking and surface functionalization treatment of waste paper, filtering, molding and drying to obtain waste paper aerogel, and calcining at 400-1000 ℃ to obtain waste paper carbon aerogel;
the surface functionalization treatment comprises the following steps: treating waste paper by using a compound A solution, wherein the pH value of the treatment is 4-4.5, the treatment temperature is 70-80 ℃, the treatment time is 2-6 h, and the compound A is one of hydrogen peroxide, sodium hypochlorite, sodium chlorite and sodium periodate;
the pH is preferably adjusted with glacial acetic acid, dilute hydrochloric acid or dilute sulfuric acid.
The soaking and deinking can adopt water.
Before the waste paper is soaked, the waste paper can be cut into pieces. The solution can also be washed before the suction filtration.
In one embodiment, compound a is sodium hypochlorite; the concentration of the sodium hypochlorite solution is preferably 0.1-0.3 mol/L; the preferable mass ratio of the sodium hypochlorite dosage to the waste paper is 0.7-3: 1.
in one embodiment, the calcination is in N2Or Ar gas atmosphere, wherein the temperature rise rate of the calcination is preferably 2-5 ℃/min, and the calcination time is preferably kept at 400-1000 ℃ for 2-3 h.
In order to solve the second technical problem of the invention, the waste paper aerogel is prepared by adopting the method for preparing aerogel from waste paper.
The aerogel manufactured by the invention is fiber aerogel formed by stacking carbon fibers formed by carbonizing waste paper fibers, and obvious hole structures are formed among the fibers, so that the aerogel has obvious structural difference from the aerogel prepared by the existing waste paper.
In order to solve the third technical problem of the invention, the preparation method of the metal organic framework derivative @ composite carbon aerogel comprises the following steps:
a. mixing the aerogel with a metal organic framework precursor solution to obtain a mixed solution, and aging or hydro-thermal treating to obtain metal organic framework @ carbon aerogel;
preferably, the mass ratio of the aerogel to the metal organic framework precursor is 3-5: 50 to 100
b. Phosphating or phosphorylating a metal organic framework @ carbon aerogel, and obtaining a metal organic framework derivative @ composite carbon aerogel by using a high-temperature carbonization or hydrothermal treatment method;
the metal organic framework precursor solution is a mixed solution of at least one of cobalt nitrate, ferric nitrate, zinc nitrate, cerium nitrate and zirconium nitrate and an organic ligand, wherein the organic ligand is at least one of isophthalic acid, terephthalic acid and 2-methylimidazole;
the metal organic framework is preferably at least one of ZIF-67, ZIF-8, MIL-88 and UiO-66;
the aerogel in the step a is preferably prepared by adopting the method for preparing the aerogel from the waste paper.
In a specific embodiment, the aging treatment in the step a is aging at 20-30 ℃ for 3-24 h, and the hydrothermal treatment in the step a is hydrothermal treatment at 120-160 ℃ for 2-5 h.
In one embodiment, the phosphating treatment in step b uses at least one of sodium hypophosphite and sodium phosphite as the phosphorus source, and the phosphating treatment in step b uses at least one of sodium phosphate and potassium phosphate as the phosphorus source.
In a specific embodiment, when the high-temperature carbonization is adopted in the step b, the mass ratio of the phosphorus source to the metal organic framework @ aerogel is 2-10: 1;
preferably, the high-temperature carbonization in the step b is kept for 2-3 h at 300-350 ℃ in Ar atmosphere, and preferably, the heating rate of the high-temperature carbonization is 2-5 ℃/min.
In a specific embodiment, when the hydrothermal treatment is adopted in the step b, the concentration of the phosphorus source is 0.5-1.5 g/L;
b, preferably carrying out hydrothermal treatment at 100-150 ℃ for 10-24 h;
preferably, before hydrothermal treatment, the metal organic framework @ carbon aerogel and at least one of nickel nitrate or nickel sulfate solution are subjected to ultrasonic or water bath heating treatment to obtain layered double hydroxide @ composite carbon aerogel, and then the layered double hydroxide @ composite carbon aerogel is mixed with a phosphorus source and subjected to hydrothermal treatment; more preferably, the ultrasonic time is 10-120 min or the water bath heating temperature is 30-80 ℃, the heating time is 60-180 min, and the concentration of the nickel nitrate or nickel sulfate solution is preferably 1-5 g/L.
In order to solve the fourth technical problem, the metal organic framework derivative @ composite carbon aerogel is prepared by adopting the preparation method of the metal organic framework derivative @ composite carbon aerogel;
preferably, the density of the metal organic framework derivative @ composite carbon aerogel is 30-80 mg/cm3；
More preferably, the metal organic framework derivative @ composite carbon aerogel is at 10mA/cm2The OER overpotential under the current density is 300-410 mV.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
10g of printing waste paper is cut into pieces, 1L of deionized water is added, and the mixture is mechanically stirred for 6 hours. Until the waste paper was stirred into chips, 0.14mol of sodium hypochlorite was added and the pH was adjusted to 4.5 with glacial acetic acid. Stirring the waste paper pulp liquid in a water bath kettle at the temperature of 80 ℃ for 2 hours. And repeatedly filtering and washing the waste paper pulp liquid for 3 times by using water and ethanol. And finally, adding 1L of ethanol into the waste paper, uniformly dispersing, performing suction filtration to obtain waste paper aerogel, and drying to obtain the waste paper aerogel. And (3) putting the waste paper aerogel into a tubular furnace, introducing Ar, heating at the heating speed of 5 ℃/min, carrying out carbon treatment at the specified temperature of 1000 ℃ for 2h, and naturally cooling to obtain the waste paper carbon aerogel. 300mg of cobalt nitrate and 600mg of 2-methylimidazole were dissolved in 20ml of methanol, respectively. And (3) quickly adding the cobalt nitrate solution into the 2-methylimidazole solution, and stirring for 3 minutes to obtain a purple ZIF-67 precursor solution. And adding 47mg of waste paper carbon aerogel into 900mg of purple precursor solution, aging for 24h at 25 ℃, cleaning and drying to obtain ZIF-67@ waste paper-based composite carbon aerogel.
Mixing sodium hypophosphite and ZIF-67@ waste paper-based composite carbon aerogel according to the weight ratio of 5: the proportion of 1 is respectively put into two porcelain boats, the porcelain boats are sequentially placed in a tube furnace, the temperature is raised to 350 ℃ for 2 hours at the temperature raising speed of 5 ℃/min in the Ar atmosphere, and the porcelain boats are naturally cooled and then taken out to obtain the cobalt phosphide @ waste paper based composite carbon aerogel.
The properties of the metal organic framework derived cobalt phosphide @ waste paper based composite carbon aerogel obtained in example 1 are as follows:
the density of the metal organic framework derived cobalt phosphide @ waste paper-based composite carbon aerogel is 36mg/cm3
The conductivity was 4.8S/m
The overpotential is 403mV (. eta.)10)
The Tafel slope was 93.3 mV/dec.
Example 2
10g of printing waste paper is cut into pieces, 1L of deionized water is added, and the mixture is mechanically stirred for 6 hours. Until the waste paper was stirred into chips, 0.14mol of sodium hypochlorite was added and the pH was adjusted to 4.5 with glacial acetic acid. Stirring the waste paper pulp liquid in a water bath kettle at the temperature of 80 ℃ for 2 hours. And repeatedly filtering and washing the waste paper pulp liquid for 3 times by using water and ethanol. And finally, adding 1L of ethanol into the waste paper, uniformly dispersing, performing suction filtration to obtain waste paper aerogel, and drying to obtain the waste paper aerogel. And (3) putting the waste paper aerogel into a tubular furnace, introducing Ar, heating at the heating speed of 5 ℃/min, carrying out carbon treatment at the specified temperature of 1000 ℃ for 2h, and naturally cooling to obtain the waste paper carbon aerogel. 300mg of cobalt nitrate and 600mg of 2-methylimidazole were dissolved in 20ml of methanol, respectively. And (3) quickly adding the cobalt nitrate solution into the 2-methylimidazole solution, and stirring for 3 minutes to obtain a purple ZIF-67 precursor solution. Adding 43mg of waste paper carbon aerogel into 900mg of purple precursor solution, aging for 24h at 25 ℃, cleaning and drying to obtain ZIF-67@ waste paper-based composite carbon aerogel.
Adding 80mg of nickel nitrate into 25ml of ethanol solution, adding the prepared ZIF-67@ waste paper-based composite carbon aerogel, and carrying out ultrasonic oscillation for 1h to obtain the layered double hydroxide @ waste paper-based composite carbon aerogel, also called LDH @ waste paper-based composite carbon aerogel. Adding 40mg of sodium phosphate into 25ml of deionized water, pouring the sodium phosphate solution into the nickel nitrate solution, continuing ultrasonic treatment for 20min, then putting the mixture into a reaction kettle, and carrying out hydrothermal treatment for 15h in a forced air drying oven at 110 ℃. And cleaning and drying to obtain the cobalt phosphate @ waste paper based composite carbon aerogel.
The properties of the metal organic framework derived cobalt phosphate @ waste paper based composite carbon aerogel obtained in example 2 are as follows:
the density of the metal organic framework derived cobalt phosphate @ waste paper based composite carbon aerogel is 38.5mg/cm3
The conductivity was 4.8S/m
The overpotential is 360mV (eta)10)
The Tafel slope was 68.8 mV/dec.
Example 3
10g of printing waste paper is cut into pieces, 1L of deionized water is added, and the mixture is mechanically stirred for 6 hours. Until the waste paper was stirred into chips, 0.2mol of sodium hypochlorite was added and the pH was adjusted to 4.5 with glacial acetic acid. Stirring the waste paper pulp liquid in a water bath kettle at the temperature of 80 ℃ for 2 hours. And repeatedly filtering and washing the waste paper pulp liquid for 3 times by using water and ethanol. And finally, adding 1L of ethanol into the waste paper, uniformly dispersing, performing suction filtration to obtain waste paper aerogel, and drying to obtain the waste paper aerogel. And (3) putting the waste paper aerogel into a tubular furnace, introducing Ar, heating at the heating rate of 5 ℃/min, carbonizing at the specified temperature of 500 ℃ for 2h, and naturally cooling to obtain the waste paper carbon aerogel. 484mg of iron nitrate nonahydrate and 500mg of terephthalic acid were dissolved in 20ml of methanol, respectively. The ferric nitrate solution was quickly added to the terephthalic acid solution and stirred for an additional 3 minutes. And adding 48mg of waste paper carbon aerogel into the mixed solution, carrying out hydrothermal reaction for 5 hours at 120 ℃, cleaning and drying to obtain MIL-88@ waste paper-based composite carbon aerogel.
Mixing sodium hypophosphite and MIL-88@ waste paper-based composite carbon aerogel according to the weight ratio of 5: the proportion of 1 is respectively put into two porcelain boats, the porcelain boats are sequentially placed in a tube furnace, the temperature is raised to 350 ℃ for 2 hours at the temperature rise speed of 5 ℃/min in the Ar atmosphere, and the porcelain boats are naturally cooled and then taken out to obtain the iron phosphide @ waste paper based composite carbon aerogel.
The performance of the metal organic framework derived iron phosphide @ waste paper-based composite carbon aerogel obtained in example 3 is as follows:
the density of the metal organic framework derived iron phosphide @ waste paper-based composite carbon aerogel is 41.3mg/cm3
The conductivity was 8.3S/m
The overpotential is 385mV (eta)10)
The Tafel slope was 78.1 mV/dec.
The preparation method disclosed by the invention is simple in preparation process and good in chemical stability, and the obtained aerogel is excellent in electrocatalysis performance and has a wide application prospect in the aspect of energy conversion.
Claims (10)
1. The method for preparing aerogel from waste paper is characterized by comprising the following steps: soaking, deinking and surface functionalization treatment of waste paper, filtering, molding and drying to obtain waste paper aerogel, and calcining at 400-1000 ℃ to obtain waste paper carbon aerogel;
the surface functionalization treatment comprises the following steps: treating waste paper by using a compound A solution, wherein the pH value of the treatment is 4-4.5, the treatment temperature is 70-80 ℃, the treatment time is 2-6 h, and the compound A is one of hydrogen peroxide, sodium hypochlorite, sodium chlorite and sodium periodate;
the pH is preferably adjusted with glacial acetic acid, dilute hydrochloric acid or dilute sulfuric acid.
2. The waste paper aerogel production process according to claim 1, wherein the compound a is sodium hypochlorite; the concentration of the sodium hypochlorite solution is preferably 0.1-0.3 mol/L; the preferable mass ratio of the sodium hypochlorite dosage to the waste paper is 0.7-3: 1.
3. the process for producing aerogels from waste paper according to claim 1 or 2, characterized in that the calcination is in N2Or Ar gas atmosphere, wherein the temperature rise rate of the calcination is preferably 2-5 ℃/min, and the calcination time is preferably kept at 400-1000 ℃ for 2-3 h.
4. The waste paper aerogel is characterized by being prepared by the method for preparing the aerogel from the waste paper according to any one of claims 1 to 3.
5. The preparation method of the metal organic framework derivative @ composite carbon aerogel is characterized by comprising the following steps:
a. mixing the aerogel with a metal organic framework precursor solution to obtain a mixed solution, and aging or hydro-thermal treating to obtain metal organic framework @ carbon aerogel;
preferably, the mass ratio of the aerogel to the metal organic framework precursor is 3-5: 50-100 parts;
b. phosphating or phosphorylating a metal organic framework @ carbon aerogel, and obtaining a metal organic framework derivative @ composite carbon aerogel by using a high-temperature carbonization or hydrothermal treatment method;
the metal organic framework precursor solution is a mixed solution of at least one of cobalt nitrate, ferric nitrate, zinc nitrate, cerium nitrate and zirconium nitrate and an organic ligand, wherein the organic ligand is at least one of isophthalic acid, terephthalic acid and 2-methylimidazole;
the metal organic framework is preferably at least one of ZIF-67, ZIF-8, MIL-88 and UiO-66;
the aerogel in the step a is prepared by the method for preparing the aerogel by using the waste paper of any one of claims 1 to 3.
6. The preparation method of metal organic framework derivative @ composite carbon aerogel according to claim 5, wherein the aging treatment in the step a is aging at 20-30 ℃ for 3-24 hours, and the hydrothermal treatment in the step a is hydrothermal at 120-160 ℃ for 2-5 hours.
7. The process for preparing metal organic framework derivative @ composite carbon aerogel according to claim 5 or 6, wherein at least one of sodium hypophosphite and sodium phosphite is used as a phosphorus source in the phosphating treatment in the step b, and at least one of sodium phosphate and potassium phosphate is used as a phosphorus source in the phosphating treatment in the step b.
8. The preparation method of metal organic framework derivative @ composite carbon aerogel according to claim 7, wherein in the step b, when high-temperature carbonization is adopted, the mass ratio of the phosphorus source to the metal organic framework @ aerogel is 2-10: 1;
preferably, the high-temperature carbonization in the step b is kept for 2-3 h at 300-350 ℃ in Ar atmosphere, and preferably, the heating rate of the high-temperature carbonization is 2-5 ℃/min.
9. The preparation method of metal organic framework derivative @ composite carbon aerogel according to any one of claims 5 to 8, wherein when the hydrothermal treatment is adopted in the step b, the concentration of the phosphorus source is 0.5 to 1.5 g/L;
b, preferably carrying out hydrothermal treatment at 100-150 ℃ for 10-24 h;
preferably, before hydrothermal treatment, the metal organic framework @ carbon aerogel and at least one of nickel nitrate or nickel sulfate solution are subjected to ultrasonic or water bath heating treatment to obtain layered double hydroxide @ composite carbon aerogel, and then the layered double hydroxide @ composite carbon aerogel is mixed with a phosphorus source and subjected to hydrothermal treatment; more preferably, the ultrasonic time is 10-120 min or the water bath heating temperature is 30-80 ℃, the heating time is 60-180 min, and the concentration of the nickel nitrate or nickel sulfate solution is preferably 1-5 g/L.
10. The metal organic framework derivative @ composite carbon aerogel is characterized in that the metal organic framework derivative @ composite carbon aerogel is prepared by the preparation method of the metal organic framework derivative @ composite carbon aerogel as claimed in any one of claims 5 to 9;
preferably, the density of the metal organic framework derivative @ composite carbon aerogel is 30-80 mg/cm3；
More preferably, the metal organic framework derivative @ composite carbon aerogel is at 10mA/cm2The OER overpotential under the current density is 300-410 mV.
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