CN110436430A - The preparation method and applications of bifunctional electrocatalyst with unique hierarchical structure - Google Patents
The preparation method and applications of bifunctional electrocatalyst with unique hierarchical structure Download PDFInfo
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- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
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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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Abstract
The invention discloses a kind of preparation method and applications of bifunctional electrocatalyst with unique hierarchical structure, belong to rechargeable type zinc and air cell catalyst technical field.Technical solution of the present invention main points are as follows: using MOF material ZIF-67(transition metals cobalt as center ion, 2-methylimidazole is organic ligand) it is presoma, adsorption and dephosphorization is carried out to the secondary effluent of the sewage plant, modification is generated to ZIF-67 using the phosphate during adsorption and dephosphorization, in conjunction with controllable derivative synthesis condition, it is prepared for the bifunctional electrocatalyst with unique hierarchical structure, effectively optimize the structure and morphology and electronic structure of catalysis material, specific surface area with higher and good catalytic activity.The present invention provides based on the high-performance bifunctional electrocatalyst preparation method for taking into account environmentally friendly process, there is good comprehensive benefit and application prospect.
Description
Technical field
The invention belongs to rechargeable type zinc and air cell catalyst technical fields, and in particular to a kind of with unique hierarchical structure
The preparation method and applications of bifunctional electrocatalyst.
Background technique
In the rapid developing country of economic development, water pollution has become a serious problem.Mistake containing phosphorus product
Amount consumption inevitably will cause a large amount of pollutants, cause water eutrophication, and many has been directed to the method for treating water of dephosphorization
It is widely studied and applied.Adsorption technology because its have the characteristics that it is simple, efficient, it has also become a kind of current widely used dephosphorization
Method, the phosphorus removing method for being particularly suitable for wide concentration range phosphorus-containing wastewater are gradually taken seriously in recent years.
Metal-organic framework materials (MOF) can be multiple by being self-assembly of by organic ligand and metallic ion coordination
Miscellaneous network structure has the characteristics that high porosity, low-density and bigger serface, can directly adsorb various organic dirts in water
Object is contaminated, there is huge application potential in environment remediation field.
Clean energy resource catalysis material of new generation can be synthesized using metal-organic framework materials, and passes through metal-air
The development of the clean energy technologies such as battery, fuel cell, thus it is possible to vary the energy needed for mankind's activity is largely dependent upon stone
The status of the fossil fuels such as oil, coal and natural gas.The microscopic appearance and structure composition and preparation method of catalyst are closely related,
Its catalyst activity is often also very different, for example is modified using distinct methods MOF, and different-shape composition can be formed
MOF material, adopt this method the composite material constructed and be expected to obtain excellent electrocatalysis characteristic.
The comprehensive adsorption and dephosphorization technology for solving phosphorus-containing wastewater of the present invention is synthesized with the innovation of novel green power supply catalysis material
Technology has developed the preparation method for taking into account the high-performance bifunctional electrocatalyst of environmentally friendly process, have significant comprehensive benefit and
Good application prospect.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of systems of bifunctional electrocatalyst with unique hierarchical structure
Preparation Method, the adsorption and dephosphorization technology that this method fully utilizes phosphorus-containing wastewater are synthesized with the innovation of novel green power supply catalysis material
Technology, it is living that the bifunctional electrocatalyst with unique hierarchical structure obtained shows the difunctional electro-catalysis of preferable OER, ORR
Property, in preparing zinc and air cell field with good application prospect.
The present invention adopts the following technical scheme that there is the difunctional electricity of unique hierarchical structure to urge to solve above-mentioned technical problem
The preparation method of agent, it is characterised in that specific steps are as follows:
Step S1: cabaltous nitrate hexahydrate 1.0mmol and 2-methylimidazole 4.0mmol are dissolved in respectively in 25.0mL methanol and obtain six
The methanol solution of cabaltous nitrate hexahydrate is poured into 2- methyl by the methanol solution of nitric hydrate cobalt and the methanol solution of 2-methylimidazole
In the methanol solution of imidazoles and be stirred well to it is uniformly mixed, at room temperature stand 36h obtain purple precipitating, topple over supernatant,
With ethyl alcohol centrifuge washing 6 times, then it is dried to obtain purple ZIF-67 solid powder at normal temperature；
Step S2: the ZIF-67 solid powder that step S1 is obtained carries out adsorption and dephosphorization to the secondary effluent of the sewage plant, wherein ZIF-
67 solid powders are 0.005g/L to the dosage proportion of the secondary effluent of the sewage plant, then adjusting the pH value of absorption system is 6.5, with
Solid precursor is obtained by filtration through 0.1 micron membrane filter after the constant speed magnetic agitation 1h of 600r/min, while realizing to sewage
The removal of factory's Phosphorus Removal from Secondary Water hydrochlorate；
Step S3: the obtained solid precursor of step S2 being placed in 60 DEG C of vacuum ovens and is dried to constant weight, then by gained sample
Product tile to porcelain boat, are warming up to 400 DEG C of calcining 2h in nitrogen atmosphere with the heating rate of 1 DEG C/min, finally obtain average
Partial size is 600nm and has the bifunctional electrocatalyst Co of unique hierarchical structure2P2O7。
It is in the preparation of the bifunctional electrocatalyst with unique hierarchical structure of the present invention that phosphate in waste water is dirty
Object is contaminated as phosphorus source needed for catalyst material synthesis, is matched using the local that phosphate radical changes metal organic framework compound surface
Position environment forms surface folding structure, and the structure feature of this elaborate assigns catalysis material high specific surface area, and increases
The active edge for having added exposure, effectively increases the electro catalytic activity of bifunctional electrocatalyst, by drawing on catalysis material surface
Enter P elements, provides abundant and evenly dispersed active site, the optimizing regulation electronic structure of catalysis material, significantly
Improve the difunctional electrocatalysis characteristic of OER, ORR of catalysis material.
The bifunctional electrocatalyst with unique hierarchical structure of the present invention is preparing the application in zinc and air cell,
It is characterized in that detailed process are as follows: there is the bifunctional electrocatalyst of unique hierarchical structure to mix with 485 μ L isopropanols 2mg
Even, ultrasonic 5min takes 15 μ L 5wt% Nafion and above-mentioned mixed system to be mixed with out containing double with microsyringe
The homogeneous sample liquid of black slurry of energy energy elctro-catalyst, then carries out ultrasonic treatment 25min, then 25.1 μ L are contained difunctional electricity and are urged
Electrode is made in the platinum carbon electrode surface that pre-polish(ing) diameter is 4mm in the homogeneous sample liquid drop of the black slurry of agent, wherein difunctional electricity
The load capacity of catalyst is 275.6 μ g cm-2, prepared bifunctional electrocatalyst has biggish take-off potential and half wave potential
And biggish current density and have preferable stability.
Compared with the prior art, the invention has the following beneficial effects:
1, the phosphorus removing method that the present invention introduces green economy in the synthesis process of New-type bifunctional elctro-catalyst, is simple and efficient,
Directly phosphorus-containing wastewater can be handled.
2, the present invention is dexterously using the phosphate contaminants in the secondary effluent of the sewage plant as phosphorus needed for catalyst synthesis
Source changes the local coordination environment on metal organic framework compound surface using phosphate radical, forms surface folding structure, this essence
Thin complicated structure feature assigns catalyst high specific surface area, and increases the active edge of catalyst exposure, effectively mentions
The high electro catalytic activity of catalyst.
3, the present invention provides catalytic active site abundant and evenly dispersed by introducing P elements in catalyst surface
Point, the optimizing regulation electronic structure of catalyst, significantly improves the difunctional electrocatalysis characteristic of catalyst.
Detailed description of the invention
Fig. 1 is that the FESEM of catalyst is made in embodiment 1 and first vegetarian noodles sweeps figure；
Fig. 2 is the ORR figure that catalyst is made in embodiment 1；
Fig. 3 is the OER figure that catalyst is made in embodiment 1；
Fig. 4 is the ORR figure that catalyst is made in comparative example 1；
Fig. 5 is the OER figure that catalyst is made in comparative example 1；
Fig. 6 is that the durability test of the obtained catalyst of embodiment and comparative example compares figure.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
Step S1: cabaltous nitrate hexahydrate 1.0mmol and 2-methylimidazole 4.0mmol are dissolved in respectively in 25.0mL methanol and obtain six
The methanol solution of cabaltous nitrate hexahydrate is poured into 2- methyl by the methanol solution of nitric hydrate cobalt and the methanol solution of 2-methylimidazole
In the methanol solution of imidazoles and be stirred well to it is uniformly mixed, at room temperature stand 36h obtain purple precipitating, topple over supernatant,
With ethyl alcohol centrifuge washing 6 times, then it is dried to obtain purple ZIF-67 solid powder at normal temperature；
Step S2: the ZIF-67 solid powder that step S1 is obtained carries out adsorption and dephosphorization (phosphoric acid in water to the secondary effluent of the sewage plant
The initial concentration of salt is 0.6mg/L), wherein ZIF-67 solid powder is to the dosage proportion of the secondary effluent of the sewage plant
0.005g/L, then adjust absorption system pH value be 6.5, and with after the constant speed magnetic agitation 1h of 600 r/min through 0.1
Solid precursor is obtained by filtration in micron membrane filter；
After reaction, it takes supernatant to filter through 0.1 micron membrane filter, measures the phosphate concn in filtrate, test result shows:
Remaining phosphate concn is 0.007mg/L, i.e., is 99.83% to removal rate phosphatic in the secondary effluent of the sewage plant；
Step S3: the obtained solid precursor of step S2 being placed in 60 DEG C of vacuum ovens and is dried to constant weight, then by gained sample
Product tile to porcelain boat, are warming up to 400 DEG C of calcining 2h in nitrogen atmosphere with the heating rate of 1 DEG C/min, finally obtain tool
There is the bifunctional electrocatalyst of unique hierarchical structure.
Electrochemical property test: CHI 660D work station that electro-chemical test is controlled in computer (CH Instruments,
Chenhua, Shanghai, China) on carry out, the work station is equipped with 616 type electrode rotary devices in standard three electrode battery
(Princeton Applied Research).Electrochemical measurement carries out in three-electrode battery system, rotating disk electrode (r.d.e)
It (RDE) be working electrode, saturated calomel electrode is reference electrode, carbon-point is that three-electrode system is formed to electrode, the electricity of ORR test
Solution liquid is 0.1M KOH solution, and the electrolyte of OER test is 1M KOH solution, passes through the bifunctional electrocatalyst that will be prepared
2mg is uniformly mixed with 485 μ L isopropanols, ultrasonic 5min, is taken 15 μ L 5wt% Nafion to be mixed with out with microsyringe and is contained
There is the homogeneous sample liquid of the black slurry of bifunctional electrocatalyst, then carries out ultrasonic treatment 25min.Next, 25.1 μ L are contained
The homogeneous sample liquid drop of the black slurry of bifunctional electrocatalyst is in the RDE(platinum carbon electrode that pre-polish(ing) diameter is 4mm) surface, wherein double
The load capacity of function elctro-catalyst is 275.6 μ g cm-2.Electric performance test result is as shown in Figure 2 and Figure 3.
It is Co that XRD characterization, which analyzes the product,2P2O7。
Show that the catalyst surface forms the surface with obvious fold by FESEM test, size is uniform, and structure is complete
Whole, average grain diameter is about 600nm.
Photoelectron spectroscopy characterization confirms the catalyst containing Co, P, O element and each element is uniformly distributed, as shown in Figure 1.
Comparative example 1
Step S1: cabaltous nitrate hexahydrate 1.0mmol and 2-methylimidazole 4.0mmol are dissolved in respectively in 25.0mL methanol and obtain six
The methanol solution of cabaltous nitrate hexahydrate is poured into 2- methyl by the methanol solution of nitric hydrate cobalt and the methanol solution of 2-methylimidazole
In the methanol solution of imidazoles and be stirred well to it is uniformly mixed, at room temperature stand 36h obtain purple precipitating, topple over supernatant,
With ethyl alcohol centrifuge washing 6 times, then it is dried to obtain purple ZIF-67 solid powder at normal temperature；
Step S2: the ZIF-67 solid powder that step S1 is obtained being placed in 60 DEG C of vacuum ovens and is dried to constant weight, then by institute
Sample tiles to porcelain boat, 400 DEG C of calcining 2h are warming up to the heating rate of 1 DEG C/min in nitrogen atmosphere, it is final must
To catalyst.
Electrochemical property test: CHI 660D work station that electro-chemical test is controlled in computer (CH Instruments,
Chenhua, Shanghai, China) on carry out, the work station is equipped with 616 type electrode rotary devices in standard three electrode battery
(Princeton Applied Research).Electrochemical measurement carries out in three-electrode battery system, rotating disk electrode (r.d.e)
It (RDE) be working electrode, saturated calomel electrode is reference electrode, carbon-point is that three-electrode system is formed to electrode, the electricity of ORR test
Solution liquid is 0.1M KOH solution, and the electrolyte of OER test is 1M KOH solution, passes through the catalyst 2mg and 485 μ L that will be prepared
Isopropanol is uniformly mixed, and ultrasonic 5min takes 15 μ L 5wt% Nafion to be mixed with out containing catalyst with microsyringe
The homogeneous sample liquid of black slurry, then carries out ultrasonic treatment 25min.Next, the black slurry that 25.1 μ L are contained catalyst is equal
Phase sample liquid drop is in the RDE(platinum carbon electrode that pre-polish(ing) diameter is 4mm) surface, wherein the load capacity of catalyst is 275.6 μ g cm-2。
Electric performance test result is as shown in Figure 4,5.
It is CoO that XRD characterization, which analyzes the product,.
It is the smooth polyhedron pattern in surface by catalyst synthesized known to FESEM test characterization, average grain diameter is about
For 500nm.
By comparing catalyst ORR and OER prepared by embodiment 1 and comparative example 1 it is found that being urged prepared by embodiment 1
Agent has biggish take-off potential and half wave potential and biggish current density；Compared by the durability of Fig. 6 it is found that embodiment 1
Prepared catalyst has obviously good stability compared with catalyst prepared by comparative example 1.Therefore embodiment 1 has compared with comparative example 1
Preferable activity and durability.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. the preparation method with the bifunctional electrocatalyst of unique hierarchical structure, it is characterised in that specific steps are as follows:
Step S1: cabaltous nitrate hexahydrate 1.0mmol and 2-methylimidazole 4.0mmol are dissolved in respectively in 25.0mL methanol and obtain six
The methanol solution of cabaltous nitrate hexahydrate is poured into 2- methyl by the methanol solution of nitric hydrate cobalt and the methanol solution of 2-methylimidazole
In the methanol solution of imidazoles and be stirred well to it is uniformly mixed, at room temperature stand 36h obtain purple precipitating, topple over supernatant,
With ethyl alcohol centrifuge washing 6 times, then it is dried to obtain purple ZIF-67 solid powder at normal temperature；
Step S2: the ZIF-67 solid powder that step S1 is obtained carries out adsorption and dephosphorization to the secondary effluent of the sewage plant, wherein ZIF-
67 solid powders are 0.005g/L to the dosage proportion of the secondary effluent of the sewage plant, then adjusting the pH value of absorption system is 6.5, with
Solid precursor is obtained by filtration through 0.1 micron membrane filter after the constant speed magnetic agitation 1h of 600r/min, while realizing to sewage
The removal of factory's Phosphorus Removal from Secondary Water hydrochlorate；
Step S3: the obtained solid precursor of step S2 being placed in 60 DEG C of vacuum ovens and is dried to constant weight, then by gained sample
Product tile to porcelain boat, are warming up to 400 DEG C of calcining 2h in nitrogen atmosphere with the heating rate of 1 DEG C/min, finally obtain average
Partial size is 600nm and has the bifunctional electrocatalyst Co of unique hierarchical structure2P2O7。
2. the preparation method of the bifunctional electrocatalyst with unique hierarchical structure according to claim 1, feature exist
In: using the phosphate contaminants in waste water as catalysis in the preparation of the bifunctional electrocatalyst with unique hierarchical structure
Phosphorus source needed for agent material synthesis forms table using the local coordination environment that phosphate radical changes metal organic framework compound surface
Face pleated structure, the structure feature of this elaborate assigns catalysis material high specific surface area, and increases exposed work
Property edge, effectively increase the electro catalytic activity of bifunctional electrocatalyst, by catalysis material surface introduce P elements, provide
Abundant and evenly dispersed active site, the optimizing regulation electronic structure of catalysis material, significantly improves catalysis material
The difunctional electrocatalysis characteristic of OER, ORR of material.
3. the difunctional electro-catalysis with unique hierarchical structure obtained of method described in any one of -2 according to claim 1
Agent is preparing the application in zinc and air cell.
4. application according to claim 3, it is characterised in that detailed process are as follows: 2mg is had the double of unique hierarchical structure
Function elctro-catalyst is uniformly mixed with 485 μ L isopropanols, ultrasonic 5min, with microsyringe take 15 μ L 5wt% Nafion with it is upper
It states mixed system and is mixed with out the homogeneous sample liquid of black slurry containing dual intensity energy elctro-catalyst, be then ultrasonically treated
25min, then the homogeneous sample liquid drop of black slurry that 25.1 μ L are contained bifunctional electrocatalyst is in the platinum carbon that pre-polish(ing) diameter is 4mm
Electrode is made in electrode surface, and wherein the load capacity of bifunctional electrocatalyst is 275.6 μ g cm-2, prepared difunctional electro-catalysis
Agent has biggish take-off potential and half wave potential and biggish current density and has preferable stability.
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| CN115566207A (en) * | 2022-10-12 | 2023-01-03 | 北京科技大学 | Transition metal pyrophosphate ORR catalyst anchored on MOFs derived carbon skeleton and preparation method and application thereof |
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