CN109046427B - Preparation method of Fe-N-C catalytic material with controllable edge active sites - Google Patents
Preparation method of Fe-N-C catalytic material with controllable edge active sites Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 239000002244 precipitate Substances 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical class ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000002149 hierarchical pore Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012922 MOF pore Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The invention discloses a preparation method of a Fe-N-C catalytic material with controllable edge active sites. The invention adopts a method of embedding molecular aggregates in situ and then pyrolyzing at high temperature, and aims to change the small molecular weight on the premise of keeping the original MOF appearanceThe dosage of the molecule is used for regulating and controlling the pore structure of the framework and the breaking degree of the C-N bond, and the regulation and control of the number of the edge active sites and the chemical environment around the single atom are realized for the first time, so that more excellent electrochemical performance is obtained. The invention adopts proper small molecular dosage to obtain the specific surface area of 1392.91m2The half-wave potential of the ORR catalyst in 0.1M KOH can reach 0.915V (vs. RHE), which is superior to the catalytic performance of commercial platinum carbon and similar materials. Therefore, the invention realizes the regulation of active sites at an atomic level and the regulation of structures at a molecular level, and provides reference significance for reasonably designing the high-performance monatomic catalyst.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a Fe-N-C material with controllable edge active sites, which can be applied to an electrocatalytic oxygen reduction reaction.
Background
The development and utilization of fuel cells are important ways to solve energy crisis and alleviate environmental pollution. However, as an indispensable cathode reaction of the fuel cell, the Oxygen Reduction Reaction (ORR) still requires a Pt-based material, which is expensive and has limited storage, as a catalyst, which greatly limits the commercial application of the fuel cell. Therefore, the cheap and abundant non-noble metal catalyst M-N-C material attracts a great deal of attention because it shows good catalytic activity in ORR. Wherein, the active sites with M-N-C dispersed at atomic level have unique electronic structure and high-efficiency O2The adsorption reduction efficiency shows excellent catalytic performance, and the catalyst becomes a hotspot material for research. However, the preparation of the existing atomic-scale dispersed M-N-C catalyst is difficult to realize the precise regulation and control of the active site, and is not beneficial to the exposure of the active site and the regulation of the macroscopic structure.
Therefore, to prepare an efficient and stable M-N-C material, not only the dispersibility of the catalytic active sites needs to be improved and the atom utilization rate needs to be maximized, but also as many catalytic active sites as possible need to be exposed. Recently, a literature reports that a good three-dimensional carbon skeleton can be obtained after the MOF pyrolysis, and the interior of the MOF pyrolysis contains rich small-pore structures, so that the density of active sites and the charge transport density are expected to be improved. However, if a single metal site is embedded in the MOF pore, it is not only difficult to fully expose the internal catalytic active site, but more importantly, it is difficult to precisely adjust the coordination environment of the catalytic site and improve the electronic structure of the active center by coordinating the metal with the N-containing MOF ligand. Therefore, it is very challenging to realize the molecular level dispersibility and electronic structure adjustment in the M-N-C catalyst and to realize the precise controllability of the overall macroscopic physical structure in cooperation.
Disclosure of Invention
The invention aims to meet the requirements of the field of electrochemical catalysis application, and particularly designs a Fe-N-C material with controllable edge active sites, and the control of the chemical environment around a single atom active site is realized for the first time through the breaking degree of a C-N bond, so that the performance of the electrocatalysis ORR is greatly improved. The invention adopts a method of introducing small molecules containing metal elements into MOF precursor liquid to obtain the structures of single molecules embedded into MOF pore canals and molecular aggregates embedded into MOF frameworks; after high-temperature pyrolysis and acid treatment, the Fe-N-C material with a hierarchical pore structure and atomic-level dispersion is obtained, and the material shows excellent performance in electrocatalysis ORR. The number of active sites and the porosity can be regulated and controlled by changing the dosage of the small molecules, so that the exposure degree of the active sites at the edge of the material and the regulation and control of the mass transmission performance are realized.
The Fe-N-C catalytic material with controllable edge active sites prepared by the invention is FeN with adjustable multi-stage pore channel structure and atomic-level dispersion4A carbon skeleton material of the edge active site.
The preparation method of the Fe-N-C catalytic material with controllable edge active sites comprises the following steps:
a. dispersing organic ligands and organic small molecules in a solvent, then adding a metal ion solution, centrifugally washing, and vacuum-drying the obtained precipitate;
b. b, performing high-temperature pyrolysis on the precipitate obtained in the step a;
c. and C, carrying out acid treatment on the product obtained in the step b, washing and vacuum drying to obtain the Fe-N-C catalytic material with controllable edge active sites.
The specific reaction conditions of the step a are as follows: dispersing 12-40mmol of organic ligand and 0.1-100mg of organic micromolecule in 20-80mL of methanol, quickly adding 20-80mL of 3-9M metal ion solution, stirring at room temperature for 1-36h, washing with methanol, centrifuging, and drying the obtained precipitate in a vacuum drying oven.
The tool of the step bThe reaction conditions were: transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 700-1000 ℃ and calcining for 1-5 h.
The specific reaction conditions of the step c are as follows: adding 0.1-1M H into the product of step b2SO4Soaking the materials completely, keeping the temperature at 20-80 deg.C for 1-36h, washing to neutrality, and oven drying the precipitate in a vacuum drying oven.
The organic ligand is 2-methylimidazole, and the metal ion solution is a methanol solution of zinc ions.
The organic micromolecules are iron phthalocyanine compounds or iron porphyrin compounds.
The Fe-N-C catalytic material with controllable edge active sites, which is prepared by the method, is applied to an electrocatalytic oxygen reduction reaction.
The invention has the beneficial effects that: the Fe-N-C material with controllable edge active sites is synthesized by the invention, and the designed material has FeN with atomic-level dispersion4Active sites and adjustable hierarchical pore structures, and realizes the regulation and control of C-N bond breaking degree and chemical environment around the monoatomic active sites for the first time. On the premise of keeping the original MOF morphology, the invention can regulate and control the number of active sites and the porosity by changing the dosage of small molecules, thereby realizing the regulation and control of edge active sites and mass transmission performance. Compared with the complete Fe-N-C material, the material has a hierarchical pore structure and FeN under the same conditions4The carbon skeleton material with active sites at the edges can reduce the reaction barrier in the ORR process, and further shows good ORR catalytic activity, and the electrode load is 0.612mg cm in 0.1M KOH-2The half-wave potential of the material reaches 0.915V, which is superior to that of commercial platinum carbon and most other catalysts under the same test condition. Therefore, the invention realizes the regulation of active sites at an atomic level and the regulation of structures at a molecular level, and provides reference significance for reasonably designing the high-performance monatomic catalyst.
Drawings
FIG. 1: transmission electron micrograph of N-C catalytic material prepared in example 1.
FIG. 2: transmission electron microscopy images of Fe-N-C catalytic material prepared in example 2.
FIG. 3: transmission electron microscopy images of Fe-N-C catalytic material prepared in example 3.
FIG. 4: transmission electron microscopy images of Fe-N-C catalytic material prepared in example 4.
FIG. 5: transmission electron microscopy images of Fe-N-C catalytic material prepared in example 5.
FIG. 6: the Fe-N-C catalytic materials prepared in examples 1-5 had an electrode loading of 0.408mg cm-2Comparative ORR performance chart (test conditions: three-electrode system, working electrode as catalyst, counter electrode as carbon rod, reference electrode as calomel electrode, and electrolyte as O2Saturated 0.1M KOH solution).
FIG. 7: ORR performance comparison chart of Fe-N-C catalytic material prepared in example 5 under different electrode loading (test condition: three-electrode system, working electrode as catalyst, counter electrode as carbon rod, reference electrode as calomel electrode, electrolyte as O2Saturated 0.1M KOH solution).
Detailed Description
Example 1
a. 28.71mmol of 2-methylimidazole were dispersed in 40mL of methanol and 40mL of 3.6M Zn (NO) were added rapidly3)2Stirring the methanol solution at room temperature for 24h, washing with methanol, centrifuging, and drying the obtained precipitate in a vacuum drying oven;
b. transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 900 ℃ and calcining for 3 h;
c. 0.5M H was added to the calcined material2SO4And (3) completely immersing the materials, keeping the temperature at 60 ℃ for 24 hours, washing to be neutral, and drying the precipitate in a vacuum drying oven.
Example 2
a. 28.71mmol of 2-methylimidazole and 8mg of iron phthalocyanine were dispersed in 40mL of methanol, and 40mL of 3.6M Zn (NO) was rapidly added3)2Stirring the obtained methanol solution at room temperature for 24h, washing the solution with methanol, centrifuging the solution, and placing the obtained precipitate in a vacuum drying oven to dryDrying;
b. transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 900 ℃ and calcining for 3 h;
c. 0.5M H was added to the calcined material2SO4And (3) completely immersing the materials, keeping the temperature at 60 ℃ for 24 hours, washing to be neutral, and drying the precipitate in a vacuum drying oven.
Example 3
a. 28.71mmol of 2-methylimidazole and 16mg of iron phthalocyanine were dispersed in 40mL of methanol, and 40mL of 3.6M Zn (NO) were rapidly added3)2Stirring the methanol solution at room temperature for 24h, washing with methanol, centrifuging, and drying the obtained precipitate in a vacuum drying oven;
b. transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 900 ℃ and calcining for 3 h;
c. 0.5M H was added to the calcined material2SO4And (3) completely immersing the materials, keeping the temperature at 60 ℃ for 24 hours, washing to be neutral, and drying the precipitate in a vacuum drying oven.
Example 4
a. 28.71mmol of 2-methylimidazole and 20mg of iron phthalocyanine were dispersed in 40mL of methanol, and 40mL of 3.6M Zn (NO) was added rapidly3)2Stirring the methanol solution at room temperature for 24h, washing with methanol, centrifuging, and drying the obtained precipitate in a vacuum drying oven;
b. transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 900 ℃ and calcining for 3 h;
c. 0.5M H was added to the calcined material2SO4And (3) completely immersing the materials, keeping the temperature at 60 ℃ for 24 hours, washing to be neutral, and drying the precipitate in a vacuum drying oven.
Example 5
a. 28.71mmol of 2-methylimidazole and 24mg of iron phthalocyanine were dispersed in 40mL of methanol, and 40mL of 3.6M Zn (NO) were rapidly added3)2The obtained methanol solution is stirred for 24 hours at room temperature and then washed by methanol for centrifugation,putting the obtained precipitate in a vacuum drying box for drying;
b. transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 900 ℃ and calcining for 3 h;
c. 0.5M H was added to the calcined material2SO4And (3) completely immersing the materials, keeping the temperature at 60 ℃ for 24 hours, washing to be neutral, and drying the precipitate in a vacuum drying oven.
Claims (5)
1. A preparation method of a Fe-N-C catalytic material with controllable edge active sites is characterized by comprising the following specific steps:
a. dispersing organic ligands and organic small molecules in a solvent, then adding a metal ion solution, centrifugally washing, and vacuum-drying the obtained precipitate;
b. carrying out high-temperature pyrolysis on the precipitate obtained in the step a, wherein the temperature of the high-temperature pyrolysis is 700-oC；
c. C, performing acid treatment, washing and vacuum drying on the product obtained in the step b to obtain the Fe-N-C catalytic material with controllable edge active sites;
the organic ligand is 2-methylimidazole, and the metal ion solution is a methanol solution of zinc ions;
the organic micromolecules are iron phthalocyanine compounds or iron porphyrin compounds;
the prepared Fe-N-C catalytic material with controllable edge active sites is FeN with adjustable multi-stage pore channel structure and atomic-level dispersion4A carbon skeleton material of the edge active site.
2. The method for preparing Fe-N-C catalytic material with controllable edge active sites according to claim 1, wherein the specific reaction conditions of the step a are as follows: dispersing 12-40mmol of organic ligand and 0.1-100mg of organic micromolecule in 20-80mL of methanol, quickly adding 20-80mL of 3-9M metal ion solution, stirring at room temperature for 1-36h, centrifuging and washing with methanol, and drying the obtained precipitate in a vacuum drying oven.
3. The method for preparing Fe-N-C catalytic material with controllable edge active sites according to claim 2, wherein the specific reaction conditions of the step b are as follows: transferring the dried precipitate to a porcelain boat, placing the porcelain boat in a tube furnace, and introducing N2After exhausting air, heating to 700-oC, calcining for 1-5 h.
4. The method for preparing Fe-N-C catalytic material with controllable edge active sites according to claim 3, wherein the specific reaction conditions of the step C are as follows: adding 0.1-1M H into the product of step b2SO4To complete immersion of the material, 20-80oAnd C, keeping the temperature for 1-36h, washing to be neutral, and drying the precipitate in a vacuum drying oven.
5. The application of the Fe-N-C catalytic material with controllable edge active sites, prepared according to the method of claim 1, in electrocatalytic oxygen reduction reaction.
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| CN110124718B (en) * | 2019-05-13 | 2022-02-15 | 浙江师范大学 | Vanadium-based single-atom catalyst for preparing phenol by directly oxidizing benzene and preparation method thereof |
| CN112018398B (en) * | 2019-05-29 | 2022-06-03 | 中南大学 | Cu2O/N-C oxygen reduction catalyst, preparation and application thereof |
| CN110860289A (en) * | 2019-10-29 | 2020-03-06 | 中南大学 | Preparation method and application of metal monoatomic material |
| CN111146452B (en) * | 2019-12-27 | 2021-10-22 | 大连理工大学 | Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof |
| CN114982021A (en) * | 2020-02-07 | 2022-08-30 | 香港科技大学 | Durable composite fuel cell electrocatalyst |
| CN111477889A (en) * | 2020-06-02 | 2020-07-31 | 浙江大学 | Monoatomic iron-nitrogen co-doped carbon electrocatalyst and preparation method and application thereof |
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