CN116462177A - Preparation method and application of MOF-derived mesoporous carbon - Google Patents
Preparation method and application of MOF-derived mesoporous carbon Download PDFInfo
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- CN116462177A CN116462177A CN202310373658.6A CN202310373658A CN116462177A CN 116462177 A CN116462177 A CN 116462177A CN 202310373658 A CN202310373658 A CN 202310373658A CN 116462177 A CN116462177 A CN 116462177A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
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- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 239000011259 mixed solution Substances 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 24
- 239000003575 carbonaceous material Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
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- 230000002829 reductive effect Effects 0.000 claims description 8
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- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 7
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
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- 238000000137 annealing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- -1 salt zinc nitrate Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000020477 pH reduction Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
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- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 235000019441 ethanol Nutrition 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012919 MOF-derived carbon material Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
Abstract
The invention relates to the field of catalysts, and particularly discloses a preparation method and application of MOF-derived mesoporous carbon, wherein the preparation method comprises the following steps: (1) Preparing MOF by utilizing the reaction of inorganic metal salt and organic ligand in solvent; (2) preparation of MOF-derived mesoporous carbon: performing sintering treatment at high temperature by using a mixture formed by mixing a precursor MOF, a template agent and a uniformly-mixable solvent, and then performing program cooling to obtain NCP; (3) acid acidification treatment with strong acid: and (3) acidizing the obtained NCP powder by using a strong acid solution to obtain the MOF derivative mesoporous carbon. The invention constructs a carbon carrier of the PEMFC cathode platinum-based catalyst, and the platinum-based catalyst prepared by using the carbon carrier can be applied to the field of ORR electrocatalysis as a good oxygen reduction catalyst carrier, even in a PEMFC cathode catalytic layer, so that the ORR electrocatalysis activity and stability of the platinum-based catalyst can be improved.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method and application of MOF-derived mesoporous carbon.
Background
At present, power generation, industry and transportation serve as three main sources for generating carbon emission, and if green hydrogen energy is adopted to replace the traditional power generation technology and is applied to electric automobiles, the carbon emission is greatly reduced. The hydrogen fuel cell has the advantages of extending the driving mileage, rapidly charging, cleaning tail gas and the like, and is an important way for realizing the utilization of hydrogen energy. Among them, PEMFCs (proton exchange membrane fuel cells) are a new energy hot spot research direction with great development prospects due to their unique advantages of zero carbon emission, high conversion rate, and the like. Hydrogen energy and proton exchange membrane fuel cells continue to receive attention or even importance from many countries and businesses.
However, the current proton exchange membrane fuel cell cannot well meet the demands of people, and the activity and the stability of the proton exchange membrane fuel cell still need to be improved. While one of the most important parts constituting the PEMFC is a catalyst support, which is generally used to support and disperse catalytic metal nanoparticles, the support and platinum nanoparticles and an ionomer form a catalyst layer sandwiched between a proton exchange membrane and a gas diffusion layer. The catalyst support is required to provide not only stable supporting sites for the catalytic nanoparticles, but also transport channels for protons and electrons by forming continuous porous channels. Therefore, the catalyst support plays a critical role in the performance and durability of the PEMFC. However, the electrocatalyst in PEMFCs typically undergoes degradation. Meanwhile, the carrier corrosion damages the loading part, weakens the interaction between the carrier and the nano particles, leads to agglomeration or separation of the catalytic metal nano particles, and finally accelerates the degradation of the catalyst. To avoid these problems, it is necessary to develop a catalyst support having sufficient stability, strong interaction with catalytic nanoparticles, and high conductivity and stable porous structure, which is important for improvement of PEMFC performance and reduction of cost.
With the recent progress in research on carriers, many new types of carbon carriers have also appeared in known reports, such as Ordered Mesoporous Carbons (OMCs), carbon Nanotubes (CNTs), carbon Aerogels (CAs), and the like. The features of the features are different, and the brought performances are advantageous. Although the performance of the PEMFC is improved by the new carbon materials compared with the commercial carbon materials, the pursuit of improving the stability and Pt utilization rate of the ORR catalyst by people still cannot be well satisfied, or some problems exist, so that the new carbon materials cannot be successfully applied to commercial production. Commercial carbon black is still the most widely used catalyst carrier in the prior art, but has the key problems of low specific surface area, poor mass activity, poor stability and the like to be solved. The novel carbon material, such as ordered mesoporous carbon, has a good mesoporous structure and porosity, but has poor high current density performance. The problems of graphene and carbon nanotubes are also apparent, their surface inertness and cost problems need to be solved, and the two-dimensional structure of graphene extremely limits its development as a carrier. Good progress has also been made in non-carbon supports (metal oxides) and metal oxide-carbon composites. However, there are still gaps and challenges between the performance of today's materials and practical application requirements, with the most intuitive problem being that most metal oxides have poor electrical conductivity.
Metal Organic Frameworks (MOFs) have the advantages of high specific surface area, multiple structures, uniform and ordered pore structures and the like, and are paid attention to and researched in the field of new energy materials as a novel nano porous material. Based on good controllability of MOF, attempts have been made to use MOF-derived carbon materials as carriers, and it is desired to obtain a catalyst with low cost and excellent performance. However, MOF-derived carbons have large surface areas but few defect sites and the material surface is inert. Electrochemical activity of noble metal nanoparticles directly supported as a carrier is even worse than commercial Pt/C, and particularly under acidic media, conventional MOF-derived carbon-supported noble metal nanoparticles exhibit less desirable stability.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide MOF-derived mesoporous carbon serving as a carbon carrier of a PEMFC cathode platinum-based catalyst, and the problems are solved by performing template activation and strong acid acidification treatment on a target mesoporous carbon material.
The aim of the invention is realized by adopting the following technical scheme:
the first object of the invention is to provide a preparation method of MOF-derived mesoporous carbon, comprising the following steps:
(1) Preparation of MOF:
preparing a precursor MOF by utilizing the reaction of inorganic metal salt and an organic ligand;
(2) Preparation of MOF-derived mesoporous carbon:
sintering a mixture formed by mixing a precursor MOF, a template agent (such as silicate, melamine and potassium hydroxide) and a uniformly-mixable solvent (such as water and ethanol) at a high temperature to obtain NCP;
(3) Acid treatment with strong acid:
the obtained NCP powder is acidified by using a strong acid solution (such as hydrofluoric acid) to obtain the MOF-derived mesoporous carbon.
Preferably, the preparation method of the MOF specifically comprises the following steps:
s1, weighing inorganic metal salt zinc nitrate, dissolving in a methanol solution, and fully stirring until the zinc nitrate is dissolved, and marking as a solution A;
s2, weighing and dissolving the organic ligand 2-methylimidazole in a methanol solution, and fully stirring until the organic ligand 2-methylimidazole is dissolved, and marking as a solution B;
s3, pouring the solution A into the solution B, and then aging at room temperature;
s4, centrifugally precipitating the aged mixed solution, and drying in vacuum to obtain a precursor MOF solid (ZIF-8 is taken as an example in the experiment).
Preferably, in the step S1, the inorganic metal salt includes, but is not limited to, zinc salt, cobalt salt, and the like.
Preferably, in step S2, the organic ligand includes, but is not limited to, 2-methylimidazole.
Preferably, in the step S1, the inorganic metal salt is exemplified by zinc nitrate, and the mass-volume ratio of zinc nitrate to pure methanol solution (more than or equal to 99.9%) is 0.676g:35mL.
Preferably, in the step S2, the organic ligand is exemplified by 2-methylimidazole, and the mass-volume ratio of 2-methylimidazole to methanol (. Gtoreq.99.9%) is 2.010g:10mL.
Preferably, in the step S3, the aging time is 24 hours.
Preferably, in the step S4, the vacuum drying is to dry the obtained solid in a vacuum oven at 60 ℃ for 12 hours.
Preferably, the preparation method of the MOF-derived mesoporous carbon specifically comprises the following steps:
s5, weighing the prepared MOF solid, template agent sodium silicate and water, fully grinding, and drying the obtained mixture;
s6, performing heat treatment on the mixture obtained in the step S5, and cooling to obtain an intermediate, namely NCP-a-b (wherein a is the reaction temperature and b is the reaction time).
Preferably, in the step S5, the mass ratio of the MOF solid, the template agent sodium silicate and the water is 1:1:0.5, and the drying is carried out in a blast oven at 70 ℃ for 15 minutes.
Preferably, in the step S6, heat treatment is performed in a high-temperature tube furnace, nitrogen atmosphere protection is performed, and the heating rate is 1-5 ℃/min; heating to 300-1200 deg.c and maintaining for 1-12 hr for annealing at cooling rate of 1-50 deg.c/min.
Preferably, the step of the strong acid acidification treatment specifically comprises the following steps:
s7, preparing an acid solution with the mass concentration of 1% -95% by using a strong acid solution;
s8, fully grinding NCP powder in an agate mortar, adding the fully ground NCP powder into the prepared acid solution, stirring and mixing uniformly to form a mixed solution, and aging for 1-60 hours;
s9, centrifuging the solution obtained in the step S8 to obtain a precipitate, and washing the obtained precipitate with clear water and absolute ethyl alcohol for several times to ensure that the acid solution is completely removed;
s10, drying the solid obtained after centrifugation to obtain an acidized carbon material NC-a-b, namely the product of the invention;
preferably, in the step S7, the mass concentration of the acid solution is 1% -95%, and the maximum concentration is determined according to the maximum concentration of different acids, and is not limited to 95%; .
Preferably, in S8, the mass-volume ratio of NCP powder to acid solution is 0.2g:30mL, the mixed solution was placed in a fume hood and aged for 1 hour to 60 hours.
Preferably, in the step S10, the drying is performed in a hollow oven at 60 ℃ for 12 hours.
A second object of the present invention is to provide an application of MOF-derived mesoporous carbon as a carbon carrier of a PEMFC cathode platinum-based catalyst, i.e., forming a Pt/NC-a-b catalyst.
Preferably, the preparation process of the Pt/NC-a-b catalyst comprises the following steps:
s11, preparing an EG (ethylene glycol) water mixed solution, namely a mixed solution of ethylene glycol and ultrapure water;
s12, adding 70 mgMOF-derived mesoporous carbon into the mixed solution of S11, and then performing ultrasonic treatment for 30 minutes to obtain a dispersion MOF-derived mesoporous carbon composite solution;
s13, adding a chloroplatinic acid aqueous solution into the dispersion MOF derivative mesoporous carbon composite solution, dropwise adding a NaOH-EG mixed solution in small amounts, adjusting the pH value to 10-12, and then heating the mixture in a nitrogen atmosphere;
s14, dropwise adding a small amount of dilute nitric acid solution into the mixed solution in the step S13, adjusting the pH to 4-6, adding formaldehyde solution (36% -40%), and magnetically stirring;
s15, filtering the mixed solution obtained in the S14, washing the mixed solution with deionized water for multiple times to obtain a solid, and drying the solid to obtain the product Pt/NC-a-b catalyst (a is the reaction temperature and b is the reaction time).
Preferably, in the step S11, the volume ratio of ethylene glycol to ultrapure water in the EG (ethylene glycol) water mixed solution is 3:2.
Preferably, in the step S11, 28mL of ultrapure water and 42mL of ethylene glycol are included in the EG (ethylene glycol) aqueous mixture.
Preferably, in the step S12, the mass-volume ratio of the NCP composite material to the mixed solution is 70mg:70mL.
Preferably, in the step S13, the volume of the chloroplatinic acid aqueous solution is 3mL and the concentration is 10mg/mL.
Preferably, in the step S13, the temperature of the heating treatment is 140 ℃, and the temperature is reduced to 80 ℃ after refluxing for 6 hours.
Preferably, in the step S14, the formaldehyde solution (36% -40%) has a volume of 9mL, and is stirred for 12 hours at 80 ℃ under a magnetic stirrer after the addition.
Preferably, in the step S15, the solid is dried by placing the solid in a vacuum oven at 60 ℃ for 12 hours.
The beneficial effects of the invention are as follows:
1. according to the preparation method provided by the invention, MOF-derived mesoporous carbon is constructed as a PEMFC cathode platinum-based catalyst carbon carrier. The material has the advantages of high specific surface area, ordered porous structure and the like due to the adoption of MOF as a precursor. After template activation and strong acid acidification treatment are carried out on the target mesoporous carbon material, the pore size and pore distribution of the MOFs derivative carbon material with high specific surface area are effectively controlled, so that the target mesoporous carbon material has as many mesopores and defect sites as possible, the stability of platinum nano particles is improved, and the poisoning effect of platinum on active sites is effectively reduced. And then the element composition of the carbon material is controlled while the material structure is optimized by controlling different annealing problems, so that the negative influence caused by irrelevant elements in the precursor is reduced as much as possible. The platinum-based catalyst prepared by using the carbon catalyst carbon carrier can be applied to the field of ORR electrocatalysis and even a PEMFC cathode catalytic layer as a good oxygen reduction catalyst carrier, and is expected to further improve the ORR electrocatalysis activity and the stability of the platinum-based catalyst.
2. The present invention is directed to MOFs derivativesThe method is characterized in that a series of novel MOFs-derived mesoporous carbon is constructed as a PEMFC cathode platinum-based catalyst carbon carrier, wherein the problems of poor effect of directly loading noble metal catalytic nano particles on raw carbon and poor stability of the catalyst caused by poor corrosion resistance of the carbon material as a Pt/C catalyst carrier. The material has the advantages of high specific surface area, ordered porous structure, high electronic conductivity and the like due to the adoption of MOF as a precursor. Meanwhile, the invention adopts an innovative treatment method, and the material is acidified by strong acid after mesoporous treatment by using a template method. The method aims to increase the number of mesopores in a material structure, acidify and improve the chemical property of the material, and simultaneously, the method can also play a role in etching surface active sites, and the treated material can more effectively limit platinum nano particles in pores, so that the material has excellent load stability. When the material is used as a platinum-based catalyst carrier material, the electrochemical activity of the catalyst prepared by using the catalyst in Oxygen Reduction Reaction (ORR) electrochemistry can reach the electrochemical activity area (ECSA) of 150-200cm 2 /mg Pt And kinetic current density (J) k ) Can reach 4.37mA/cm 2 Far greater than 92cm of commercial platinum carbon catalyst 2 /mg Pt And 3.182mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the In addition, the electrochemical stability of the catalyst is also of great advantage over commercial Pt/C in the literature (FIG. 6).
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a flow chart of an embodiment of the present invention for preparing a Pt/NC-a-b catalyst;
FIG. 2 is a graph showing the adsorption and desorption of nitrogen from carbon material NC (reaction temperature 900 ℃ C., reaction time 9 h) prepared in example 1 of the present invention;
FIG. 3 is a report of an X-ray photoelectron spectroscopy test of the carbon material NC (reaction temperature 900 ℃ C., reaction time 9 h) prepared in example 1 of the present invention;
FIG. 4 is a graph comparing cyclic voltammetric performance of Pt-NC-a-b catalysts with commercial Pt-C catalysts in different ratios;
FIG. 5 is a linear sweep voltammetric performance comparison of a Pt-NC-a-b catalyst versus a commercial Pt-C catalyst for different ratios (for an example of 800-9, referring to a Pt-NC-800-9 catalyst);
FIG. 6 is a test result of stability of Pt/NC-a-b catalyst prepared in the example of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
Examples
The preparation method of the MOF-derived mesoporous carbon provided by the embodiment comprises the following steps:
(1) Preparation of MOF:
preparing a precursor MOF by utilizing the reaction of inorganic metal salt and an organic ligand;
(2) Preparation of MOF-derived mesoporous carbon:
sintering a mixture formed by mixing a precursor MOF, a template agent (such as silicate, melamine and potassium hydroxide) and a uniformly-mixable solvent (such as water and ethanol) at a high temperature to obtain NCP;
(3) Acid treatment with strong acid:
the obtained NCP powder is acidified by using a strong acid solution (such as hydrofluoric acid) to obtain the MOF-derived mesoporous carbon.
In general, MOFs-derived carbon materials are used to directly support noble metal catalytic nanoparticles. Due to the problems of low specific surface area, small pore diameter, limited loading sites and the like of the traditional MOFs derived carbon material, the problems of poor performance, even reduced capacity, reduced service life and the like of the battery are caused. Meanwhile, MOFs derived carbon materials have poor corrosion resistance, which results in reduced catalyst stability. Because corrosion of the support can damage the loading site, weakening the interaction between the support and the nanoparticles, causing agglomeration or separation of the catalytic metal nanoparticles, can accelerate degradation of the catalyst. Therefore, it is necessary to structurally perform mesoporous treatment on the target carbon material, and to effectively control the pore size and pore distribution of the MOFs-derived carbon material having a high specific surface area, so that the MOFs-derived carbon material has as many mesopores and defect sites as possible, thereby improving the stability of the platinum nanoparticles and effectively reducing the poisoning effect of platinum on the active sites. In addition, ZIFs derived carbon is even less effective as a carrier-supported MNP than commercial Pt/C electrodes due to problems such as poor electronegativity. In addition, MOFs derived carbons also face a critical problem to be solved when used as catalyst supports. For example, MOFs inevitably lose their elements during carbonization to derived carbon at high temperatures, even under a protective atmosphere, and some specific groups or pore structures are still severely affected by the high temperatures.
The following examples are based on examples in which starting materials, reagents or apparatus used, unless otherwise specified, are available from conventional commercial sources or may be obtained by methods known in the art.
The invention will be further described with reference to the following examples.
Example 1
A preparation method of MOF-derived mesoporous carbon, taking ZIF-8 as an example, comprising the following steps:
first, preparing MOF materials:
(1) 0.676g of zinc nitrate is weighed and dissolved in 35mL of methanol solution, and the mixture is fully stirred until the zinc nitrate is dissolved and is marked as solution A;
(2) 2.010g of 2-methylimidazole is weighed and dissolved in 10mL of methanol solution, and the mixture is stirred fully until the 2-methylimidazole is dissolved and marked as solution B;
(3) Pouring the solution A into the solution B, and then aging for 24 hours at room temperature;
(4) Centrifugally precipitating the mixed solution obtained in the step (3), and drying the obtained solid in a vacuum oven at 60 ℃ for 12 hours to obtain dodecahedral precursor ZIF-8 solid;
second, preparing MOF derivative mesoporous carbon:
(5) Weighing 1g of ZIF-8 solid prepared in the step (4), fully grinding with 0.5g of sodium silicate and 0.5g of water, and drying the obtained mixture in a blast oven at 70 ℃ for 15 minutes;
(6) And (3) heating the mixture obtained in the step (5) to a high temperature of 800-1000 ℃ in a high temperature tube furnace under the protection of nitrogen atmosphere at a heating rate of 5 ℃/min (hereinafter, heating at the heating rate), and preserving heat for 3-9 h for annealing. After the furnace is cooled, collecting annealed products in the quartz boat to obtain an intermediate, which is denoted as NCP-a-b (wherein a is the reaction temperature and b is the reaction time);
thirdly, acidizing by strong acid:
(7) Preparing HF (hydrofluoric acid) solution with mass concentration of 5% by using concentrated hydrofluoric acid solution;
(8) 0.2g of NCP powder was thoroughly ground in an agate mortar. The well-ground NCP powder was added to 30ml of the 5% HF (hydrofluoric acid) solution prepared in (7). Placing the mixed solution in a fume hood and standing for more than 24 hours;
(9) Centrifuging the solution obtained in the step (8) to obtain a precipitate, and washing the precipitate with clear water and absolute ethyl alcohol for several times to ensure complete removal of HF (hydrofluoric acid);
(10) And drying the solid obtained after centrifugation in a hollow oven at 60 ℃ for 12 hours to obtain the HF-treated carbon material NC-a-b (a is the reaction temperature and b is the reaction time), namely the ZIF-8-derived mesoporous carbon.
Example 2
An application of MOF-derived mesoporous carbon as a carbon carrier of a PEMFC cathode platinum-based catalyst, comprising the steps of:
first, preparing a Pt/NC catalyst:
(11) A 70mLEG (ethylene glycol) -water mixed solution was prepared, and the solvent was a mixed solution of ethylene glycol and ultrapure water (ethylene glycol: ultrapure water=3:2). The specific operation is as follows: 28mL of ultrapure water and 42mL of ethylene glycol were measured separately with a measuring cylinder, and mixed in a 100mL beaker.
(12) 70mgNC-a-b was added to the solution of step (11), followed by ultrasonic treatment for 30 minutes to obtain a dispersion NC-a-b complex solution.
(13) And (3) adding about 3mL of chloroplatinic acid aqueous solution with the concentration of 10mg/mL into the NC-a-b composite solution prepared in the step (12), dropwise adding a small amount of NaOH-EG mixed solution in a divided manner, dipping a small amount of NaOH-EG mixed solution on PH test paper after each dripping, and comparing the standard colorimetric card until the pH is adjusted to 10-12. The mixture was then refluxed at 140 ℃ for 6 hours under nitrogen atmosphere and then cooled to 80 ℃.
(14) And (3) dropwise adding a small amount of dilute nitric acid solution into the mixed solution in the step (13), dipping a small amount of the mixed solution on PH test paper after each dropwise adding, and comparing the standard color chart until the pH is adjusted to 4-6. Then 9ml of 38% formaldehyde solution was added, followed by stirring at 80℃for 12 hours under a magnetic stirrer.
(15) Filtering the mixed solution obtained in the step (14) and washing the mixed solution with deionized water for multiple times to obtain a solid. Then at 60 ℃. And then placing the solid into a vacuum furnace at 60 ℃ for drying for 12 hours to obtain the Pt/NC-a-b catalyst (a is the reaction temperature and b is the reaction time).
Experimental example
The electrochemical test of the experimental example of the invention was carried out in a three-electrode two-circuit electrochemical cell using a Rotating Disk Electrode (RDE) as the working electrode, a platinum sheet as the counter electrode, and a Reversible Hydrogen Electrode (RHE) as the reference electrode. Electrochemical experiments were performed using an electrochemical workstation.
To prepare the catalyst ink, the prepared catalyst was suspended in an isopropyl alcohol/DI water mixture (1:4) by sonication, and a quantity of 20wt% Nafion solution was added and ice-bath sonicated to disperse uniformly. The ink was then quantitatively dropped onto the platinum carbon electrode and spin-coated dry.
By applying a force on N before performing an electrochemical test 2 Saturated 0.1MHClO 4 The catalyst was electrochemically cleaned by cycling between 0.05 and 1.2V (vs. RHE) at a rate of 500 mV/s. Then, cyclic Voltammetry (CV) scans were performed at a scan rate of 20mV/s from 0.05V to 1V (relative to RHE) and electrochemical active area (ECSA) measurements were performed. At O 2 Saturated 0.1MHClO 4 In aqueous solution, a scan speed of 20mV/s was swept from 0.2V (for RHE) and the polarization curve of ORRs on RDE was recorded, with a spin speed of 1600rpm. All mass activities were calculated from the current density at 0.9V versus RHE potential, andnormalization was performed by the mass loading of platinum on RDE.
As shown in FIGS. 5 and 6, NC-900-0 was measured to have an electrochemical active area (ECSA) of about 150-200cm when used as a platinum-based catalyst support for ORR electrochemical testing 2 /mg Pt And a kinetic current density of 4.37mA/cm at 0.9V measured at 1600rpm rotation 2 . Under the same test conditions, the comparative sample of a 20wt% commercial platinum carbon catalyst with XC-72 as catalyst support exhibited an electrochemical active area of about 92cm 2 /mg Pt The mass activity at 0.9V measured at 1600rpm was 3.182mA/cm 2 . Furthermore, in the electrochemical stability test, the Pt-N-C-a-b catalyst showed excellent stability performance, and the electrochemical activity was lost by less than 30% after 30000 cycles.
In addition, the comparative commercial Pt-C selected in the present invention was 20wt% commercial Pt-C catalyst (Pt/XC-72 based catalyst with XC-72 as carbon support) produced by TANAKA in Japanese fields.
According to the embodiment of the invention, the carbon carrier of the PEMFC cathode platinum-based catalyst is constructed, and the platinum-based catalyst prepared by using the carbon carrier of the carbon catalyst can be applied to the field of ORR electrocatalysis as a good oxygen reduction catalyst carrier, even in a PEMFC cathode catalytic layer, so that the ORR electrocatalysis activity and stability of the platinum-based catalyst can be improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the MOF-derived mesoporous carbon is characterized by comprising the following steps of:
(1) Preparation of MOF:
preparing a precursor MOF by utilizing the reaction of inorganic metal salt and an organic ligand;
(2) Preparation of MOF-derived mesoporous carbon:
sintering the mixture formed by mixing the precursor MOF and the template agent at high temperature to obtain NCP;
(3) Acid treatment with strong acid:
and (3) acidizing the obtained NCP powder by using a strong acid solution to obtain the MOF derivative mesoporous carbon.
2. The method for preparing MOF-derived mesoporous carbon according to claim 1, wherein the MOF comprises ZIF-8, and the preparation method of the ZIF-8 specifically comprises:
s1, weighing inorganic metal salt zinc nitrate, dissolving in a methanol solution, and fully stirring until the zinc nitrate is dissolved, and marking as a solution A;
s2, weighing and dissolving the organic ligand 2-methylimidazole in a methanol solution, and fully stirring until the organic ligand 2-methylimidazole is dissolved, and marking as a solution B;
s3, pouring the solution A into the solution B, and then aging at room temperature;
s4, centrifugally precipitating the aged mixed solution, and drying in vacuum to obtain dodecahedron precursor MOF solid.
3. The method of preparing MOF-derived mesoporous carbon according to claim 2, wherein in step S1, the inorganic metal salt includes, but is not limited to, zinc nitrate;
in step S2, the organic ligands include, but are not limited to, 2-methylimidazole;
in the step S1, the inorganic metal salt is exemplified by zinc nitrate, and the mass volume ratio of the zinc nitrate to the methanol pure solution (more than or equal to 99.9%) is 0.676g:35mL;
in the step S2, the organic ligand is exemplified by 2-methylimidazole, and the mass-volume ratio of the 2-methylimidazole to methanol (more than or equal to 99.9%) is 2.010g:10mL;
in the step S3, the aging time is 24 hours;
in the step S4, the obtained solid was dried in a vacuum oven at 60 ℃ for 12 hours.
4. The method for preparing MOF-derived mesoporous carbon according to claim 1, wherein the method for preparing MOF-derived mesoporous carbon specifically comprises:
s5, weighing the prepared MOF solid, template agent sodium silicate and water, fully grinding, and drying the obtained mixture;
s6, performing heat treatment on the mixture obtained in the step S5, and obtaining an intermediate after cooling, wherein the intermediate is named NCP-a-b.
5. The method for preparing MOF-derived mesoporous carbon according to claim 4, wherein in the step S5, sodium silicate is taken as an example of the template agent, and the template agent includes, but is not limited to, sodium silicate;
in the step S5, the mass ratio of MOF solid to template agent sodium silicate to water is 1:1:0.5, and the drying is carried out in a blast oven at 70 ℃ for 15 minutes;
in the step S6, heat treatment is carried out in a high-temperature tube furnace, nitrogen atmosphere protection is carried out, and the heating rate is 1-5 ℃/min; heating to 300-1200 deg.c and maintaining for 1-12 hr for annealing at cooling rate of 1-50 deg.c/min.
6. The method for preparing MOF-derived mesoporous carbon according to claim 1, wherein the step of acidic treatment with a strong acid comprises:
s7, preparing an acid solution with the mass concentration of 1% -95% by using a strong acid solution;
s8, fully grinding NCP powder in an agate mortar, adding the fully ground NCP powder into the prepared acid solution, stirring and mixing uniformly to form a mixed solution, and aging for 1-60 hours;
s9, centrifuging the solution obtained in the step S8 to obtain a precipitate, and washing the obtained precipitate with clear water and absolute ethyl alcohol for several times to ensure that the acid solution is completely removed;
s10, drying the solid obtained after centrifugation to obtain the acidized carbon material NC-a-b, namely the product of the invention.
7. The method for preparing MOF-derived mesoporous carbon according to claim 6, wherein in the step S7, the mass concentration of the acid solution is 1% -95%, and the maximum concentration is not limited to 95% depending on the maximum concentration of different acids;
in the step S8, the mass-volume ratio of NCP powder to acid solution is 0.2g:30mL, placing the mixed solution in a fume hood and aging for 1 hour to 60 hours;
in the step S10, the drying is performed in a hollow oven at 60 ℃ for 12 hours.
8. Use of a MOF-derived mesoporous carbon prepared by the method of any one of claims 1 to 7, as a carbon support for a PEMFC cathode platinum-based catalyst, to form a Pt/NC-a-b catalyst.
9. The use of MOF-derived mesoporous carbon according to claim 8, wherein the preparation process of the Pt/NC-a-b catalyst comprises the steps of:
s11, preparing EG water mixed solution, namely, mixed solution of glycol and ultrapure water;
s12, adding 70 mgMOF-derived mesoporous carbon into the mixed solution of S11, and then performing ultrasonic treatment for 30 minutes to obtain a dispersion MOF-derived mesoporous carbon composite solution;
s13, adding a chloroplatinic acid aqueous solution into the dispersion MOF derivative mesoporous carbon composite solution, dropwise adding a small amount of NaOH-EG mixed solution in a multiple way, dipping a small amount of NaOH-EG mixed solution on PH test paper after each dripping, comparing a standard color chart until the pH is adjusted to 10-12, and then heating the mixture in a nitrogen atmosphere;
s14, dropwise adding a small amount of dilute nitric acid solution into the mixed solution in the step S13, adjusting the pH to 4-6, adding formaldehyde solution, and magnetically stirring;
s15, filtering the mixed solution obtained in the S14, washing the mixed solution with deionized water for multiple times to obtain a solid, and drying the solid to obtain the product Pt/NC-a-b catalyst.
10. The use of MOF-derived mesoporous carbon according to claim 9, wherein in step S11, the volume ratio of ethylene glycol to ultrapure water in the EG water mixed solution is 3:2;
in the step S11, the EG water mixed solution comprises 28mL of ultrapure water and 42mL of ethylene glycol;
in the step S12, the mass-volume ratio of the NCP composite material to the mixed solution is 70mg:70mL;
in the step S13, the volume of the chloroplatinic acid aqueous solution is 3mL, and the concentration is 10mg/mL;
in the step S13, the temperature of the heating treatment is 140 ℃, and after refluxing for 6 hours, the temperature is reduced to 80 ℃;
in the step S14, the mass concentration of the formaldehyde solution is 36% -40%, the volume of the formaldehyde solution is 9mL, and the formaldehyde solution is stirred for 12 hours at 80 ℃ under a magnetic stirrer after being added;
in the step S15, the solid is dried by placing the solid in a vacuum furnace at 60 ℃ for 12 hours.
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