CN107126974B - ZIF-67 modifies Fe3O4The preparation of@PZS core-shell particles and its application of ORR catalyst - Google Patents
ZIF-67 modifies Fe3O4The preparation of@PZS core-shell particles and its application of ORR catalyst Download PDFInfo
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- CN107126974B CN107126974B CN201710423396.4A CN201710423396A CN107126974B CN 107126974 B CN107126974 B CN 107126974B CN 201710423396 A CN201710423396 A CN 201710423396A CN 107126974 B CN107126974 B CN 107126974B
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- 239000002245 particle Substances 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- -1 hydroxyl diphenyl sulphone Chemical compound 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000003763 carbonization 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
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- B01J35/398—
Abstract
The present invention relates to the Fe of ZIF-67 modification3O4The preparation of@PZS core-shell particles and its application as ORR catalyst, the present invention prepare Fe using solvent-thermal method3O4Magnetic microsphere, and Fe is prepared using condensation methods as core3O4@PZS core-shell particles realize ZIF-67 to Fe using in situ synthesis3O4The modification of@PZS core-shell particles.The magnetic microsphere of preparation is doped with Fe, Co, N, P and S multiple element, has good ORR catalytic activity, preferable cyclical stability and methanol tolerant, can be absorbed by magnet and repeatedly be recycled.
Description
Technical field
The present invention relates to magnetic core-shell field of nanometer material technology and ORR catalytic field, are specifically prepared using solvent-thermal method
Surface has the Fe of hydroxyl and carboxyl modified3O4Magnetic microsphere, and Fe is prepared using condensation methods as core3O4@PZS nucleocapsid
Microballoon realizes ZIF-67 to Fe using in situ synthesis3O4The modification of@PZS core-shell particles is adulterated using polyatom and improves its ORR
Catalytic activity.
Background technique
The dynamics of redox reaction (ORR) is very slow, limits the electrochemistry such as fuel cell and metal-air battery
Conversion and storage device, although platinum and its alloy are considered as best ORR catalyst, expensive price, lower storage
Key issues of storage, poor durability, easy methanol poisoning effect, hinders its large-scale practical application.Therefore, it is necessary to
The higher non-precious metal catalyst of a kind of catalytic activity is developed to replace platinum catalyst.
Fe3O4Nanoparticle be it is a kind of be readily synthesized and surface-functionalized nano magnetic material, there is good biology
Compatibility, biological degradability, low toxicity, repeatable the advantages that recycling, it is widely used in the fields such as biomedical engineering, army
The fields such as thing, protection, catalysis.Currently, preparation Fe3O4There are many method of microballoon, mainly have coprecipitation, microemulsion method, hydro-thermal/
Solvent-thermal method, high-temperature decomposition, sonochemical method, electrochemical process and colloidal sol~gel method.The present invention mainly uses solvent-thermal method
Synthesize Fe3O4Microballoon.
Metal-organic framework (Metal-Orgaic Frameworks), abbreviation MOFs, be by organic ligand and metal from
The hybrid inorganic-organic materials with molecule inner pore that son or cluster are self-assembly of by coordinate bond.It is organic in MOFs
The arrangement of ligand and metal ion or cluster has apparent directionality, different frame pore structures can be formed, thus table
Reveal different absorption properties, optical property, electromagnetic property etc., MOFs shows huge hair in terms of modern materials science
Open up potentiality and tempting development prospect.
Summary of the invention
The object of the present invention is to provide a kind of simple synthetic method preparation ZIF-67 to modify Fe3O4@PZS core-shell particles, and
It is used as ORR catalyst.
To achieve the goals above, the present invention takes following technical scheme:
The first, Fe3O4The preparation of@PZS core-shell particles
5~25mg hexachlorocyclotriph,sphazene is added in single neck bottle of 50mL, 25.2~126mg is to hydroxyl diphenyl sulphone (DPS), and 30.2
The Fe that~151mg is 100~300nm by diameter prepared by solvent-thermal method3O4, 50mL acetonitrile or acetone are as solvent, ultrasound
10min be completely dissolved with it is evenly dispersed.Then it is sealed with rubber stopper, inject 0.5mL triethylamine rapidly with syringe or rubbed together
Other tertiary amines (tri-n-butyl amine or trioctylphosphine amine) of your amount are used as acid binding agent, and 10s~1min is (slightly poor according to solvent difference
Not, acetonitrile internal ratio is very fast, slow in acetone), form white emulsion.Then 50Hz ultrasound, the reaction was continued 3 hours, then
8000rpm is centrifuged 10min, is washed 2 times with acetone, ethyl alcohol and deionized water respectively, final product is 40 DEG C in vacuum drying oven
It is dry.The second, ZIF-67 is to Fe3O4The modification of@PZS core-shell particles:
Take 10~60mg Fe3O4@PZS core-shell particles are dispersed in 10mL and contain 145.5~1455.1mg Co (NO3)2·
6H2In the methanol solution of O, it is molten that the methanol that 10mL contains 82.1~821.0mg 2-methylimidazole is added after 30min for ultrasonic disperse
Liquid stands 30min at room temperature, then collects particle with magnet, with ethanol washing 2 times, final product is 40 in vacuum drying oven
DEG C drying.
ZIF-67 modifies Fe3O4Application of the@PZS core-shell particles as ORR catalyst, method particularly includes:
The first, by the microballoon of synthesis in tube furnace 800~1000 DEG C of 1~3h of carbonization treatment under nitrogen atmosphere；
The second, the sample for taking 5.0mg step 1 to obtain, is added 1mL ethyl alcohol and 100 μ L mass fractions are 10%
Nafion solution, ultrasonic 30min, makes it be uniformly dispersed, and obtains catalyst solution；
Third tests its ORR catalytic activity, cyclical stability and methanol tolerant, electrolyte O with electrochemical workstation2
The 0.1M KOH of saturation, 5~10mV of sweep speed s-1, rotation speed 400-2500rpm.Compared with prior art, of the invention
The advantages of be:
Preparation method of the invention is simple, and raw material is cheap and easy to get, and it is more that the magnetic microsphere of preparation is doped with Fe, Co, N, P and S
Kind element, has good ORR catalytic performance, preferable cyclical stability and methanol tolerant, can be absorbed by magnet and repeatedly be returned
It receives and utilizes.
Detailed description of the invention
Fig. 1 is the Fe prepared in embodiment 13O4The TEM of@PZS core-shell particles schemes.
Fig. 2 is the Fe of the ZIF-67 modification prepared in embodiment 13O4The TEM of@PZS core-shell particles schemes.
Fig. 3 is the Fe of the ZIF-67 modification prepared in embodiment 13O4The LSV curve of@PZS core-shell particles.
Fig. 4 is the Fe of the ZIF-67 modification prepared in embodiment 13O4The stable circulation linearity curve of@PZS core-shell particles.
Fig. 5 is the Fe of the ZIF-67 modification prepared in embodiment 13O4The methanol tolerant stability curve of@PZS core-shell particles.
Specific embodiment
The present invention presented below-ZIF-67 modifies Fe3O4The application of the preparation and its ORR catalyst of@PZS core-shell particles
Specific embodiment.
Embodiment 1
10mg hexachlorocyclotriph,sphazene is added in single neck bottle of 50mL, 50.4mg is to hydroxyl diphenyl sulphone (DPS), and 60.4mg is by solvent
The Fe of the diameter about 250nm of thermal method preparation3O4, as solvent, ultrasonic 10min is completely dissolved and uniformly for 50mL acetonitrile or acetone
Dispersion.Then it is sealed with rubber stopper, injects 0.5mL triethylamine rapidly with syringe or (three just with other tertiary amines of mole
Butylamine or trioctylphosphine amine) be used as acid binding agent, about 10s~1min (difference is slightly had according to solvent difference, acetonitrile internal ratio is very fast,
It is slow in acetone), form white emulsion.Then 50Hz ultrasound, the reaction was continued 3 hours, and then 8000rpm is centrifuged 10min and receives
Collect particle, is washed 2 times with acetone, ethyl alcohol and deionized water respectively, the 40 DEG C of dryings in vacuum drying oven of final product.
Take 30mg Fe3O4@PZS core-shell particles are dispersed in 10mL and contain 291.0mg Co (NO3)2·6H2The methanol solution of O
In, the methanol solution that 10mL contains 410.5mg 2-methylimidazole is added after 30min, stands 30min at room temperature for ultrasonic disperse,
Then 8000rpm is centrifuged 10min, with ethanol washing 2 times, the 40 DEG C of dryings in vacuum drying oven of final product.
The Fe of ZIF-67 modification3O4@PZS core-shell particles 800 DEG C of carbonization treatment 1h under nitrogen atmosphere in tube furnace.It takes
The sample that 5.0mg is carbonized, is added the Nafion solution of 1mL ethyl alcohol and 100 μ L 5%, and ultrasonic 30min keeps its dispersion equal
It is even, obtain catalyst solution.
Its ORR catalytic activity, cyclical stability and methanol tolerant, electrolyte O are tested with electrochemical workstation2Saturation
0.1M KOH, sweep speed 10mV s-1, rotation speed 1600rpm.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (2)
1.ZIF-67 modifies Fe3O4The preparation method of@PZS core-shell particles, which comprises the following steps:
The first, Fe3O4The preparation of@PZS core-shell particles: addition 5 ~ 25mg hexachlorocyclotriph,sphazene in single neck bottle of 50mL, 25.2 ~
126mg is to hydroxyl diphenyl sulphone (DPS), the Fe that 30.2 ~ 151mg is 100 ~ 300nm by diameter prepared by solvent-thermal method3O4, 50mL acetonitrile or
Person's acetone as solvent, ultrasonic 10min be completely dissolved with it is evenly dispersed, then sealed with rubber stopper, injected rapidly with syringe
For 0.5mL triethylamine as acid binding agent, 10s ~ 1min forms white emulsion, then 50Hz ultrasound, the reaction was continued 3 hours, then
8000rpm is centrifuged 10min, is washed 2 times with acetone, ethyl alcohol and deionized water respectively, final product is 40 °C in vacuum drying oven
It is dry；
The second, ZIF-67 is to Fe3O4The modification of@PZS core-shell particles: 10 ~ 60mg Fe is taken3O4@PZS core-shell particles are dispersed in 10mL
Contain 145.5 ~ 1455.1mg Co (NO3)2•6H2In the methanol solution of O, ultrasonic disperse, be added after 30min 10mL contain 82.1 ~
The methanol solution of 821.0mg 2-methylimidazole stands 30min at room temperature, then particle is collected with magnet, with ethanol washing 2
It is secondary, the 40 °C of dryings in vacuum drying oven of final product.
2. the ZIF-67 that preparation method as described in claim 1 obtains modifies Fe3O4@PZS core-shell particles are as ORR catalyst
Application, which is characterized in that specific steps are as follows:
The first, by the microballoon of synthesis in tube furnace 800 ~ 1000 DEG C of 1 ~ 3h of carbonization treatment under nitrogen atmosphere；
The second, the Nafion solution that 1mL ethyl alcohol and 100 μ L mass fractions are 10% is added in the sample for taking 5.0mg step 1 to obtain,
Ultrasonic 30min, makes it be uniformly dispersed, and obtains catalyst solution；
Third tests its ORR catalytic activity, cyclical stability and methanol tolerant, electrolyte O with electrochemical workstation2Saturation
0.1 M KOH, 5 ~ 10 mVs of sweep speed−1, rotation speed is 400-2500 rpm.
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| CN112774713A (en) * | 2021-01-25 | 2021-05-11 | 华南理工大学 | Bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613534A (en) * | 2009-07-23 | 2009-12-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Water-soluble nano-carrier and preparation method thereof |
| CN102585517A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Hollow polyphosphazenes microsphere with magnetic particles embedded in casing layer and preparation method thereof |
| CN102583312A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
| CN103638979A (en) * | 2013-11-04 | 2014-03-19 | 北京化工大学 | Magnetic zeolite imidazate metal organic skeletal material, preparation thereof and application to liquid phase condensation catalytic reaction |
| CN103896246A (en) * | 2014-02-19 | 2014-07-02 | 上海交通大学 | Preparation method and application of heteroatom-doped porous carbon nano-tube |
| WO2017042564A1 (en) * | 2015-09-08 | 2017-03-16 | Johnson Matthey Fuel Cells Limited | Oxygen reduction reaction catalyst |
| CN106549163A (en) * | 2016-11-03 | 2017-03-29 | 大连理工大学 | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate |
-
2017
- 2017-06-07 CN CN201710423396.4A patent/CN107126974B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613534A (en) * | 2009-07-23 | 2009-12-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Water-soluble nano-carrier and preparation method thereof |
| CN102585517A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Hollow polyphosphazenes microsphere with magnetic particles embedded in casing layer and preparation method thereof |
| CN102583312A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
| CN103638979A (en) * | 2013-11-04 | 2014-03-19 | 北京化工大学 | Magnetic zeolite imidazate metal organic skeletal material, preparation thereof and application to liquid phase condensation catalytic reaction |
| CN103896246A (en) * | 2014-02-19 | 2014-07-02 | 上海交通大学 | Preparation method and application of heteroatom-doped porous carbon nano-tube |
| WO2017042564A1 (en) * | 2015-09-08 | 2017-03-16 | Johnson Matthey Fuel Cells Limited | Oxygen reduction reaction catalyst |
| CN106549163A (en) * | 2016-11-03 | 2017-03-29 | 大连理工大学 | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate |
Non-Patent Citations (1)
| Title |
|---|
| 新型功能聚合物微球的制备、表征及其应用研究;潘元佳;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150315;第85-86、92、132-133页 * |
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