CN110137509A - A kind of CoO/NPC@SnO obtained by metal organic frame2Bifunctional catalyst and preparation method thereof - Google Patents

A kind of CoO/NPC@SnO obtained by metal organic frame2Bifunctional catalyst and preparation method thereof Download PDF

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CN110137509A
CN110137509A CN201910264291.8A CN201910264291A CN110137509A CN 110137509 A CN110137509 A CN 110137509A CN 201910264291 A CN201910264291 A CN 201910264291A CN 110137509 A CN110137509 A CN 110137509A
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npc
preparation
catalyst
coo
sno
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邹金龙
于洋
蒋保江
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Heilongjiang University
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Heilongjiang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of direct methanol fuel cell CoO/NPC@SnO2The preparation method of composite catalyst includes the following steps: the preparation of (1) MOFs；(2) MOFs of heat treatment step (1) obtains the catalyst precursor (Co/NPC) of granatohedron structure N doping porous carbon package cobalt；(3) presoma for obtaining step (2) and tin source stir, and are then restored to obtain the Co/NPC@Sn catalyst precursor of core-shell structure with reducing agent；(4) presoma that step (3) obtains further is heat-treated the cathode in direct methanol fuel cells catalyst for obtaining and haveing excellent performance；(5) then finely dispersed Pt nano particle is deposited, the direct methanol fuel cell catalyst of high catalytic activity is obtained using the composite catalyst of step (4) preparation as carrier.This method is easy to operate, catalyst morphology is controllable, high catalytic efficiency, has a good application prospect.

Description

A kind of CoO/NPC@SnO obtained by metal organic frame2Bifunctional catalyst and its Preparation method
Technical field
The present invention relates to electro-catalysis and fuel cell field, specifically a kind of water chestnut obtained by metal organic frame (MOFs) Shape dodecahedron core-shell structure CoO/NPC@SnO2Composite nano-catalyst as direct methanol fuel cell (DMFCs) anode and Cathode bifunctional catalyst and preparation method thereof.
Background technique
In the past few decades, direct methanol fuel cell (DMFCs) is due to its high efficiency, secure storage, low work Temperature and environment friendly and be considered as the promising energy, and be applied to portable electronic device and electric vehicle ?；The efficiency of DMFCs depends primarily on two important reactions: the hydrogen reduction of the methanol oxidation (MOR) and cathode of anode is anti- Answer (ORR)；Therefore, it is necessary to develop the effective catalyst that both can be promoted to react；So far, Pt base catalyst is Most common catalyst in DMFCs, because they all have good catalytic activity to the MOR of anode and the ORR of cathode；Especially Ground, Pt base catalyst show irreplaceable catalytic activity to MOR；But the active site on Pt is easy the intermediate production of absorption Object CO and cause catalyst poisoning, this causes the durability of Pt base catalyst during MOR poor；In addition, Pt belongs to noble metal Resource, the high cost and scarcity of Pt base catalyst are the commercialized major obstacles of DMFC；Therefore, a kind of high there is an urgent need to explore Effect and relatively cheap MOR catalyst carrier, the carrier can be poisoned to avoid the carbon monoxide (CO) of Pt active site, and can be with The Pt load capacity of catalyst is reduced, meanwhile, there is good promoting catalysis；The selection of cathod catalyst also greatly influences The performance and cost of DMFCs；In general, the ORR of cathode is being kinetically slowly, this needs catalyst to accelerate to react；Tool There is the Pt base catalyst of high activity to be typically considered preferred cathod catalyst；However, being made due to the infiltration of anode chamber's methanol The catalytic activity and efficiency for obtaining Pt base catalyst significantly reduce, and this problem has attracted extensive attention；Therefore, Pt base catalyst Easily poisoning and high cost to develop it is a series of there is high activity, the catalyst carrier of availability (low cost) and durability becomes It is more urgent.
It has recently been demonstrated that transition metal ions can be with organic ligand by being self-assembly of with periodic network The porous crystalline material (MOFs) of structure, the aperture of rule and shape and higher specific surface area cause great pass Note；Wherein, zeolite imidazole skeleton (ZIFs, such as ZIF-67 and ZIF-8) is considered as the ideal for preparing nitrogen-doped porous carbon material Precursor, because it has excellent chemical and thermal stability compared with other MOFs；Most of all, ZIF is in an inert atmosphere Pyrolysis carbon precursor, and the nitrogen source having using itself can be provided, the mesh structural porous carbon of N doping can be formed, these are special Point is so that it has great application prospect in a fuel cell；SnO2MOR take-off potential can be reduced by difunctional mechanism, and The anti-poisoning capability for improving methanol oxidation, because of SnO2It can be in Pt-SnO2Interface generates OH-, to effectively remove surface COads；Meanwhile the interaction between metal (Pt)-metal oxide can make charge be transferred to Pt from metal oxide, increase The local electron density of Pt nano particle；And transition metal oxide CoO also has similar property, Co2+Can in water O atom coordination, makes H atom be distributed to catalyst surface, then, Co2+Protonate ligand oxygen, to generate OH-, final to generate Metal-OH-And improve CO tolerance catalysts ability；The granatohedron nucleocapsid that the present invention is obtained by metal organic frame (MOFs) Structure C oO/NPC@SnO2Composite nano-catalyst, NPC are mutually cooperateed with two kinds of metal oxides, collectively promote the sun of DMFCs The electrocatalysis characteristic of pole MOR and cathode ORR.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, invent a kind of CoO/ that can be used as DMFCs catalyst carrier NPC@SnO2Composite nano materials and preparation method thereof；The method operating condition for preparing this kind of carrier is mild, controllable, has good Application prospect, transport the CoO/NPC SnO for preparing in this way2Catalyst carrier is after supporting Pt, since bimetallic aoxidizes The synergistic effect of object and NPC improve Pt-CoO/NPC@SnO2Electro catalytic activity of the catalyst to anode MOR and cathode ORR.
Granatohedron core-shell structure CoO/NPC@SnO2Composite nano-catalyst the preparation method is as follows:
One, soluble cobalt and 2-methylimidazole are dissolved in respectively in 25mL methanol, sufficiently after ultrasound and stirring, by 2- methyl miaow The methanol solution of azoles is quickly poured into the methanol solution of soluble cobalt, is continued to stir, is then allowed to stand, after methanol centrifuge washing It is dry, obtain the MOFs of purple；
Two, it takes MOFs made from step 1 to be put into tube type resistance furnace, is heat-treated under inert gas shielding atmosphere, to certainly Sample is so taken out after cooling and uses acid and water centrifuge washing respectively for several times, can be prepared by Co/NPC；
Three, the sample and pink salt for taking step 2 are sufficiently stirred in methyl alcohol, and it is molten that sodium borohydride is then added to mixing above In liquid, Co/NPC@Sn can be prepared by；
Four, it takes sample made from step 3 to be put into tube type resistance furnace, is heat-treated under inert gas protection, obtaining property Excellent DMFCs cathod catalyst (the i.e. CoO/NPC@SnO of granatohedron, core-shell structure of energy2)；
Five, it takes sample made from step 4 to mix with the aqueous solution of chloroplatinic acid, is sufficiently ultrasonic, it then, under stirring conditions, will Freshly prepd sodium borohydride solution is slowly dropped into above-mentioned solution with buret, after continuing stirring, with deionized water and anhydrous second Alcohol centrifuge washing for several times, obtains the DMFCs anode catalyst (Pt- of granatohedron, core-shell structure of high catalytic activity CoO/NPC@SnO2)；
Wherein soluble cobalt described in step 1 selects Co (NO3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2·4H2O It is one such or a variety of；Stirring and ultrasonic time are 5min ~ 12h；
Inert gas selects argon gas or nitrogen in step 2, and heat treatment temperature is 500 ~ 1000 DEG C, holds time as 1 ~ 4h；Centrifugation Revolving speed is 4000 ~ 10000rpm；
Pink salt described in step 3 selects SnCl4·5H2O or SnCl2·2H2O；The mass ratio of Co/NPC and pink salt is 1: 0.01~5；Mixing time is 1 ~ 72h；
Inert gas selects argon gas or nitrogen in step 4, and heat treatment temperature is 300 ~ 1000 DEG C, holds time as 1 ~ 4h；
Ultrasonic time is 10 ~ 120min in step 5, and mixing time is 12 ~ 72h, and centrifugal rotational speed is 4000 ~ 10000rpm, Pt's Load capacity is 0.1 ~ 30%；
The CoO/NPC@SnO of the granatohedron, core-shell structure that are obtained with above-mentioned preparation method2Catalyst is in DMFCs Using.
Detailed description of the invention
Fig. 1 is prepared CoO/NPC@SnO2The X-ray diffractogram of nanoparticle.
Fig. 2 is prepared Pt-CoO/NPC@SnO2The X-ray diffractogram of nanoparticle.
Fig. 3 is prepared CoO/NPC@SnO2Nanoparticle is in O2Cyclic voltammetric (CV) in the KOH solution of the 0.1M of saturation Curve graph.
Fig. 4 is prepared Pt-CoO/NPC@SnO2Circulation volt of the nanoparticle in the methanol solution of the KOH and 1M of 1M Pacify (CV) curve graph；
Specific implementation method.
Specific implementation method one: granatohedron core-shell structure CoO/NPC@SnO2The preparation side of composite nano-catalyst Method is as follows:
One, soluble cobalt and 2-methylimidazole are dissolved in respectively in 25mL methanol, sufficiently after ultrasound and stirring, by 2- methyl miaow The methanol solution of azoles is quickly poured into the methanol solution of soluble cobalt, is continued to stir, is then allowed to stand, with methanol centrifuge washing Afterwards, dry, obtain the MOFs of purple；
Two, it takes MOFs made from step 1 to be put into tube type resistance furnace, is heat-treated under inert gas shielding atmosphere, it is natural After cooling, takes out sample and use acid and deionized water centrifuge washing respectively for several times, can be prepared by Co/NPC；
Three, the sample and pink salt for taking step 2 are sufficiently stirred in methyl alcohol, and it is molten that sodium borohydride is then added to mixing above In liquid, Co/NPC@Sn can be prepared by；
Four, it takes sample made from step 3 to be put into tube type resistance furnace, is heat-treated, that is, made under inert gas shielding atmosphere DMFCs cathod catalyst (the CoO/NPC@SnO of granatohedron, core-shell structure that must be had excellent performance2)；
Five, take the aqueous solution of sample made from step 4 and chloroplatinic acid sufficiently ultrasonic, under stirring conditions, by freshly prepd boron Sodium hydride solution is slowly dropped into above-mentioned solution with buret, after continuing stirring, with deionized water and dehydrated alcohol centrifuge washing For several times, DMFCs anode catalyst (the Pt-CoO/NPC@of granatohedron, core-shell structure of high catalytic activity is obtained SnO2)；
Specific implementation method two: present implementation is unlike specific implementation method one: selected solubility cobalt in step 1 Salt is Co (NO3)2·6H2O, ultrasound and mixing time are 20min, other are same as the specific embodiment one；
Specific implementation method three: present embodiment is unlike specific embodiment one or mode two: indifferent gas in step 2 Body selects nitrogen, and heat treatment temperature is 700 DEG C, holds time as 2h；Centrifugal rotational speed is 10000rpm, other and specific embodiment party Formula one or mode two are identical；
Specific implementation method four: present embodiment is unlike specific embodiment one to mode three: described in step 3 Pink salt selects SnCl2·2H2O；The mass ratio of Co/NPC and pink salt is 1:1；Mixing time is 72h, other and specific embodiment One to identical described in mode three；
Specific implementation method five: present embodiment is unlike specific embodiment one to mode four: indifferent gas in step 4 Body selects nitrogen, and heat treatment temperature is 800 DEG C, holds time as 2h, other with described in specific embodiment one to mode four It is identical；
Specific implementation method six: present embodiment is unlike specific embodiment one to mode five: when ultrasonic in step 5 Between be 30min, mixing time 48h, the load capacity of centrifugal rotational speed 10000rpm, Pt is 5%, other and specific embodiment One to identical described in mode five.
The CoO/NPC@SnO of the granatohedron, core-shell structure that are obtained with above-mentioned preparation method2Catalyst is in DMFCs In application.
Fig. 3 can be seen that the Pt-CoO/NPC@SnO prepared by cyclic voltammetry relatively this implementation2With business Pt/C Catalyst is respectively 1500mA mg to the electro catalytic activity of anode MORPt -1With 480 mA mgPt -1, show Pt-CoO/NPC@ SnO2The MOR performance of nanocatalyst is significantly larger than business Pt/C catalyst.
Fig. 4 can be seen that the CoO/NPC@SnO prepared by cyclic voltammetry relatively this implementation2It is urged with business Pt/C Agent is respectively 0.8144V and 0.8054V to the spike potential of cathode ORR, shows CoO/NPC@SnO2The ORR of nanocatalyst is living Property be better than business Pt/C catalyst.

Claims (6)

1. granatohedron, core-shell structure CoO/NPC@SnO2 composite Nano that one kind is obtained by metal organic frame (MOFs) Catalyst is as direct methanol fuel cell (DMFCs) anode and cathode bifunctional catalyst and preparation method thereof, characterized in that Include the following steps:
1) preparation of MOFs: soluble cobalt and 2-methylimidazole are dissolved in methanol respectively, will after sufficiently ultrasound and stirring The methanol solution of 2-methylimidazole is quickly poured into the methanol solution of soluble cobalt, is continued to stir, is then allowed to stand, with methanol from It is dry after heart washing, obtain the MOFs of purple；
2) preparation of Co/NPC: taking MOFs made from step 1) to be put into tube type resistance furnace, under inert gas shielding atmosphere into Row is heat-treated, and takes out sample after Temperature fall, respectively for several times with acid and deionized water centrifuge washing, can be prepared by Co/NPC；
3) it the preparation of Co/NPC@Sn: takes the sample of step 2 to be sufficiently stirred in methyl alcohol with pink salt, then sodium borohydride is added Into mixed solution above, Co/NPC@Sn can be prepared by；
4) CoO/NPC@SnO2Preparation: take sample made from step 3) to be put into tube type resistance furnace, in inert gas shielding atmosphere Under be heat-treated, obtain DMFCs cathod catalyst (the CoO/NPC@of granatohedron, core-shell structure haveing excellent performance SnO2)；
5) Pt-CoO/NPC@SnO2Preparation: take the aqueous solution of sample made from step 4) and chloroplatinic acid to be sufficiently mixed, ultrasound, Under conditions of stirring, freshly prepd sodium borohydride solution is slowly dropped into above-mentioned solution with buret, after continuing stirring, is spent Ionized water and dehydrated alcohol centrifuge washing for several times, obtain high catalytic activity DMFCs anode catalyst (granatohedron, The Pt-CoO/NPC@SnO of core-shell structure2).
2. preparation method as described in claim 1, which is characterized in that soluble cobalt described in step (1) selects Co (NO3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2·4H2O is one such or a variety of；Stirring and ultrasonic time be 5min ~ 12h。
3. preparation method as described in claim 1, which is characterized in that inert gas selects argon gas or nitrogen, heat in step (2) Treatment temperature is 500 ~ 1000 DEG C, is held time as 1 ~ 4h；Centrifugal rotational speed is 4000 ~ 10000rpm.
4. preparation method as described in claim 1, which is characterized in that pink salt described in step (3) selects SnCl4·5H2O Or SnCl2·2H2O；The mass ratio of Co/NPC and pink salt is 1:0.01 ~ 5；Mixing time is 1 ~ 72h.
5. preparation method as described in claim 1, which is characterized in that inert gas selects argon gas or nitrogen, heat in step (4) Treatment temperature is 300 ~ 1000 DEG C, is held time as 1 ~ 4h.
6. preparation method as described in claim 1, which is characterized in that ultrasonic time is 10 ~ 120min, stirring in step (5) Time is 12 ~ 72h, and the load capacity of Pt is 0.1 ~ 30%.
CN201910264291.8A 2019-04-03 2019-04-03 A kind of CoO/NPC@SnO obtained by metal organic frame2Bifunctional catalyst and preparation method thereof Pending CN110137509A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931798A (en) * 2019-12-12 2020-03-27 哈尔滨理工大学 Preparation method of 3DPC/Co/CoO lithium battery negative electrode material
CN111559761A (en) * 2020-04-27 2020-08-21 温州大学 Synthesis method of ZIF-67 derived CoO
CN112164809A (en) * 2020-10-06 2021-01-01 青岛蓝创科信新能源科技有限公司 Preparation method of PtCo @ NC catalyst for direct methanol fuel cell
CN113231071A (en) * 2021-03-29 2021-08-10 同济大学 Mesoporous Co/CoO/SnO carbon nano-cubic composite catalyst and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931798A (en) * 2019-12-12 2020-03-27 哈尔滨理工大学 Preparation method of 3DPC/Co/CoO lithium battery negative electrode material
CN111559761A (en) * 2020-04-27 2020-08-21 温州大学 Synthesis method of ZIF-67 derived CoO
CN112164809A (en) * 2020-10-06 2021-01-01 青岛蓝创科信新能源科技有限公司 Preparation method of PtCo @ NC catalyst for direct methanol fuel cell
CN112164809B (en) * 2020-10-06 2021-12-24 江西东醇新能源科技有限公司 Preparation method of PtCo @ NC catalyst for direct methanol fuel cell
CN113231071A (en) * 2021-03-29 2021-08-10 同济大学 Mesoporous Co/CoO/SnO carbon nano-cubic composite catalyst and preparation method and application thereof

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Application publication date: 20190816