CN103165916A - High-stability Pt-M/MOFs-graphene electro-catalytic agents and preparation method thereof - Google Patents
High-stability Pt-M/MOFs-graphene electro-catalytic agents and preparation method thereof Download PDFInfo
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- CN103165916A CN103165916A CN2013100660312A CN201310066031A CN103165916A CN 103165916 A CN103165916 A CN 103165916A CN 2013100660312 A CN2013100660312 A CN 2013100660312A CN 201310066031 A CN201310066031 A CN 201310066031A CN 103165916 A CN103165916 A CN 103165916A
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- 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
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- 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 high-stability Pt-M/MOFs-graphene electro-catalytic agents and a preparation method thereof. A carrier of catalytic agents is composed of metal-organic frameworks (MOFs) and graphene, and an active component is composed of Pt and metal M. The preparation method comprises the following steps: respectively dissolving H2PtCl6 6H2O and compound M with alcohol, merging, and then conducting ultrasonic processing; conducting dry dipping onto the carrier of MOFs- graphene, and conducting microwave dehydrating to a constant weight; adding water for slurrying, and adding reducing agents for reduction; and finally conducting filtering, washing and microwave dehydrating to obtain Pt-M/MOFs-graphene compound electro-catalytic agents. According to the high-stability Pt-M/MOFs-graphene electro-catalytic agents prepared by the method, the active component is small in particle size, is highly dispersed, has strong CO anti-poisoning capacity, and therefore the activity and the stability of the electro-catalytic agents are greatly improved.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst and preparation method.
Background technology
Fuel cell is 21 century one of of paramount importance new energy technology, it is a kind ofly directly the chemical energy of fuel to be converted into the energy device of electric energy in the mode of chemical reaction without burning, have that Conversion of Energy density is high, pollution is little, fuel is diversified, reliability is high, noise is low and be convenient to the advantages such as maintenance, oneself is subject to the great attention of countries in the world.Wherein the research of direct methanol fuel cell more attracts people's attention.It can be used for electrical source of power, mobile phone and kneetop computer power supply etc., is considered to one of alternative energy source technology that most possibly obtains the large-scale commercial applications application.But the catalyst of direct methanol fuel cell exists electro catalytic activity low, and can make catalyst poisoning at the produced simultaneously CO of Electrocatalytic Oxidation of Methanol, thus the activity stability performance of decrease battery.Therefore, improve the anti-poisoning ability of catalyst, oneself becomes the key technical problem that the fuel cell studies urgent need solves to improve electro catalytic activity and stability.
Summary of the invention
The object of the present invention is to provide a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst and preparation method, the catalyst activity component particles of the inventive method preparation is little, and high degree of dispersion has very strong anti-CO poisoning capability, has greatly improved catalyst activity stability.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst, its carrier is comprised of metallic organic framework (MOFs) and Graphene, and active component is comprised of Pt and metal M.
A kind of preparation method of high stability Pt-M/MOFs-Graphene eelctro-catalyst follows these steps to carry out:
(1) H
2PtCl
66H
2O and M compound add nonactive ion phosphoric acid or citric acid after merging with the alcoholic solvent dissolving respectively, are ultrasonic 15～30min under 20～65 ℃ of conditions in temperature;
(2) the active forerunner's soma of the Pt-M that makes in step (1) soaked be adsorbed on carrier MOFs-Graphene, with microwave dehydration to constant weight;
(3) step (2) is added the deionized water pulp, add the reducing agent reduction;
(4) filtration, washing, microwave dehydration obtain Pt-M/MOFs-Graphene composite electrocatalyst.
Described M is, Mn, Cr, Mo, Ni, Co, Zn etc., and wherein the preparation mol ratio of noble metal platinum and M is 1:0.5～5.
In described step (1) alcoholic solvent used be one or both in methyl alcohol, ethanol, propylene glycol, glycerol, ethylene glycol, polyvinyl alcohol in the formulated solvent of arbitrary volume ratio, the preparation of alcoholic solution and metal is according to the criterion calculation of metal concentration 1～20mol/L.
The phosphoric acid that adds in described step (1) or the mol ratio of citric acid and metal are 1:1～15.
In described MOFs-Graphene, MOFs used is MOFs (Ti), MOFs (Fe), and the mass ratio of MOFs and Graphene is 1:1.
The active forerunner's soma of described Pt-M soaks adsorption temp and is-10～20 ℃, adsorption time 20-40h, and microwave dehydration to the temperature of constant weight is 60～90 ℃.
Described reducing agent is one or both formulated mixtures of methyl alcohol, formaldehyde, formic acid, sodium borohydride, hydrazine hydrate, and concentration is 0.05～10mol/L, and reduction temperature is 40～95 ℃, and reducing agent calculates by the consumption that the 1g metal adds 2～30mL.
In described step (4), the microwave dehydration temperature is 90～120 ℃, and the time is 0.5～5h.
The catalyst activity component particles of the inventive method preparation is little, and high degree of dispersion, has very strong anti-CO poisoning capability, has greatly improved catalyst activity stability.
Embodiment
Embodiment 1
Metallic organic framework (MOFs) material preparation:
MOFs's (Ti) is synthetic: the butyl titanate of 0.50g terephthalic acid (TPA) and 0.26mL joins mixed solvent (9mLN, dinethylformamide (DMF)+1mL methyl alcohol), stir 30min under room temperature, be transferred in the teflon-lined stainless steel autoclave of 50mL, place 150 ℃ of lower crystallization 20h in baking oven, taking-up is cooled to room temperature, filters, and then the DMF washing is 3 times, each 10mL, methanol wash 3 times, each 10mL, 60 ℃ of dry 12h of products obtained therefrom.
MOFs's (Fe) is synthetic: 1.12gFe (NO
3)
39H
2The trimesic acid of O and 0.46g is dissolved in the DMF of 120mL, stirring at room 3h, getting brown solution changes in the teflon-lined stainless steel autoclave of 500mL, placed in baking oven 150 ℃ of crystallization 7 days, taking-up is cooled to room temperature, filters DMF washing 3 times, ethanol washing 3 times, 60 ℃ of dried overnight of products obtained therefrom.
The MOFs (Ti) that this example is prepared and the specific area of MOFs (Fe) are respectively 1000-1500m
2/ g, 2000-2500m
2/ g.
Embodiment 2
H with 9.75gPt
2PtCl
66H
2After the manganese acetate of O and 5gMn adds respectively one or both dissolvings in methyl alcohol, ethanol, propylene glycol, glycerol, ethylene glycol, polyvinyl alcohol to merge, guarantee between metal concentration 1～20mol/L, the phosphoric acid or the citric acid that add 0.01～0.4mol are ultrasonic 15～30min under 20～65 ℃ of conditions in temperature; Join in the carrier MOFs-Graphene of 44.3g, at-10～20 ℃ of stirring and adsorbing 20～40h, through microwave dehydration to constant weight; After adding the deionized water pulp, under agitation, adding 14.8～296mL concentration is methyl alcohol, formaldehyde, formic acid, the sodium borohydride of 0.05～10mo1/L, one or both solution reductions of hydrazine hydrate, and is warmed up to 40～95 ℃; Filtering, use deionized water cyclic washing catalyst, is the Pt-Mn/MOFs-Graphene eelctro-catalyst of 25wt% through the dry acquisition of 90～120 ℃ of microwave dehydrations load capacity.
The average grain diameter of the Pt-Mn alloy nano particle that the present embodiment is prepared is 2.1nm, and the alloy particle decentralization is 49%, and catalyst is dispersed fine in solvent, and this catalyst is used for methanol fuel cell, is 2.6mg/cm at Pt content
2, methanol concentration is that under 2.5mo1/L, 58 ℃, 0.10MPa condition, the current density during voltage 0.48V is 220mA/cm
2
Embodiment 3
H with 9.75gPt
2PtCl
66H
2Cr (the NO of O and 1.31gCr
3) 29H
2After O adds respectively one or both dissolvings in methyl alcohol, ethanol, propylene glycol, glycerol, ethylene glycol, polyvinyl alcohol to merge, guarantee between metal concentration 1～20mol/L, the phosphoric acid or the citric acid that add 0.00375～0.15mol are ultrasonic 15～30min under 20～65 ℃ of conditions in temperature; Join in the carrier MOFs-Graphene of 33.2g, at-10～20 ℃ of stirring and adsorbing 20～40h, through microwave dehydration to constant weight; After adding the deionized water pulp, under agitation, adding 24.8-496mL concentration is methyl alcohol, formaldehyde, formic acid, the sodium borohydride of 0.05～10mol/L, one or both solution reductions of hydrazine hydrate, and is warmed up to 40～95 ℃; Filtering, use deionized water cyclic washing catalyst, is the Pt-Cr/MOFs-Graphene eelctro-catalyst of 25wt% through the dry acquisition of 90～120 ℃ of microwave dehydrations load capacity.
The average grain diameter of the Pt-Cr alloy nano particle that the present embodiment is prepared is 2.4nm, and the alloy particle decentralization is 47%, and catalyst is dispersed fine in solvent, and this catalyst is used for methanol fuel cell, is 2.2mg/cm at Pt content
2, methanol concentration is that under 2.5mol/L, 58 ℃, 0.10MPa condition, the current density during voltage 0.50V is 300mA/cm
2
Embodiment 4
H with 9.75gPt
2PtCl
66H
2The ZnCl of O and 0.65gZn
2After adding respectively one or both dissolving merging in methyl alcohol, ethanol, propylene glycol, glycerol, ethylene glycol, polyvinyl alcohol, guarantee between metal concentration 1～20mol/L, adding 0.00625～0.25 phosphoric acid or citric acid, is ultrasonic 15～30min under 20～65 ℃ of conditions in temperature; Join in the carrier MOFs-Graphene of 31.2g, at-10～20 ℃ of stirring and adsorbing 20～40h, through microwave dehydration to constant weight; After adding the deionized water pulp, under agitation, adding 2.19～43.8mL concentration is methyl alcohol, formaldehyde, formic acid, the sodium borohydride of 0.05～10mol/L, one or both solution reductions of hydrazine hydrate, and is warmed up to 40～95 ℃; Filtering, use deionized water cyclic washing catalyst, is the Pt-Zn/MOFs-G eelctro-catalyst of 25wt% through the dry acquisition of 90～120 ℃ of microwave dehydrations load capacity.
The average grain diameter that the prepared Pt-Zn alloy nanoparticle of the present embodiment gives is 2.5nm, and the alloy particle decentralization is 45%, and catalyst is dispersed fine in solvent, and this catalyst is used for methanol fuel cell, is 2.5mg/cm at Pt content
2, methanol concentration is that under 2.5mol/L, 58 ℃, 0.10MPa condition, the current density during voltage 0.46V is 260mA/cm
2
Claims (9)
1. a high stability Pt-M/MOFs-Graphene eelctro-catalyst, is characterized in that, the carrier of catalyst is comprised of metallic organic framework (MOFs) and Graphene, and active component is comprised of Pt and metal M.
2. a method for preparing Pt-M/MOFs-Graphene eelctro-catalyst claimed in claim 1, is characterized in that, follows these steps to carry out:
(1) H
2PtCl
66H
2O and M compound add nonactive ion phosphoric acid or citric acid after merging with the alcoholic solvent dissolving respectively, are ultrasonic 15～30min under 20～65 ℃ of conditions in temperature;
(2) the active forerunner's soma of the Pt-M that makes in step (1) soaked be adsorbed on carrier MOFs-Graphene, with microwave dehydration to constant weight;
(3) step (2) is added the deionized water pulp, add the reducing agent reduction;
(4) filtration, washing, microwave dehydration obtain Pt-M/MOFs-Graphene composite electrocatalyst.
3. a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 1 and 2 and preparation method, is characterized in that, described M is, Mn, Cr, Mo, Ni, Co, Zn etc., and wherein the preparation mol ratio of noble metal platinum and M is 1:0.5～5.
4. the preparation method of a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 2, it is characterized in that, in step (1) alcoholic solvent used be one or both in methyl alcohol, ethanol, propylene glycol, glycerol, ethylene glycol, polyvinyl alcohol in the formulated solvent of arbitrary volume ratio, the preparation of alcoholic solution and metal is according to the criterion calculation of metal concentration 1～20mol/L.
5. the preparation method of a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 2, is characterized in that, the phosphoric acid that adds in step (1) or the mol ratio of citric acid and metal are 1:1～15.
6. a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 1 and 2 and preparation method, it is characterized in that, in described MOFs-Graphene, MOFs used is MOFs (Ti), MOFs (Fe), and the mass ratio of MOFs and Graphene is 1:1.
7. a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 1 and 2 and preparation method, it is characterized in that, the active forerunner's soma of described Pt-M soaks adsorption temp and is-10～20 ℃, adsorption time 20-40h, and microwave dehydration to the temperature of constant weight is 60～90 ℃.
8. a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 1 and 2 and preparation method, it is characterized in that, described reducing agent is one or both formulated mixtures of methyl alcohol, formaldehyde, formic acid, sodium borohydride, hydrazine hydrate, concentration is 0.05～10mol/L, reduction temperature is 40～95 ℃, and reducing agent calculates by the consumption that the 1g metal adds 2～30mL.
9. a kind of high stability Pt-M/MOFs-Graphene eelctro-catalyst according to claim 1 and 2 and preparation method, is characterized in that, in step (4), the microwave dehydration temperature is 90～120 ℃, and the time is 0.5～5h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655600A (en) * | 2016-03-22 | 2016-06-08 | 陈波 | Preparation method of Pt-Mn-graphene catalyst for fuel cell |
| CN106423279A (en) * | 2016-09-12 | 2017-02-22 | 哈尔滨理工大学 | Preparation method of graphene-supported Fe2Co metal-organic framework material |
| CN108110260A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel-cell catalyst and preparation method of metal-organic framework modification |
| CN110420661A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | In-situ preparation MIL-101 (Fe) composite catalyzing material and the preparation method and application thereof on a kind of 3D-rGO |
| CN110508324A (en) * | 2019-09-16 | 2019-11-29 | 温州涂屋信息科技有限公司 | A kind of Co-Zn bimetallic organic backbone electro-catalysis analysis oxygen material and its preparation method |
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Cited By (13)
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| CN105655600A (en) * | 2016-03-22 | 2016-06-08 | 陈波 | Preparation method of Pt-Mn-graphene catalyst for fuel cell |
| CN106423279A (en) * | 2016-09-12 | 2017-02-22 | 哈尔滨理工大学 | Preparation method of graphene-supported Fe2Co metal-organic framework material |
| CN106423279B (en) * | 2016-09-12 | 2019-04-09 | 哈尔滨理工大学 | A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials |
| CN108110260A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel-cell catalyst and preparation method of metal-organic framework modification |
| CN111244475A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature proton exchange membrane fuel cell membrane electrode and preparation method and application thereof |
| CN111244475B (en) * | 2018-11-28 | 2021-03-12 | 中国科学院大连化学物理研究所 | High-temperature proton exchange membrane fuel cell membrane electrode and preparation method and application thereof |
| CN110420661A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | In-situ preparation MIL-101 (Fe) composite catalyzing material and the preparation method and application thereof on a kind of 3D-rGO |
| CN110508324A (en) * | 2019-09-16 | 2019-11-29 | 温州涂屋信息科技有限公司 | A kind of Co-Zn bimetallic organic backbone electro-catalysis analysis oxygen material and its preparation method |
| CN110611105A (en) * | 2019-09-18 | 2019-12-24 | 清华大学 | Preparation method of ORR catalyst |
| CN110611105B (en) * | 2019-09-18 | 2021-05-18 | 清华大学 | Preparation method of ORR catalyst |
| CN111085275A (en) * | 2019-12-31 | 2020-05-01 | 华南理工大学 | Reductive graphene oxide/metal organic framework composite material and preparation method and application thereof |
| CN112467150A (en) * | 2020-11-26 | 2021-03-09 | 中国科学院大连化学物理研究所 | Nitrogen-phosphorus co-doped metal-organic framework packaged platinum-cobalt-based alloy and preparation method and application thereof |
| WO2022111008A1 (en) * | 2020-11-26 | 2022-06-02 | 中国科学院大连化学物理研究所 | Platinum-and-cobalt-based alloy encapsulated with nitrogen-and-phosphorus-co-doped metal organic framework, preparation method therefor and use thereof |
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Application publication date: 20130619 |