CN105363478A - One-step solvothermal preparation method and application of M-doped Sex-Ru/C - Google Patents

One-step solvothermal preparation method and application of M-doped Sex-Ru/C Download PDF

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Publication number
CN105363478A
CN105363478A CN201510650905.8A CN201510650905A CN105363478A CN 105363478 A CN105363478 A CN 105363478A CN 201510650905 A CN201510650905 A CN 201510650905A CN 105363478 A CN105363478 A CN 105363478A
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Prior art keywords
doped
catalyst
preparation
sex
solvothermal preparation
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CN201510650905.8A
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Chinese (zh)
Inventor
张传香
赵媛
陶海军
许帅
杨柳
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Nanjing University of Aeronautics and Astronautics
Nanjing Institute of Technology
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Nanjing University of Aeronautics and Astronautics
Nanjing Institute of Technology
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Priority to CN201510650905.8A priority Critical patent/CN105363478A/en
Publication of CN105363478A publication Critical patent/CN105363478A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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 one-step solvothermal preparation method and application of M-doped Sex-Ru/C. The method comprises the steps that firstly, ruthenium salt, ruthenium salt, activated carbon and an M source are taken to be added in isopropanol solvent to obtain a reaction precursor solution; secondly, a solvothermal reaction is performed to obtain a black powder intermediate; thirdly, the black powder intermediate is put into a tube furnace to be calcined, and then an M-doped Sex-Ru/C catalyst is obtained. According to the one-step solvothermal preparation method and application of the M-doped Sex-Ru/C, the M (M=Mo, Pt and Fe)-doped Sex-Ru/C composite catalyst which is excellent in in-situ growth crystallinity is prepared through a one-step solvothermal method, the oxygen reduction, methanol tolerance and stabilization properties of the M-doped (especially Pt-doped) Sex-Ru/C composite catalyst are all optimized, and the composite catalyst is a novel composite catalyst which is expected to be applied and popularized in direct methanol fuel cells.

Description

M is doped in Se xone step solvothermal preparation method and the application of-Ru/C
Technical field
The present invention relates to M and be doped in Se xone step solvothermal preparation method and the application of-Ru/C, belongs to field of material synthesis technology.
Background technology
In in recent years, the seriousness that is wide and its pollution level that is high, impact scope of haze occurrence frequency was all unprecedented.The facts such as the quick-fried table of PM2.5, air visibility reduce, middle and primary schools suspend classes, highway is closed constantly warn us, and pollution control must be picked up from source, i.e. the discharge of decreasing pollution thing, and the use wherein reducing fossil energy is one of effective method.Non-renewable simultaneously due to fossil energy, therefore the research of clean reproducible energy receives increasing attention, DMFC (Directmethanolfuelcell, DMFC) being take methyl alcohol as fuel, there is the advantage that other type low-temperature fuel cell is incomparable, as fuel source is abundant, low price, electro-chemical activity are high, being easy to carry about with one stores, is particularly suitable as compact power supply or movable power source, has broad application prospects.
DMFC has huge using value, but higher cost and shorter life-span seriously constrain its commercialization process, and the core of this two large problems is all inseparable with catalyst.At present, the cathod catalyst of DMFC is still based on Pt series catalysts, although its load capacity can be down to 0.5mg/cm 2below, but due to Pt resource scarcity, expensive, cause battery cost to remain high, limit commercialization and the large-scale production of DMFC.Meanwhile, negative electrode hydrogen reduction slowly (Oxygenreductionreaction, ORR) dynamics, anode methanol crossover and the intermediate oxidation product problem such as make Pt series catalysts poisoning also governs large-scale application and the development of DMFC technology.Therefore, explore the strong no-Pt catalyst of low cost, high cathode catalytic activity and methanol tolerance penetrating power and just seem particularly urgent, this is also one of key technology breaking through fuel cell Price Bottleneck.
At present, no-Pt catalyst mainly contains the nitrogenous carrier complexes of Transition-metal dichalcogenide, transition metal macrocyclic compound and transition metal, transition metal oxide etc.Wherein high, selective strong, the good stability of Transition-metal dichalcogenide ORR activity in acid medium, is the up-and-coming DMFC cathode catalyst material of a class.In the research of this type of catalyst, the seminar of professor Alonso-Vante leader has made important contribution.1986, they first reported the Mo with Chevrel phase structure 4.2ru 1.8se 8synthetic method, and prove its in acid medium to ORR have can catalytic activity compared with Pt (see Alonso-VanteN., TributschH.Energyconversioncatalysisusingsemiconductingt ransitionmetalclustercompounds.Nature, 1986,333:431-432).2000, they successfully prepared Ru again 1.92mo 0.08seO 4and find its there is fine electro catalytic activity while to methyl alcohol present completely inertia (see SchmidtT.J., PaulusU.A., GasteigerH.A., Alonso-VanteN., BehmR.J.OxygenreductiononRu1.92Mo0.08SeO4, Ru/carbon, andPt/carboninpureandmethanolcontainingelectrolytes.J.El ectrochem.Soc., 2000,147:2620-2624).Transition-metal dichalcogenide obtains and studies widely afterwards, but Ru alternatively noble metal, reduce its consumption, the stability and the methanol tolerance performance that strengthen catalyst have very important meaning to the commercialization promoting DMFC simultaneously.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide that a kind of preparation technology is simple, the cycle is short, oxygen reduction activity is high and the M with good methanol tolerance performance is doped in Se xone step solvothermal preparation method and application, the i.e. Ru of-Ru/C xm yse zthe solvent heat in-situ preparation method of composite catalyst and application.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
M is doped in Se xthe one step solvothermal preparation method of-Ru/C, comprises the steps:
S1, get 0.6mmol ruthenium salt, 0.2 ~ 0.6mmol selenous acid, 95.6mg active carbon and M source and join in isopropanol solvent, ultrasonic agitation obtains the reaction precursor liquid mixed, and described M source is 0.009mmol molybdenum salt or 0.06mmol platinum source or 0.06mmol molysite;
S2, the reaction precursor liquid obtained by step S1 are poured in reactor, insert after sealing in the reacting furnace with rotating rod and carry out solvent thermal reaction, 100 ~ 220 DEG C of insulation 10h, be cooled to after room temperature with washes of absolute alcohol repeatedly, be then placed in vacuum drying chamber and dry and obtain black powder intermediate product;
S3, the black powder intermediate product obtained by step S2 are put in tube furnace and are calcined, and pass into the mist of nitrogen and hydrogen, are heated to 300 ~ 1000 DEG C of insulation 2 ~ 5h;
S4, by the product of step S3 take out naturally cool to room temperature, obtain product M adulterate Se x-Ru/C catalyst.
Preferably, in abovementioned steps S1, ruthenium salt is six hydrate ruthenium trichlorides or 12 hydrated carbonyl rutheniums, and described molybdenum salt is Ammonium Molybdate Tetrahydrate or six hydrated carbonyl molybdenums, and described platinum source is chloroplatinic acid, and described molysite is ferric chloride hexahydrate or nine hydrated carbonyl iron.
More preferably, aforementioned isopropyl alcohol and absolute ethyl alcohol are and analyze pure rank.
Again preferably, in abovementioned steps S2, reaction precursor liquid compactedness is in a kettle. 60%.
Further preferably, in abovementioned steps S2, described reactor is polytetrafluoroethylene (PTFE) reactor.
Further, in abovementioned steps S3, nitrogen is 3:1 with the ratio of the gas flow of hydrogen.
In addition, the present invention also protects the M doping Se obtained by aforesaid preparation method xthe application of-Ru/C catalyst in DMFC.
Usefulness of the present invention is: the Se that the M (M=Mo, Pt, Fe) that the present invention has prepared growth in situ crystallinity excellence under a step solvent heat adulterates x-Ru/C composite catalyst, obtains at Se xadulterate in-Ru/C avtive spot elements Mo, Pt or Fe and not containing the eelctro-catalyst of dephasign, compared to other preparation method, preparation technology of the present invention is more simple, the cycle is short, efficiently convenient and environment friendly and pollution-free in preparation process, the chemical reagent used is common agents, environmental protection, cheap and easy to get, be easy to large-scale application and popularization; After testing, the M obtained by the present invention adulterates the Se of especially Pt doping xthe hydrogen reduction of-Ru/C composite catalyst, methanol tolerance and stability are all optimized, and are a kind of novel composite catalysts being expected to apply in DMFC.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the intermediate product prepared by embodiments of the invention 1;
Fig. 2 is the Se that the final products M (M=Mo, Pt, Fe) prepared by embodiments of the invention 1 adulterates xthe XRD collection of illustrative plates of-Ru/C composite catalyst;
The Se that in Fig. 3 the present invention, the prepared final products M (M=Mo, Pt, Fe) of embodiment 1 adulterates xthe hydrogen reduction performance test figure (LSV) of-Ru/C composite catalyst;
Fig. 4 is the Se of the prepared Pt doping of embodiment 1 in the present invention xthe methanol tolerance performance test figure of-Ru/C composite catalyst;
The Se of the Pt doping of Fig. 5 prepared by embodiment in the present invention 1 xthe stability test figure of-Ru/C composite catalyst.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, concrete introduction is done to the present invention.
Embodiment 1
S1, get 0.6mmol ruthenium salt, 0.2mmol selenous acid, 95.6mg active carbon and M source and join in isopropanol solvent, ultrasonic agitation obtains the reaction precursor liquid mixed, and wherein, M source is 0.009mmol molybdenum salt or 0.06mmol platinum source or 0.06mmol molysite;
S2, the reaction precursor liquid obtained by step S1 are poured in the polytetrafluoroethylene (PTFE) reactor of 25mL, insert after sealing in the reacting furnace with rotating rod and carry out solvent thermal reaction, 150 DEG C of insulation 10h, use washes of absolute alcohol 3 times after being cooled to room temperature, be then placed in vacuum drying chamber oven dry and obtain black powder intermediate product;
S3, the black powder intermediate product obtained by step S2 are put in tube furnace and are calcined, and pass into the mist of nitrogen and hydrogen (ratio of gas flow is 3:1), are heated to 300 DEG C of insulation 2h;
S4, by the product of step S3 take out naturally cool to room temperature, obtain product M adulterate Se x-Ru/C catalyst.
Embodiment 2
In the present embodiment, selenous acid taken amount is 0.4mmol, and all the other are all identical with embodiment 1.
Embodiment 3
In the present embodiment, selenous acid taken amount is 0.6mmol, and all the other are all identical with embodiment 1.
Embodiment 4
In the present embodiment, the holding temperature in step S2 is 100 DEG C, and all the other are all identical with embodiment 1.
Embodiment 5
In the present embodiment, the holding temperature in step S2 is 120 DEG C, and all the other are all identical with embodiment 1.
Embodiment 6
In the present embodiment, the holding temperature in step S2 is 200 DEG C, and all the other are all identical with embodiment 1.
Embodiment 7
In the present embodiment, the holding temperature in step S2 is 220 DEG C, and all the other are all identical with embodiment 1.
Embodiment 8
In the present embodiment, the holding temperature in step S3 is 500 DEG C, and temperature retention time is 2h, and all the other are all identical with embodiment 1.
Embodiment 9
In the present embodiment, the holding temperature in step S3 is 800 DEG C, and temperature retention time is 2h, and all the other are all identical with embodiment 1.
Embodiment 10
In the present embodiment, the holding temperature in step S3 is 1050 DEG C, and temperature retention time is 2h, and all the other are all identical with embodiment 1.
Embodiment 11
In the present embodiment, the holding temperature in step S3 is 300 DEG C, and temperature retention time is 5h, and all the other are all identical with embodiment 1.
Embodiment 12
In the present embodiment, the holding temperature in step S3 is 500 DEG C, and temperature retention time is 5h, and all the other are all identical with embodiment 1.
Embodiment 13
In the present embodiment, the holding temperature in step S3 is 800 DEG C, and temperature retention time is 5h, and all the other are all identical with embodiment 1.
Embodiment 14
In the present embodiment, the holding temperature in step S3 is 1000 DEG C, and temperature retention time is 5h, and all the other are all identical with embodiment 1.
Product characterizes and Performance Detection
The Se that M (M=Mo, Pt, Fe) prepared by the present invention adulterates x-Ru/C composite catalyst carries out structure and morphology characterization by following means: select the X-ray diffractometer (XRD) of Rigaku UltimaIV to carry out phase structure phenetic analysis to sample; Japanese HDHOKUTODENKO rotating disk electrode (r.d.e) is selected to test the hydrogen reduction performance of catalyst, methanol tolerance performance and stability.
The Se that the M (M=Mo, Pt, Fe) of Fig. 1 and Fig. 2 prepared by embodiment 1 adulterates x-Ru/C composite catalyst calcining before and after XRD collection of illustrative plates, contrast visible, catalyst after calcination all presents the feature broad peak of good Ru, and M source add the crystal property reducing catalyst.
The Se that the M (M=Mo, Pt, Fe) of Fig. 3 prepared by embodiment 1 adulterates xthe hydrogen reduction performance test figure (LSV) of-Ru/C composite catalyst, in figure, after Mo, Fe doping, hydrogen reduction performance decreases, and the carrying current of Pt doping rear catalyst increases, and catalytic performance is better than Se x-Ru/C catalyst.
The Se of the Pt doping of Fig. 4 prepared by embodiment 1 x, in the figure, there is more obvious hydrogen reduction peak after adding 1M methyl alcohol, shown the Se that Pt adulterates in the resolution chart of the methanol tolerance performance of-Ru/C composite catalyst xthe performance of-Ru/C composite catalyst is improved.
The Se of the Pt doping of Fig. 5 prepared by embodiment 1 xthe stability test figure of-Ru/C composite catalyst, as seen from Figure 5, when when 0.4V (vs.RHE), the circulation number of turns is higher than 40 circle, having there is obvious decay in the catalyst of the Pt that do not adulterate, shows that the doping of Pt substantially increases the stability of catalyst.
The catalyst that all the other each embodiments obtain especially Pt doping Se xthe hydrogen reduction of-Ru/C composite catalyst, methanol tolerance and stability are also obtained for optimization, are expected to apply in DMFC.
More than show and describe general principle of the present invention, principal character and advantage.The technical staff of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.

Claims (7)

1.M is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, comprise the steps:
S1, get 0.6mmol ruthenium salt, 0.2 ~ 0.6mmol selenous acid, 95.6mg active carbon and M source and join in isopropanol solvent, ultrasonic agitation obtains the reaction precursor liquid mixed, and described M source is 0.009mmol molybdenum salt or 0.06mmol platinum source or 0.06mmol molysite;
S2, the reaction precursor liquid obtained by step S1 are poured in reactor, insert after sealing in the reacting furnace with rotating rod and carry out solvent thermal reaction, 100 ~ 220 DEG C of insulation 10h, be cooled to after room temperature with washes of absolute alcohol repeatedly, be then placed in vacuum drying chamber and dry and obtain black powder intermediate product;
S3, the black powder intermediate product obtained by step S2 are put in tube furnace and are calcined, and pass into the mist of nitrogen and hydrogen, are heated to 300 ~ 1000 DEG C of insulation 2 ~ 5h;
S4, by the product of step S3 take out naturally cool to room temperature, obtain product M adulterate Se x-Ru/C catalyst.
2. M according to claim 1 is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, in described step S1, ruthenium salt is six hydrate ruthenium trichlorides or 12 hydrated carbonyl rutheniums, described molybdenum salt is Ammonium Molybdate Tetrahydrate or six hydrated carbonyl molybdenums, and described platinum source is chloroplatinic acid, and described molysite is ferric chloride hexahydrate or nine hydrated carbonyl iron.
3. M according to claim 1 is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, described isopropyl alcohol and absolute ethyl alcohol are analyzes pure rank.
4. M according to claim 1 is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, in described step S2, reaction precursor liquid compactedness is in a kettle. 60%.
5. M according to claim 1 is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, in described step S2, described reactor is polytetrafluoroethylene (PTFE) reactor.
6. M according to claim 1 is doped in Se xthe one step solvothermal preparation method of-Ru/C, is characterized in that, in described step S3, nitrogen is 3:1 with the ratio of the gas flow of hydrogen.
7. the M doping Se obtained by the preparation method described in any one of claim 1-6 xthe application of-Ru/C catalyst in DMFC.
CN201510650905.8A 2015-10-10 2015-10-10 One-step solvothermal preparation method and application of M-doped Sex-Ru/C Pending CN105363478A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545240A (en) * 2020-05-29 2020-08-18 西安凯立新材料股份有限公司 In-situ one-pot preparation method of Pt/Fe3O4Method and application of/C-N catalyst
CN114744176A (en) * 2022-04-29 2022-07-12 东南大学 Ruthenium-doped amorphous selenium material for anode of water-based zinc ion battery and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN100998948A (en) * 2006-12-13 2007-07-18 太原理工大学 Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery
CN101779319A (en) * 2007-08-09 2010-07-14 丰田自动车株式会社 Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst
CN101807701A (en) * 2010-04-23 2010-08-18 上海理工大学 Direct methanol fuel cell anodic nano-catalyst and preparation method thereof
CN103050714A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst
CN103143717A (en) * 2011-12-06 2013-06-12 中国科学院大连化学物理研究所 Platinoid bimetallic nanometer material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100998948A (en) * 2006-12-13 2007-07-18 太原理工大学 Preparation method of oxygen electric reduction catalyst for direct methanol fuel battery
CN101779319A (en) * 2007-08-09 2010-07-14 丰田自动车株式会社 Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst
CN101807701A (en) * 2010-04-23 2010-08-18 上海理工大学 Direct methanol fuel cell anodic nano-catalyst and preparation method thereof
CN103050714A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst
CN103143717A (en) * 2011-12-06 2013-06-12 中国科学院大连化学物理研究所 Platinoid bimetallic nanometer material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545240A (en) * 2020-05-29 2020-08-18 西安凯立新材料股份有限公司 In-situ one-pot preparation method of Pt/Fe3O4Method and application of/C-N catalyst
CN114744176A (en) * 2022-04-29 2022-07-12 东南大学 Ruthenium-doped amorphous selenium material for anode of water-based zinc ion battery and preparation method thereof

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Application publication date: 20160302