CN106622301B - A kind of MoS of hierarchical structure2Difunctional VPO catalysts of nanosphere and its preparation method and application - Google Patents
A kind of MoS of hierarchical structure2Difunctional VPO catalysts of nanosphere and its preparation method and application Download PDFInfo
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- 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
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- B01J27/051—Molybdenum
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- H01M4/90—Selection of catalytic material
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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
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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
- 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 present invention relates to a kind of MoS of hierarchical structure2Difunctional VPO catalysts of nanosphere and preparation method thereof and in alkaline medium to the electro-catalysis application of oxygen.The catalyst is with Na2MoO4It is raw material, the MoS with hierarchical structure synthesized using hydro-thermal method with KSCN2Nanosphere, this nanosphere is by countless MoS2Nanometer sheet is built-up, causes it with big specific surface area, and make MoS2The edge site of nanometer sheet has obtained abundant exposure.And ultra-thin MoS2The multi-pore channel flower-like nanometer ball that nanometer blade unit is formed increases its effective electrochemical catalysis area and catalytic site, accelerate electronics conduction velocity, therefore, effectively reduce the overpotential of oxygen evolution reaction and oxygen reduction reaction, show that its hydrogen reduction process is 4 electronic catalytic mechanism by rotating disk electrode (r.d.e) and rotating ring disk electrode (r.r.d.e), is ideal oxygen reduction reaction process.
Description
Technical field:
The invention belongs to novel energy resource material technology and electrochemical catalysis fields, and in particular to the MoS of hierarchical structure2It receives
The rice difunctional VPO catalysts of ball；It further relates to the preparation method of the catalyst and its reacts and fire in electrolyzed alkaline water Oxygen anodic evolution
Expect the electro-catalysis application in cell cathode oxygen reduction reaction.
Background technique:
As the mankind are continuously increased cleaning and sustainable energy demand, great effort has been put into height by scientists
In terms of the research and development of effect, low cost and environmentally friendly energy conversion and stocking system.Wherein oxygen reduction reaction (ORR) exists
Generally existing cathode reaction in fuel cell and metal-air battery, oxygen evolution reaction (OER) then solar energy fuel synthesis and
It plays an important role in water-splitting energy storage system.Therefore, catalyst especially VPO catalysts have been to restrict new energy dress
The main bottleneck set.In view of the activity and stability of catalyst, the catalyst for ORR reaction mainly has Pt and its alloy,
And the catalyst for being used for OER mainly has IrO2Or RuO2, but these noble metals are very rare in nature, and it is expensive, make
Power supply device cost is too high at present.Exploitation high-performance, low-cost dual-function oxygen catalysis material are to push fuel cell and its technology
Develop critical issue urgently to be resolved, and developing base metal VPO catalysts becomes hot spot class concerned by people in the field
Topic.
In recent years, because of the structure of class graphene and big specific surface area and unsaturated dangling bonds abundant, transition group gold
Belong to sulfide two-dimensional semiconductor material and causes the extensive concern of people in electro-catalysis field.Wherein Typical Representative is molybdenum sulfide
(MoS2), it is sandwiched one layer of molybdenum atom layer by two layers of vertically opposite sulphur atom layer and is accumulated with triangular prism shaped, and these
The S-Mo-S layers of layer structure for being joined together to form class graphene by Van der Waals force.Due to sufficiently exposed edge, rich
Rich active site and big specific surface area, MoS2It is widely applied in electro-catalysis field.Such as in recent years MoS2Because
Its special structure and characteristic electron have proved to be excellent evolving hydrogen reaction (HER) catalyst [Wu Z, Fang B, Wang Z,
Wang C, Liu Z, Liu F. ACS Catal.2013,3,2101-2107.], also there are some researches prove it to have potential ORR to urge
Change performance [Kibsgaard J, Chen Z, Reinecke B N, Jaramillo T F.Nat.Mater.2012,11,963-
969.].Current research is also shown that design MoS2The sufficiently exposed nanostructure in edge site is to improve its electrocatalysis characteristic
One of effective way.On the other hand, it yet there are no related MoS2The report of bifunctional catalyst as OER and ORR.
The present invention is with Na2MoO4It is raw material with KSCN, the MoS with hierarchical structure has been synthesized using hydro-thermal method2Nanosphere,
This nanosphere is by countless MoS2Nanometer sheet is built-up, causes it with big specific surface area, and make MoS2The edge of nanometer sheet
Site has obtained abundant exposure, therefore, as difunctional VPO catalysts, hierarchical structure MoS2Nanosphere effectively reduce OER with
And the overpotential of ORR, show that its ORR process is 4 electronics by rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE)
Catalytic mechanism is ideal ORR reaction process.The resulting hierarchical structure MoS of this method2Nanosphere VPO catalysts are sufficiently sent out
MoS is waved2The electro-catalysis advantages such as nanometer blade unit large specific surface area, active site be more, to exploitation novel electrochemical catalyst and
Energy conversion and memory device have important theoretical and practical significance.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
The MoS of kind hierarchical structure2The difunctional VPO catalysts of nanosphere, i.e., with Na2MoO4It is raw material with KSCN, is synthesized using hydro-thermal method
MoS with hierarchical structure2The difunctional VPO catalysts of nanosphere.
The second object of the present invention is to provide a kind of MoS of hierarchical structure2The preparation side of the difunctional VPO catalysts of nanosphere
Method, specifically includes the following steps:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
In kettle, in 120~220 DEG C of 12~36h of hydro-thermal reaction after lid is sealed, it is centrifuged after being cooled to room temperature, then successively use deionized water
After dehydrated alcohol washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere.
The MoS being prepared2Catalyst is the nanosphere with hierarchical structure, the partial size of the nanosphere is about 200~
300nm, by the MoS with a thickness of 2~3nm2Nanometer sheet is built-up, is rendered as porous structure, with big specific surface area and rich
Rich edge site.
The three of the object of the invention are to provide a kind of MoS of hierarchical structure2The difunctional VPO catalysts of nanosphere are in alkaline electro
Solve the application in water anode OER and fuel battery negative pole ORR.
The present invention is with Na2MoO4It is raw material with KSCN, the MoS with hierarchical structure has been synthesized using hydro-thermal method2Nanosphere,
This nanosphere is by countless MoS2Nanometer sheet is built-up, causes it with big specific surface area, and make MoS2The edge of nanometer sheet
Site has obtained abundant exposure, therefore, as difunctional VPO catalysts, hierarchical structure MoS2Nanosphere effectively reduce OER with
And the overpotential of ORR, RDE and RRDE show that its ORR process is 4 electronic catalytic mechanism, are ideal ORR reaction process.
The result shows that its ORR process is largely 4 electronic catalytic mechanism, it is ideal ORR reaction process.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) difunctional VPO catalysts of the present invention are base metal homogenous material, and raw material is easy to get inexpensively, and preparation is convenient
And it is at low cost, it can be prepared on a large scale；
2) methanol tolerance of difunctional VPO catalysts of the present invention is substantially better than the MoS of business2With business
20%Pt/C catalyst, is added 1mol/L methanol in 0.1mol/L KOH electrolyte, the catalytic activity of catalyst almost without
Decaying；
3) difunctional VPO catalysts of the present invention are a kind of MoS with hierarchical structure2Nanosphere, with business
MoS2Nano material and noble metal catalyst are compared, it has more superior OER and ORR double-function catalyzing activity；
4) MoS of difunctional VPO catalysts and business of the present invention2With the Pt/C catalyst phase of commercialization 20wt%
Than stability is significantly improved, and can keep good catalytic activity in fuel cell long-time service；
5) difunctional VPO catalysts preparation method of the present invention is simple, easily operated, convenient for large-scale production.
Detailed description of the invention:
Fig. 1 is 4 gained MoS of embodiment2The scanning electron microscopic picture of nano-sphere catalyst.
Fig. 2 is 4 gained MoS of embodiment2The XRD diagram of nanosphere.
Fig. 3 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2And IrO2The linear volt-ampere curve figure of OER.
Fig. 4 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the ORR of the Pt/C catalyst modification RDE of 20wt%
Linear volt-ampere curve figure.
Fig. 5 is 4 gained MoS of embodiment2Nanosphere (a and b) and commercialization MoS2The ORR that (c and d) catalyst modifies RDE is dynamic
Force diagram.
Fig. 6 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the ORR of the Pt/C catalyst modification RDE of 20wt%
Methanol tolerance chronoa mperometric plot.
Fig. 7 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the timing of the Pt/C catalyst modification RDE of 20wt%
Potential curve figure.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
It in kettle, in 140 DEG C of hydro-thermal reaction 32h after lid is sealed, is centrifuged after being cooled to room temperature, then successively uses deionized water and dehydrated alcohol
After washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere, specific surface area are
197.26m2/g。
Embodiment 2:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
It in kettle, in 160 DEG C of hydro-thermal reaction 18h after lid is sealed, is centrifuged after being cooled to room temperature, then successively uses deionized water and dehydrated alcohol
After washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere, specific surface area be,
202.38m2/g。
Embodiment 3:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
It in kettle, in 180 DEG C of hydro-thermal reaction 20h after lid is sealed, is centrifuged after being cooled to room temperature, then successively uses deionized water and dehydrated alcohol
After washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere, specific surface area be,
186.46m2/g。
Embodiment 4:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
It in kettle, after lid is sealed for 24 hours in 200 DEG C of hydro-thermal reactions, is centrifuged after being cooled to room temperature, then successively uses deionized water and dehydrated alcohol
After washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere, specific surface area be,
216.66m2/g。
Embodiment 5:
By 5mmol Na2MoO4·2H2O is dissolved in 60ml water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
Enter 15mmol KSCN, stirring after completely dissolution, then is added the dense HCl of 8ml thereto, stirs evenly, be transferred to 100ml hydro-thermal reaction
It in kettle, in 220 DEG C of hydro-thermal reaction 20h after lid is sealed, is centrifuged after being cooled to room temperature, then successively uses deionized water and dehydrated alcohol
After washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere, specific surface area be,
194.14m2/g。
Fig. 1 is 4 gained MoS of embodiment2The scanning electron microscopic picture of nano-sphere catalyst.It can be seen from the figure that MoS2It is in
It is now flower-shaped nanosphere, the MoS that nanosphere is about 2~3nm by countless thickness2Nanometer sheet is constructed, phase between nanometer sheet
Interconnection is connected together, and spherome surface presents uniform nano pore.Such structure certainly will will lead to MoS2Nanometer sheet edge
Site sufficiently exposes, and flower-shaped nanosphere has high specific surface area and catalytic site abundant, mentions to improve electrocatalysis characteristic
Condition is supplied.
Fig. 2 is 4 gained MoS of embodiment2The XRD diagram of nanosphere.It can be seen from the figure that MoS obtained2Nanosphere difference
There is MoS at 14.38 °, 35.5 °, 38.8 ° and 56.8 °2Typical 002,100,103 and 110 diffraction maximum, but its peak shape is simultaneously
It is not sharp, it was demonstrated that due to the heap of nanometer sheet, MoS obtained2Its crystallinity of nanosphere is not very high.
Embodiment 6:
Respectively by the resulting catalyst of 15mg embodiment 4, the resulting MoS of business2And IrO2Be scattered in 400 μ L ethyl alcohol and
In 20 μ L polytetrafluoroethylsolution solutions, after ultrasound mixes solution, 5 μ L slurry drops is taken to be applied to change disc electrode (RDE, 0.07065cm2)
On, its OER electrocatalysis characteristic is measured on CHI660D electrochemical workstation after it is completely dried；Similarly, respectively by 10mg
The resulting catalyst of embodiment 4, the resulting MoS of business2And IrO2Catalyst is scattered in 400 μ L ethyl alcohol and 15 μ L Nafion are molten
In liquid, after ultrasound mixes solution, 2 μ L slurry drops is taken to be applied to rotating ring disk electrode (r.r.d.e) (RRDE, 0.1256cm2) on, it is completely dry to its
Its ORR electrocatalysis characteristic is measured after dry on CHI660D electrochemical workstation.
Above-mentioned electrocatalysis characteristic test is to be saturated Ag/AgCl electrode as reference electrode, and Pt electrode is to electrode, and sweeping speed is
10mV/s, electrolyte are 0.1M KOH, need to carry out O before ORR catalytic performance test2Saturated process.RDE test result is passed through
After Koutecky-Levich formula manipulation, electron transfer number (n) can be calculated by the K-L slope of curve (B).
J-1=Jk -1+(Bω1/2)-1
B=0.62n F C0D0 2/3v1/6
Wherein F=96485C/mol, C0=1.2 × 10-3Mol/L, D0=1.9 × 10-5cm2/ s, v=0.01cm2/s。
RRDE test result can obtain electron transfer number (n) and H by following formula manipulation2O2Content:
N=4Id·(Id+Ir/N)
HO- 2%=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Fig. 3 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2And IrO2The linear volt-ampere curve figure of OER.By in figure
The available MoS of curve2Nanosphere, commercialization MoS2And IrO2OER take-off potential be respectively 1.467V, 1.488V and
1.663V, it is evident that MoS2It is 237mV that nanosphere, which originates overpotential, far superior to business commercialization MoS2(originating overpotential is
433mV), and better than the noble metal IrO of business2Catalyst (starting overpotential is 258mV).When current density is 10mA/cm2
When, MoS2The overpotential of nanosphere is 285mV, is also much better than commercialization MoS2And IrO2(overpotential is respectively 495mV and 387
mV).The above result shows that due to ultra-thin MoS2The abundant exposure in nanometer sheet edge site, increases the electrochemistry of its crystal unit
Catalytic site；By ultra-thin MoS2The flower-like nanometer ball that nanometer blade unit is formed provides not only big surface area, and is moisture
The absorption of son and the precipitation of oxygen provide good site and channel.Therefore, MoS2Flower-like nanometer ball shows excellent
OER catalytic performance.
Fig. 4 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the ORR of the Pt/C catalyst modification RDE of 20wt%
Linear volt-ampere curve figure.As shown, MoS2Nanosphere, commercialization MoS2ORR take-off potential with 20%Pt/C is respectively
0.995V, 0.868V and 0.979V, MoS2Nanosphere shows optimal ORR catalytic performance, and MoS2The limit of nanosphere
Diffusion current density is also significantly larger than commercialized MoS2, it is almost suitable with the Pt/C catalyst of 20wt%, also sufficiently demonstrate
MoS2Flower-like nanometer ball has very high ORR catalytic performance.MoS2The excellent ORR catalytic performance of flower-like nanometer sphere catalyst is main
It is due to ultra-thin MoS2The abundant exposure in nanometer sheet edge site, and by ultra-thin MoS2The multi-pore channel flower that nanometer blade unit is formed
Shape nanosphere increases its effective electrochemical catalysis area and catalytic site, accelerates electronics conduction velocity, shows as in ORR
Steady-state process in, take-off potential is shuffled, and current density has obtained significant increase, to realize ORR catalytic performance
Enhancing.
Fig. 5 is 4 gained MoS of embodiment2Nanosphere (a and b) and commercialization MoS2The ORR that (c and d) catalyst modifies RDE is dynamic
Force diagram.The results show that MoS2Nanosphere and commercialization MoS2ORR catalytic process in average electron transfer number be respectively
3.974 and 3.74, it is evident that MoS2Flower-like nanometer sphere catalyst is much better than commercialization MoS2, average electron shifts number closer to nothing
HO2 -4 electronic transfer process of product, to illustrate MoS2The ORR process of flower-like nanometer ball modified electrode catalysis is almost ideal
4 electron reaction mechanism.
Fig. 6 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the ORR of the Pt/C catalyst modification RDE of 20wt%
Methanol tolerance chronoa mperometric plot.It can be seen from the figure that three kinds of modified electrodes are without bright in oxygen-free environment under 0.45V constant voltage
Aobvious operating current, after starting to be passed through oxygen, their response currents are gradually promoted, and illustrate that ORR reaction, and total overall reaction has occurred
It is ORR process, when ORR proceeds to about 4h, their electric currents have almost no change, and it is good to illustrate that three kinds of elctro-catalysts have
Stability, good catalytic activity can be kept in the long-time service of fuel cell, at this time instill 1M methanol after (about 50mL
1mL is instilled in electrolyte) after, MoS2The electric current of flower-like nanometer sphere catalyst has almost no change, and is commercialized MoS2And 20wt%
The current density of Pt/C catalyst decayed 17.8% and 40.6% respectively, show MoS2Flower-like nanometer sphere catalyst has
Better than the ORR methanol tolerance jamming performance of commercialization noble metal electrocatalyst, it can be used as the decorative material of pluralities of fuel cell cathode.
Fig. 7 is 4 gained MoS of embodiment2Nanosphere, commercialization MoS2With the timing of the Pt/C catalyst modification RDE of 20wt%
Potential curve figure.It can be seen from the figure that MoS2Nanosphere, commercialization MoS2It has passed through 9h's with the Pt/C catalyst of 20 wt%
After time-measuring electric potential measurement, their current potential decays to original 94.52%, 87.78% and 60.75% respectively, shows MoS2
Stability when flower-like nanometer sphere catalyst has the ORR long for being substantially better than commercial catalysts.
Claims (2)
1. a kind of MoS of hierarchical structure2The difunctional VPO catalysts of nanosphere, it is characterised in that the catalyst is with Na2MoO4With
KSCN is raw material, the MoS with hierarchical structure synthesized using hydro-thermal method2Nanosphere；
The MoS of the hierarchical structure2The preparation method of the difunctional VPO catalysts of nanosphere, it is characterised in that specific step is as follows:
By 5mmol Na2MoO4·2H2O is dissolved in 60mL water, after being thoroughly mixed uniformly, is added in Xiang Shangshu solution
15mmol KSCN, stirring after completely dissolution, then are added the dense HCl of 8mL thereto, stir evenly, be transferred to 100mL hydrothermal reaction kettle
In, in 120~220 DEG C of 12~36h of hydro-thermal reaction after lid is sealed, be centrifuged after being cooled to room temperature, then successively with deionized water and
After dehydrated alcohol washing, at 50 DEG C of one nights of vacuum drying, the MoS of hierarchical structure is obtained2The difunctional VPO catalysts of nanosphere；
The catalyst is the nanosphere with hierarchical structure, and the partial size of the nanosphere is about 200~300nm, by with a thickness of 2~
The MoS of 3nm2Nanometer sheet is built-up, is rendered as porous structure, has big specific surface area and edge site abundant.
2. a kind of MoS of hierarchical structure according to claim 12The difunctional VPO catalysts of nanosphere, it is characterised in that described
Application of the catalyst in the Oxygen anodic evolution reaction of electrolyzed alkaline water and the Cathodic oxygen reduction of fuel cell.
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