CN105762375B - A kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen - Google Patents
A kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen Download PDFInfo
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- CN105762375B CN105762375B CN201410788979.3A CN201410788979A CN105762375B CN 105762375 B CN105762375 B CN 105762375B CN 201410788979 A CN201410788979 A CN 201410788979A CN 105762375 B CN105762375 B CN 105762375B
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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
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Abstract
The present invention relates to a kind of graphite alloy compound electrocatalysts of the cathodic reduction for oxygen.The catalyst is using the nano-graphite that price is low, chemical stability is high as matrix, it is the second constituent element so that there is highly selective, high activity mercury system alloy as hydrogen peroxide to O_2 cathodic reduction, form nano-graphite alloy intercalation configuration elctro-catalyst, stabilisation, the nanosizing of mercury system alloy are realized using " double team " effect of graphite linings, so as to solve high activity, losing issue existing for highly selective mercury system alloy elctro-catalyst and reduce its use cost.Catalyst proposed by the present invention can be applied to the fields such as the electrochemical treatments of hydrogen peroxide electrochemistry formated, organic sewage as cathod catalyst.
Description
Technical field
The invention belongs to electro-catalysis technical field, a kind of particularly elctro-catalyst for hydrogen reduction.
Background technology
The cathodic reduction of oxygen is a kind of important electrochemical reaction, is distinguished by the electron number shifted in unit process,
It can be divided mainly into four electronics oxygen reduction reactions (4e-ORR) and two electronics oxygen reduction reactions (2e-ORR).Wherein, four electronics oxygen are also
Original reaction by whether living through oxidation state intermediate product process, and can be divided into four electron reaction paths of series connection and direct four electronics
Response path.The reaction equation that above-mentioned each process is related to is as follows：
Acid or neutral environment
Connect 4e-ORR:O2+2H++2e- → H2O2, H2O2+2H++2e- → 2H2O
Direct 4e-ORR:O2+4H++4e-→2H2O
2e-ORR:O2+2H++2e-→H2O2
Alkaline environment
Connect 4e-ORR:O2+H2O+2e- → HO2-+OH-, HO2-+H2O+2e- → 3OH-
Direct 4e-ORR:O2+2H2O+4e-→4OH-
2e-ORR:O2+H2O+2e-→HO2-+OH-
For many years, for this important application background of fuel cell, domestic and foreign scholars carry out four electronics oxygen reduction reactions
Extensively, in-depth study, shows important value and status of the oxygen reduction reaction on fuel cell technology.It is ground above-mentioned
During studying carefully, oxygen is made efficiently to be converted into water (acid battery) or hydroxide ion (alkalescence through direct four electronics hydrogen reduction path
Battery) it is the target that researcher makes great efforts, and " four electronics of series connection in two electronics oxygen reduction reactions and four electronics oxygen reduction reactions
Response path ", since its product or transition state intermediate product hydrogen peroxide are (with HO under alkaline condition2 -Form presence) to electrolyte
The critical materials such as film have accelerated degradation effect, and " side reaction " is all taken as to treat always.
However, in recent years, with the development of science and technology with the reinforcement of cross-disciplinary interviewing cooperation, two electronics oxygen reduction reactions
Research significance examined closely again.In terms of high concentrated organic wastewater processing, emerging advanced electrochemical oxidation process
(EC-AOPs, Electrochemical Advanced Oxidation Processes) is exactly anti-using two electronics hydrogen reduction
Answer fabricated in situ hydrogen peroxide, then with Fe2+Effect forms oxidability and is only second to F2Hydroxyl radical free radical (OH), so as to real
Now the efficient oxidation of various organic pollution non-selectivities is removed.With traditional H2O2/Fe2+System is compared, and EC-AOPs is solved
Fe2+Oxidation loss problem.Compared with other oxidation technologies, EC-AOPs have method is simple, quick, normal temperature and pressure operation with
And the features such as environment green, especially suitable for handling industrial organic wastewater toxic, biodegradability is poor.Chlorine industry is always
There is the title of electricity-eating tiger, according to the present art, using China's caustic soda productions in 2011 and gross generation as foundation, can extrapolate
Section power consumption just occupies national gross generation nearly 2% is only electrolysed in chlorine industry.Currently, oxygen cathode technology is just in chlor-alkali work
It is promoted in industry, and if can make two electronics oxygen reduction reactions occur on oxygen cathode, then, chlorine industry will not only drop
Low energy consumption, while the hydrogen peroxide raw material of high added value can be also obtained, it is to kill two birds with one stone.In addition, in oxygen-iodine chemical laser
The multiple fields such as the regeneration of device raw material, hydrogen peroxide electrochemistry formated, papermaking, two electronics oxygen reduction reactions also have important application
Prospect.
Carbon material good conductivity, chemical stability are high, cheap, and live with certain two electronics hydrogen reduction catalysis
Property.Therefore, all the time, carbon material is studied and urges the cathodic oxygen reduction electricity for hydrogen peroxide synthesis with the most use
Agent, if graphite, glass carbon, activated carbon, carbon black, carbon fiber, graphite felt, carbon nanotubes etc. are by as hydrogen peroxide composite cathode
Reducing catalyst was investigated.Existing research is it is believed that structure-oxygen-containing class quinonyl group is that such is urged the defects of carbon electrodes
Agent plays two electronics oxygen reduction reactions of oxygen in the activated centre of catalytic action.However, carbon material two from the point of view of result of study
Electronics oxygen reduction catalytic activity and selectivity are not ideal enough, and cathode hydrogen peroxide is (with HO under alkaline condition2 -Form presence) output
Concentration is relatively low.This may be non-defective with carbon surface carbon atom have relation, carbon atom surface in this section, hydrogen peroxide is only with mistake
Intermediate state presence is crossed, can continue to obtain electronics and be reduced to water or hydroxide ion, what oxygen was walked is four electron paths of series connection.
For carbon material there are the problem of, researcher has carried out Research on Surface Modification to it.Wherein, using anthraquinone and its spread out
Biology is modified carbon material the favor for receiving researcher, and cardinal principle is that anthraquinone and its derivative can be effectively increased carbon
Material surface class quinone radical concentration.Kaido Tammeveski et al. are grafted anthraquinone on glass-carbon electrode, the experimental results showed that through
Electrode catalyst activity after surface modification compares 15 times of unmodified electrode lifting.However, on the other hand, researcher has found anthraquinone
And its derivative be easy to come off from carbon material surface (Journal of Electroanalytical Chemistry, 515:
101-112,2001)。
Based on this, researcher has also been proposed using conducting polymer and substitutes carbon material as matrix, by anthraquinone or derivatives thereof
It is doped in conducting polymer, body doping is risen to so as to which the surface of anthraquinone and derivative be modified, to reduce or delay anthraquinone
And derivative comes off the influence brought.Zhang Guoquan et al. is using anthraquinone disulfonate as to anion (AQDS), in pyrrole monomer
The doping to polypyrrole film (PPy) is realized during polymerization, AQDS/PPy composite membranes have been made.However, experimental result confirms
The chemical stability of conducting polymer and anthraquinone derivative in hydrogen peroxide is still undesirable.
Some transition metal (such as gold, mercury) have good conductive capability, higher chemical stability, preferable oxygen also
Former activity and two certain electronics hydrogen reduction selectivity, appropriate alloying or electronic structure modulation are carried out to it can also be into one
Step is promoted secondly electronics hydrogen reduction selectivity and activity.Just because of this, transition metal and alloy are urged as two electronics hydrogen reduction electricity
Agent is becoming the research hotspot of a new round.Metal and alloy elctro-catalyst have preferable Research Prospects, particularly nearest
The alloys such as Pt-Hg are found secondly electronics oxygen reduction activity is far above traditional carbon material, and selectivity is up to more than 96%
(Nature Materials,12:1137-1144,2013).But metal alloy composition is easy to be lost in, and the use of noble metal
Cost is also relatively high.
The present invention propose using the nano-graphite that price is low, chemical stability is high as matrix, using to O_2 cathodic reduction as peroxide
It is the second constituent element to change hydrogen to have highly selective, high activity mercury system alloy, forms nano-graphite-alloy intercalation configuration electro-catalysis
Agent realizes stabilisation, the nanosizing of mercury system alloy using " double team " effect of graphite linings, so as to solve high activity, highly selective
Mercury system alloy elctro-catalyst existing for losing issue and reduce its use cost.Catalyst proposed by the present invention can be used as cathode
Catalyst is applied to the fields such as the electrochemical treatments of hydrogen peroxide electrochemistry formated, organic sewage.
The content of the invention
The present invention proposes a kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen.The catalyst is with valency
The nano-graphite that lattice are low, chemical stability is high is matrix, to have highly selective, high activity as hydrogen peroxide to O_2 cathodic reduction
Mercury system alloy for the second constituent element, form nano-graphite-alloy intercalation configuration elctro-catalyst, utilize " doubles team " effect of graphite linings
Stabilisation, the nanosizing of mercury system alloy are realized, so as to solve high activity, stream existing for highly selective mercury system alloy elctro-catalyst
Mistake problem simultaneously reduces its use cost.
A kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen, it is characterised in that：Composite catalyst
The first component be nano-graphite as matrix, the second component is mercury system alloy, and mercury system alloy is sandwiched in nano-graphite
Between layers, the mass content of alloy is 10-50% to graphite in catalyst, and the mass content of mercury is 50%-90% in alloy；
Nano-graphite particle size range is 10-100nm；
Wherein described mercury system alloy can be the conjunction that Hg is formed with any one in Pt, Au, Pd, Ag or two or more metals
Gold；Graphite forms intercalation compound with alloy.
It is of the invention that there is following advantage compared with existing material and technology：
(1) high chemical stability：Used by composite catalyst proposed by the present invention basis material be graphite, second group
It is divided into alloy, there is preferable chemical stability, the oxidative environment residing to hydrogen peroxide synthesis has well adapting to property
And stability.
(2) it is inexpensive：Alloy catalyst higher price, the present invention come " double team " alloy, make its nanometer using nano-graphite
Change, use cost can be greatly lowered.
(3) high activity, highly selective：Graphite is the elctro-catalyst for being commonly used in hydrogen peroxide electrochemistry formated, itself
There is certain activity and selectivity for hydrogen peroxide to catalytic oxidation-reduction, it is selective compared to other carbon materials on it is excellent
Gesture, and alloy-type catalyst has preferable selectivity and activity.The composite catalyst that the two is formed, maintains catalyst height
While active, highly selective, catalyst stability is improved, reduces catalyst use cost.
Description of the drawings
Used heat treatment process when Fig. 1 mixing methods prepare nano-graphite (30nm) Pt-Hg alloy compound catalyst
Heating curve.
Fig. 2 is the Rotation ring disk electrode of nano-graphite (30nm) Pt-Hg alloy compounds catalyst and conventional activated carbon XC-72
Test curve compares.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings.
Embodiment 1
Graphite-alloy compound elctro-catalyst is prepared using mixing method.Take Hong the quick-fried method nanometer stone that average grain size is 30nm
Ink powder 100mg, mercury chloride 149.2mg are uniformly mixed spare.Chloroplatinic acid 70mg is taken, 1ml ethyl alcohol is added to dissolve, solution is obtained, by it
It adds in the mixture of graphite powder and mercury chloride, is uniformly mixed.Mixture is dried under 50 DEG C of vacuum conditions.Dried powder
End is transferred in tube type resistance furnace.Temperature program is set, as shown in Figure 1.After heat treatment, natural air cooling obtains black powder
Powder.By black powder pour into 100ml concentration be 1wt.% sodium borohydride solution in, magnetic agitation, reaction 4 it is small when after centrifuge
Separation, until clear liquid PH close to until 7.When obtained material is put into 60 DEG C of dryings 12 are small in vacuum drying chamber, nanometer can be obtained
Graphite-alloy compound catalyst.It can determine the hierarchical structure of nano-graphite-alloy by XRD analysis, it is electric using removable disk is rotated
Pole technology (RRDE) can test the selectivity of its catalytic oxidation-reduction.Fig. 2 is what the rotating ring disk electrode (r.r.d.e) of itself and XC-72 were tested
Circular current curve comparison.Test condition：The KOH aqueous solutions of 0.1mol/L be electrolyte, room temperature condition, oxygen blow 30 before test
Minute or more.
Claims (3)
1. a kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen, it is characterised in that：Composite catalyst
First component is nano-graphite as matrix, and the second component is mercury system alloy, and mercury system alloy is sandwiched stone in nano-graphite
Between layers, the mass content of alloy is 10-50% to ink in catalyst, and the mass content of mercury is 50%-90% in alloy；
Mercury system alloy is the alloy that Hg is formed with any one in Pt, Au, Pd or Ag or two or more metals.
2. graphite-alloy compound elctro-catalyst of the cathodic reduction according to claim 1 for oxygen, feature exist
In：Nano-graphite particle size range is 10-100 nm.
3. graphite-alloy compound elctro-catalyst of the cathodic reduction according to claim 1 for oxygen, feature exist
In：Graphite forms intercalation compound with alloy.
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| CN201410788979.3A CN105762375B (en) | 2014-12-17 | 2014-12-17 | A kind of graphite-alloy compound elctro-catalyst of cathodic reduction for oxygen |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631922A (en) * | 2012-03-28 | 2012-08-15 | 长沙星城微晶石墨有限公司 | Method for preparing metallic cladding expansion graphite |
| CN103296277A (en) * | 2012-03-01 | 2013-09-11 | 复旦大学 | Graphite intercalation compound lithium-ion battery negative electrode material, as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296277A (en) * | 2012-03-01 | 2013-09-11 | 复旦大学 | Graphite intercalation compound lithium-ion battery negative electrode material, as well as preparation method and application thereof |
| CN102631922A (en) * | 2012-03-28 | 2012-08-15 | 长沙星城微晶石墨有限公司 | Method for preparing metallic cladding expansion graphite |
Non-Patent Citations (2)
| Title |
|---|
| 《Carbon monoxide poisoning of platinum-graphite ca+alysts for polymer electrolyte fuel cells: comparison between platinum-supported on graphite and intercalated in graphite》;J.Y. Tilquin等;《loumat of Power Sources》;19961231;第61卷;第193-200段 * |
| 《Enabling direct H2O2 production through rational electrocatalyst design》;Samira Siahrostami等;《NATURE MATERIALS》;20131117;第12卷;第1137-1143页 * |
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