CN105762375A - Graphite-alloy composite-type electrocatalyst used for oxygen cathodic reduction - Google Patents
Graphite-alloy composite-type electrocatalyst used for oxygen cathodic reduction Download PDFInfo
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- CN105762375A CN105762375A CN201410788979.3A CN201410788979A CN105762375A CN 105762375 A CN105762375 A CN 105762375A CN 201410788979 A CN201410788979 A CN 201410788979A CN 105762375 A CN105762375 A CN 105762375A
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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
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Abstract
The present invention relates to a graphite-alloy composite-type electrocatalyst used for oxygen cathodic reduction. The catalyst is a nano-graphite-alloy intercalated structure electrocatalyst comprising low-price high-chemical-stability nano-graphite as a matrix and a mercury-based alloy as a second component, the mercury-based alloy has high selectivity and high activity for cathodic reduction of oxygen into hydrogen peroxide, stabilization and nanocrystallization of the mercury-based alloy can be realized by use of graphite layer ''sandwich'' effect, the problem the loss of the high activity and high selectivity mercury-based alloy electrocatalyst can be solved, and use cost is reduced. The graphite-alloy composite-type electrocatalyst as a cathode catalyst can be used in the fields of electrochemical synthesis of hydrogen peroxide, organic sewage electrochemical treatment and the like.
Description
Technical field
The invention belongs to electro-catalysis technical field, particularly a kind of eelctro-catalyst for hydrogen reduction.
Background technology
The cathodic reduction of oxygen is the electrochemical reaction that a class is important, makes a distinction by the electron number of transfer in unit process, can be divided mainly into four electronics oxygen reduction reactions (4e-ORR) and two electronics oxygen reduction reactions (2e-ORR).Wherein, four electronics oxygen reduction reactions, by whether living through oxidation state intermediate product process, series connection four electron reaction paths and direct four electron reaction paths can be divided into again.The reaction equation that above-mentioned each process relates to is as follows:
Acidity or neutral environment
Series connection 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
Series connection 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, four electronics oxygen reduction reactions have been carried out extensive, deep research by Chinese scholars, it is shown that oxygen reduction reaction important value on fuel cell technology and status.In the studies above process, oxygen is made to be converted into water (acid battery) efficiently or hydroxide ion (alkaline battery) is the target that researcher is made great efforts through direct four electronics hydrogen reduction paths, and " the four electron reaction paths of connecting " in two electronics oxygen reduction reactions and four electronics oxygen reduction reactions, owing to its product or transition state intermediate product hydrogen peroxide are (with HO under alkali condition2 -Form exists) critical materials such as dielectric film there are is accelerated degradation effect, all it is taken as " side reaction " to treat always.
But, in recent years, along with the reinforcement of scientific and technical development and cross-disciplinary interviewing cooperation, the Research Significance of two electronics oxygen reduction reactions is examined closely again.In high concentrated organic wastewater process, emerging advanced electrochemical oxidation process (EC-AOPs, ElectrochemicalAdvancedOxidationProcesses) utilizes two electronics oxygen reduction reaction fabricated in situ hydrogen peroxide just, then with Fe2+Effect forms oxidability and is only second to F2Hydroxyl radical free radical (OH), thus realizing the efficient oxidation of various organic pollution non-selectivities is removed.With traditional H2O2/Fe2+System is compared, and EC-AOPs solves Fe2+Oxidation loss problem.Compared with other oxidation technologies, EC-AOPs have method simple, quickly, the feature such as normal temperature and pressure operation and environment green, be particularly well-suited to process industrial poisonous, organic wastewater that biodegradability is poor.Chlorine industry has the title of electricity-eating tiger always, according to the present art, using China's caustic soda productions in 2011 and gross generation as foundation, can extrapolate only electrolysis section power consumption in chlorine industry and just occupy nearly the 2% of whole nation gross generation.Currently, oxygen cathode technology is just promoted in chlorine industry, and if able to make oxygen cathode occurs two electronics oxygen reduction reactions, then, chlorine industry will not only reduce energy consumption, also can obtain the hydrogen peroxide raw material of high added value simultaneously, be kill two birds with one stone.Additionally, in multiple fields such as the regeneration of COIL raw material, hydrogen peroxide electrochemical synthesis, papermaking, two electronics oxygen reduction reactions also have important application prospect.
Material with carbon element good conductivity, chemical stability are high, cheap, and have two certain electronics oxygen reduction catalytic activity.Therefore, all the time, material with carbon element is studied and makes the cathodic oxygen reduction eelctro-catalyst for hydrogen peroxide synthesis with the most use, and such as graphite, glass carbon, activated carbon, carbon black, carbon fiber, graphite felt, CNT etc. is all taken as hydrogen peroxide composite cathode reducing catalyst and investigated.Existing research is it is believed that the defect sturcture of carbon electrodes oxygen-containing class quinonyl group is the active center that such catalyst two electronics oxygen reduction reactions to oxygen play catalytic action.But, not ideal enough from result of study material with carbon element two electronics oxygen reduction catalytic activity and selectivity, negative electrode hydrogen peroxide is (with HO under alkali condition2 -Form exists) output concentration is relatively low.This is likely to there is relation with the carbon atom of carbon surface non-defective, carbon atom surface in this section, and hydrogen peroxide only exists with transition intermediate state, can continue to obtain electronics and be reduced to water or hydroxide ion, and what oxygen was walked is series connection four electron paths.
For material with carbon element Problems existing, it has been carried out Research on Surface Modification by researcher.Wherein, utilizing anthraquinone and derivant thereof that material with carbon element is modified receiving the favor of researcher, cardinal principle is in that anthraquinone and derivant thereof can be effectively increased carbon material surface class quinone radical concentration.KaidoTammeveski et al. is grafting anthraquinone on glass-carbon electrode, test result indicate that the electrode catalyst activity after surface modification compares unmodified electrode lifting 15 times.But, on the other hand, researcher finds that anthraquinone and derivant thereof are prone to come off (JournalofElectroanalyticalChemistry, 515:101-112,2001) from carbon material surface.
Based on this, researcher also been proposed and substitutes material with carbon element as matrix using conducting polymer, anthraquinone or derivatives thereof is doped in conducting polymer, thus the surface modification of anthraquinone and derivant being risen to body doping, to reduce or to delay anthraquinone and derivant to come off the impact brought.Anthraquinone disulfonate as to anion (AQDS), is realized the doping to polypyrrole film (PPy) in the process that pyrrole monomer is polymerized, has prepared AQDS/PPy composite membrane by Zhang Guoquan et al..But, experimental result confirms that conducting polymer and anthraquinone derivative chemical stability in hydrogen peroxide are still undesirable.
Some transition metal (such as gold, hydrargyrum) etc. has good conductive capability, higher chemical stability, good oxygen reduction activity and two certain electronics hydrogen reduction selectivitys, it is carried out suitable alloying or electronic structure modulation also can promote its two electronics hydrogen reduction selectivity and activity further.Just because of this, transition metal and alloy are becoming the study hotspot of a new round as two electronics oxygen reduction electro-catalysts.Metal and alloy eelctro-catalyst have good Research Prospects, particularly recently the alloy such as Pt-Hg is found its two electronics oxygen reduction activity far above traditional material with carbon element, and selectivity reaches more than 96% (NatureMaterials, 12:1137-1144,2013).But metal alloy composition is prone to run off, and the use cost of noble metal is also of a relatively high.
It is matrix that the present invention proposes nano-graphite low with price, that chemical stability is high, so that O_2 cathodic reduction is had high selectivity for hydrogen peroxide, highly active hydrargyrum system alloy is the second constituent element, constitute nano-graphite-alloy intercalation configuration eelctro-catalyst, " double team " effect utilizing graphite linings realizes the stabilisation of hydrargyrum system alloy, nanorize, thus solving high activity, the high optionally losing issue that hydrargyrum system alloy eelctro-catalyst exists and reducing its use cost.The catalyst that the present invention proposes can be applied to the fields such as the electrochemical treatments of hydrogen peroxide electrochemical synthesis, organic sewage as cathod catalyst.
Summary of the invention
The present invention proposes the graphite-alloy compound eelctro-catalyst of a kind of cathodic reduction for oxygen.The nano-graphite that this catalyst is low with price, chemical stability is high is matrix, so that O_2 cathodic reduction is had high selectivity for hydrogen peroxide, highly active hydrargyrum system alloy is the second constituent element, constitute nano-graphite-alloy intercalation configuration eelctro-catalyst, " double team " effect utilizing graphite linings realizes the stabilisation of hydrargyrum system alloy, nanorize, thus solving high activity, the high optionally losing issue that hydrargyrum system alloy eelctro-catalyst exists and reducing its use cost.
A kind of graphite-alloy compound eelctro-catalyst of the cathodic reduction for oxygen, it is characterized in that: the first component of composite catalyst is the nano-graphite as matrix, second component is hydrargyrum system alloy, hydrargyrum system alloy by sandwich in nano-graphite graphite between layers, in catalyst, the mass content of alloy is 10-50%, and in alloy, the mass content of hydrargyrum is 50%-90%；Nano-graphite particle size range is 10-100nm；
Wherein said hydrargyrum system alloy can be the alloy that in Hg and Pt, Au, Pd, Ag, any one or two or more metal are formed；Graphite forms intercalation compound with alloy.
The present invention has the advantage that compared with existing material and technology
(1) high chemical stability: the matrix material that the composite catalyst that the present invention proposes adopts is graphite, second component is alloy, all there is good chemical stability, the oxidative environment that hydrogen peroxide synthesis is residing is had well adapting to property and stability.
(2) low cost: alloy catalyst price is higher, the present invention adopts nano-graphite " double team " alloy so that it is nanorize, and use cost can be greatly lowered.
(3) high activity, high selectivity: graphite is the eelctro-catalyst being commonly used in hydrogen peroxide electrochemical synthesis, catalytic oxidation-reduction is that hydrogen peroxide has certain activity and selectivity by itself, compare other material with carbon element all selective on advantage, and alloy-type catalyst has good selectivity and activity.The composite catalyst that both are constituted, maintain high activity of catalyst, high selective simultaneously, improve catalyst stability, reduce catalyst use cost.
Accompanying drawing explanation
The heat treatment process heating curve that Fig. 1 mixing method adopts when preparing nano-graphite (30nm) Pt-Hg alloy compound catalyst.
Fig. 2 is the Rotation ring disk electrode test curve contrast of nano-graphite (30nm) Pt-Hg alloy compound catalyst and conventional activated carbon XC-72.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
Embodiment 1
Mixing method is adopted to prepare graphite-alloy compound eelctro-catalyst.It is averaged Hong quick-fried method Nano graphite powder 100mg, the mercuric chloride 149.2mg mix homogeneously that particle diameter is 30nm standby.Take chloroplatinic acid 70mg, add 1ml ethanol and dissolve, obtain solution, be added in the mixture of graphite powder and mercuric chloride, mix homogeneously.Mixture is dried under 50 DEG C of vacuum conditions.Dried powder is transferred in tube type resistance furnace.Set heating schedule, as shown in Figure 1.After heat treatment terminates, natural air cooling, obtain black powder powder.Being poured into by black powder in the sodium borohydride solution that 100ml concentration is 1wt.%, magnetic agitation, centrifugation after reacting 4 hours, till clear liquid PH is close to 7.The material obtained is put into 60 DEG C dry 12 hours in vacuum drying oven, nano-graphite-alloy compound catalyst can be obtained.Be can determine that the hierarchical structure of nano-graphite-alloy by XRD analysis, utilize rotation to change disc electrode technology (RRDE) and the selectivity of its catalytic oxidation-reduction can be tested.Fig. 2 is it and the rotating ring disk electrode (r.r.d.e) of XC-72 tests the circular current curve comparison obtained.The KOH aqueous solution of test condition: 0.1mol/L is electrolyte, room temperature condition, oxygen blow more than 30 minutes before test.
Claims (5)
1. graphite-alloy compound the eelctro-catalyst for the cathodic reduction of oxygen, it is characterized in that: the first component of composite catalyst is the nano-graphite as matrix, second component is hydrargyrum system alloy, hydrargyrum system alloy by sandwich in nano-graphite graphite between layers, in catalyst, the mass content of alloy is 10-50%, and in alloy, the mass content of hydrargyrum is 50%-90%.
2. graphite-alloy compound the eelctro-catalyst of the cathodic reduction for oxygen according to claim 1, it is characterised in that: nano-graphite particle size range is 10-100nm.
3. graphite-alloy compound the eelctro-catalyst of the cathodic reduction for oxygen according to claim 1, it is characterised in that: wherein said hydrargyrum system alloy can be the alloy that in Hg and Pt, Au, Pd, Ag, any one or two or more metal are formed.
4. graphite-alloy compound the eelctro-catalyst of a kind of cathodic reduction for oxygen according to claim 1 or 3, it is characterised in that: in alloy, the content of hydrargyrum is 50%-90%.
5. graphite-alloy compound the eelctro-catalyst of the cathodic reduction for oxygen according to claim 1, it is characterised in that: 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112968184A (en) * | 2021-02-04 | 2021-06-15 | 陕西科技大学 | Electrocatalyst with sandwich structure and preparation method and application thereof |
Citations (2)
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| 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)
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| J.Y. TILQUIN等: "《Carbon monoxide poisoning of platinum-graphite ca+alysts for polymer electrolyte fuel cells: comparison between platinum-supported on graphite and intercalated in graphite》", 《LOUMAT OF POWER SOURCES》 * |
| SAMIRA SIAHROSTAMI等: "《Enabling direct H2O2 production through rational electrocatalyst design》", 《NATURE MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112968184A (en) * | 2021-02-04 | 2021-06-15 | 陕西科技大学 | Electrocatalyst with sandwich structure and preparation method and application thereof |
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