CN106629814A - Sulfur-doped three-dimensional porous cuprous oxide nano-material and application thereof to electrochemical hydrogen evolution reaction - Google Patents
Sulfur-doped three-dimensional porous cuprous oxide nano-material and application thereof to electrochemical hydrogen evolution reaction Download PDFInfo
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- CN106629814A CN106629814A CN201710050434.6A CN201710050434A CN106629814A CN 106629814 A CN106629814 A CN 106629814A CN 201710050434 A CN201710050434 A CN 201710050434A CN 106629814 A CN106629814 A CN 106629814A
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- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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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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- 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 invention discloses a sulfur-doped three-dimensional porous cuprous oxide nano-material and application thereof to electrochemical hydrogen evolution reaction. A cuprous sulfide nano-rod is synthesized on three-dimensional copper foam as a precursor mainly by virtue of a normal temperature impregnation method, and the sulfur-doped porous cuprous oxide nano-material is obtained in an electrochemical preparation process. The sulfur-doped three-dimensional porous cuprous oxide nano-material is mainly applied to electrochemical hydrogen evolution, the catalytic activity is detected by adopting a linear scanning curve (polarization curve), and the stability of the material is tested by virtue of a cyclic voltammetry curve. According to the sulfur-doped three-dimensional porous cuprous oxide nano-material, a porous Cu2OxS(1-x) nano-structure is synthesized by a method which is convenient to operate to enlarge the specific surface area of the material, copper is combined with oxygen to collaborate active sites around the copper and improve the adsorbability of the copper for hydrogen, and anionic sulfur is further doped to greatly improve the catalytic activity of the material, improve the catalysis efficiency of electrochemical hydrogen evolution and effectively improve the stability of the catalyst.
Description
Technical field
The invention belongs to sustainable novel energy application and preparation field is cleaned, more particularly to a kind of cuprous oxide of sulfur doping
Application in three-D nano-porous material and its electrochemistry evolving hydrogen reaction.
Background technology
At present, fossil fuel remains industrial primary raw material, and its burning not only causes serious pollution to environment,
Product CO2Greenhouse effects are produced, and fossil fuel is a kind of non-renewable energy resources, therefore substantial amounts of effort is used for searching cleaning
Regenerative resource is used for replacing fossil fuel.Because hydrogen energy source derives from water, burning generates water, is that one kind preferably can be used for generation
For the energy of fossil fuel, and can be used as energy carrier.At present the main method of industrial hydrogen production has three kinds：Steam methane weight
Whole, Coal Gasification and electrolysis water, first two method accounts for the 95% of hydrogen output, and electrolysis water only accounts for 4%, and first two method is consumed not
Renewable resource, and produce CO2, greenhouse effects are produced, therefore electrolysis water is a kind of promising, sustainable work for recycling
Industry hydrogen production process.
The class of chemical element one for electrochemistry hydrogen manufacturing is precious metals pt, although its hydrogen manufacturing performance is superior, but noble metal valency
Lattice are expensive, earth's crust content is few, limit the development in commercial Application；Another kind of is transition metal and nonmetalloid knot
Share in structure electrocatalysis material.The transition metal for being most commonly applied to electrochemistry hydrogen manufacturing is Mo, Co, Ni, with these three units
Element is compared, and Cu has higher earth's crust content, and cheap price, hypotoxicity, more preferable biological selectivity, more rich is oxidable
Reducing condition, abundant chemical coordination.It is weaker to the adsorption capacity of hydrogen but copper is compared with other transition metals, therefore will
Cu is modified, is combined to optimize the electronic structure of its electric conductivity and catalytic center with other base metals.
Used as a kind of transition metal oxide, its stability is difficult control to cuprous oxide, and cuprous oxide is a kind of half
Conductor, electric conductivity is poor, so as to reduce the catalytic performance of catalyst, therefore using less in terms of electrochemistry hydrogen manufacturing.Here
The method that we are prepared using electrochemistry, the cuprous nano that the cuprous sulfide that soak at room temperature is obtained is changed into sulfur doping is more
Porous materials, the material for synthesizing have higher specific surface area, and be applied to acidity, alkaline electrolyte hydrogen production by water decomposition with
And full decomposition water in alkaline electrolyte, all achieve preferable effect.The anion doped ternary transition metal for synthesizing
Compound Cu2OxS1-x, a small amount of sulfur doping is optimal the performance of catalyst, wherein S2-Instead of O2-Position, effective drop
In the middle of low electro-catalysis hydrogen manufacturing can, improve the energy of adsorption to hydrogen, so as to improve electrochemistry hydrogen manufacturing performance, high yield hydrogen is lived
Property plays positive role.So the three-D nano-porous material of the cuprous oxide of this sulfur doping is by with very big development and application
Prospect.
The purpose of the present invention is for the deficiencies in the prior art, there is provided cheap, prepares a kind of simple sulfur doping
The three-D nano-porous material of cuprous oxide, and it is applied to the full decomposition water catalytic field of electrochemistry.The cuprous oxide three of the sulfur doping
The features such as dimension nano-porous materials have high catalysis activity, good stability.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of cuprous oxide three-dimensional manometer of sulfur doping is more
Porous materials and its application in electrochemistry evolving hydrogen reaction.
The purpose of the present invention is achieved through the following technical solutions：
The invention has the beneficial effects as follows：The present invention has obtained sulphur by simple soak at room temperature and Electrochemical Scanning process
The three-D nano-porous material of the cuprous oxide of doping, the electrode prepared using the material can apply to electrochemistry liberation of hydrogen.
Catalysis activity aspect, the anion doped ternary transition metal compound Cu for synthesizing2OxS1-x, a small amount of sulfur doping makes catalysis
The performance of agent is optimal, wherein S2-Instead of part O2-Position, effectively reduce electro-catalysis hydrogen manufacturing in the middle of can, carry
The high energy of adsorption to hydrogen, so as to improve electrochemistry hydrogen manufacturing performance, to high yield hydrogen activity positive role is played, and is improve
The stability of catalysis material.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram piece (SEM) of the cuprous sulfide that soak at room temperature prepared by the present invention is obtained.
Fig. 2 is the scanning electron microscope diagram of the three-D nano-porous material of the cuprous oxide of sulfur doping prepared by the present invention
Piece (SEM).
Fig. 3 is during the present invention is sent out using cyclic voltammetric and prepares the cuprous oxide of sulfur doping, enclose 500 respectively,
The polarization curve that 1000 circles, 1500 circles are obtained, wherein 1500 circles are the final materials for obtaining.
Fig. 4 is the energy spectrum diagram of the three-D nano-porous material of the cuprous oxide of sulfur doping prepared by the present invention, from figure
It is simultaneous to three kinds of elements, and is the oxidation oxygen copper of a small amount of sulfur doping.
Fig. 5 is that the three-D nano-porous material of the cuprous oxide of sulfur doping prepared by the present invention is electric in 0.5M sulfuric acid solutions
The polarization curve (Polarization curves) of chemical liberation of hydrogen, respectively with Cu2S、Cu2O and Pt/C are contrasted.
Fig. 6 is three-D nano-porous material the stablizing in 0.5M sulfuric acid of the cuprous oxide of sulfur doping prepared by the present invention
Property test curve (Durability test).
Specific embodiment
With reference to embodiment the invention will be further described the present invention technical solution, these embodiments can not
It is not understood as the restriction to technical solution.
Embodiment 1：The present embodiment prepares the three-D nano-porous material of the cuprous oxide of sulfur doping, specifically includes following step
Suddenly：
(1) 6.4g NaOH and 1.368g ammonium persulfates are dissolved in 60ml deionized waters, are stirred, mixed
Solution.
(2) foam copper obtained after cleaning is put into mixed solution, 25 DEG C of immersion 20min of normal temperature take out deionization
Water is rinsed, N2It is dried up, and obtains the foam copper that surface forms Kocide SD；
(3) foam copper after step 2 is processed is soaked in Na2In S solution, normal temperature 25 DEG C of immersions 24h, the Na2S's is dense
Spend for 0.05mol/L, solvent is by deionized water and methyl alcohol according to volume ratio 1:1 composition；Then take out deionized water flushing, N2
Dry up, obtain the foam copper of area load cuprous sulfide.
(4) the foam copper electricity consumption chemical cycle volt-ampere cv after step 3 is processed is activated, and the oxidation for obtaining sulfur doping is sub-
The three-D nano-porous material of copper, the potential window of cv activation is 0.1V～-0.8V vs RHE, and sweep speed is 100mV/s, electricity
Solution liquid is 0.5M H2SO4, the circulation number of turns is 1500 circles, is Pt pieces to electrode.
Fig. 1 is the scanning electron microscope diagram (SEM) of the cuprous sulfide that soak at room temperature prepared by the present invention is obtained, from figure
It can be seen that cuprous sulfide is formed with the nanometer rods self assembly on foam copper surface by homogeneous growth, as can be seen from Figure 1
The diameter of cuprous sulfide nanometer rods is about 1 μm.Fig. 2 is the three-D nano-porous material of the cuprous oxide of sulfur doping prepared by the present invention
Material scanning electron microscope diagram (SEM).As can be seen from the figure the continuous pore passage structure of the three-dimensional manometer of the cuprous oxide of sulfur doping,
Hole wall diameter is about 20nm, has increased considerably the specific surface area of material.
The three-D nano-porous materials application of the cuprous oxide of sulfur doping prepared by embodiment 1 in electrochemistry hydrogen manufacturing, specifically
For：By the three-D nano-porous material of the cuprous oxide of sulfur doping be working electrode (WE), saturation silver/silver chloride electrode be reference
Electrode (RE), platinized platinum are to constitute three-electrode system to electrode (CE), with 0.5M sulfuric acid as electrolyte.Carrying out electro-chemical test
Before, saturation nitrogen is passed through, remove the oxygen in solution.And electrode is carried out to calibrate positive E (RHE)=E (Ag/AgCl)+0.197V.
Fig. 3 be the present invention sulfur doping is prepared using cyclic voltammetry cuprous oxide three-D nano-porous materials process in, 0 circle, 500
Circle, 1000 circles, the corresponding polarization curve (Polarization curves) of 1500 circle difference, it can be seen that with cyclic voltammetric
The increase of the number of turns, the catalytic performance of material gradually optimizes, when stable performance is reached after activation to 1500 circles, so corresponding sample
For the cuprous oxide of our the final sulfur dopings for obtaining.Fig. 4 be the present invention be the present invention prepare sulfur doping cuprous oxide
Three-D nano-porous material energy spectrum diagram, see that three kinds of elements are simultaneous from figure, and be a small amount of sulfur doping
Oxidation oxygen copper.
In addition, existing cuprous sulfide and cuprous oxide are obtained respectively according to the activation method method of sulfur doping cuprous oxide
The materials application for arriving is in electrochemistry evolving hydrogen reaction, as shown in figure 5, it is 10mA/cm to work as current density2, the overpotential of cuprous sulfide
For 268mA, the overpotential of cuprous oxide is 205mV, and the overpotential of sulfur doping cuprous oxide is 51mV.Cuprous sulfide, oxygen in figure
Change cuprous less stable in an acidic solution, wherein cuprous sulfide utilizes cyclic voltammetry in acid solution test process
Change to the cuprous oxide of sulfur doping always, and cuprous oxide is easily dissolved in an acidic solution, therefore we are to sulfur doping
The stability of cuprous oxide tested, Fig. 6 is the three-D nano-porous material of the cuprous oxide of sulfur doping prepared by the present invention
The cyclic voltammetric stability of material, this figure is by Cu2S is circulated after volt-ampere 1500 is enclosed and obtains sulfur doping cuprous oxide, and material reaches
To stable state, following sulfur doping cuprous oxide is circulated under identical condition a volt-ampere stability test, can from figure
After to find out circulation 1000 times, linearity curve does not continue optimization, but has reached more stable state, and show compared with
High stability.
By upper comparative analysis, the present invention has obtained sulfur doping by the process of simple soak at room temperature and Electrochemical Scanning
Cuprous oxide three-D nano-porous material, the electrode prepared using the material can apply in electrochemistry evolving hydrogen reaction.
In terms of catalysis activity, the anion doped ternary transition compound Cu for synthesizing2OxS1-x, generate unexpected technology
Effect.A small amount of sulfur doping is optimal the performance of catalyst, wherein S2-Instead of O2-Position, effectively reduce electricity
Energy, improves the energy of adsorption to hydrogen in the middle of catalyzing manufacturing of hydrogen, so as to improve electrochemistry hydrogen manufacturing performance, high yield hydrogen activity is played
Positive role, and improve the stability of catalysis material.
Embodiment 2：The present embodiment have studied activation process, specific as follows：
The foam copper of area load cuprous sulfide is activated with electrochemical cyclic voltammetry cv, is obtained by cuprous sulfide
The cuprous oxide of the sulfur doping of conversion, the potential window of cv activation is 0.1V～-0.8V vs RHE, and sweep speed is 100mV/
S, the circulation number of turns 1500 is enclosed, and electrolyte is 0.5M H2SO4, it is Pt pieces to electrode.
As shown in figure 3, the three-D nano-porous of the cuprous oxide of sulfur doping is prepared by cuprous sulfide using cyclic voltammetry
In materials process, 0 circle, 500 circles, 1000 circles, the corresponding polarization curve (Polarization curves) of 1500 circle difference can
To find out, with the increase of the cyclic voltammetric number of turns, the catalytic performance of material gradually optimizes, and after activation to 1500 is enclosed performance is reached
It is stable, so corresponding sample is the cuprous oxide of our the final sulfur dopings for obtaining.
Claims (3)
1. a kind of three-D nano-porous material of the cuprous oxide of sulfur doping, it is characterised in that the material is followed by electrochemistry
Ring voltammetry is obtained after cuprous sulfide nano material is activated.
2. the three-D nano-porous material of the cuprous oxide of sulfur doping according to claim 1, it is characterised in that the material
Can be prepared by following steps：
(1) 6.4g NaOH and 1.368g ammonium persulfates are dissolved in 60ml deionized waters, are stirred, obtain mixing molten
Liquid.
(2) foam copper obtained after cleaning is put into mixed solution, 25 DEG C of immersion 20min of normal temperature take out deionized water punching
Wash, N2It is dried up, and obtains the foam copper that surface forms Kocide SD；
(3) foam copper after step 2 is processed is soaked in Na2In S solution, normal temperature 25 DEG C of immersions 24h, the Na2The concentration of S is
0.05mol/L, solvent is by deionized water and methyl alcohol according to volume ratio 1:1 composition；Then take out deionized water flushing, N2Blow
It is dry, obtain the foam copper of area load cuprous sulfide.
(4) the foam copper electricity consumption chemical cycle volt-ampere cv after step 3 is processed is activated, and obtains the cuprous oxide three of sulfur doping
Dimension nano-porous materials, the potential window of cv activation is 0.1V～-0.8V vs RHE, and sweep speed is 100mV/s, electrolyte
It is 0.5M H2SO4, the circulation number of turns is 1500 circles, is Pt pieces to electrode.
3. a kind of three-D nano-porous material of the cuprous oxide of the sulfur doping described in claim 1 is in electrochemistry evolving hydrogen reaction
Using.
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| CN108682857A (en) * | 2018-06-14 | 2018-10-19 | 商丘师范学院 | A kind of preparation method of porous flower piece shape anode material of lithium battery |
| CN108889264A (en) * | 2018-07-13 | 2018-11-27 | 北京京盛国泰科技有限公司 | A kind of preparation method of the foam copper of adsorption-decomposition function formaldehyde |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418130A (en) * | 2011-11-02 | 2012-04-18 | 西南交通大学 | Preparation method of grid CuxS/Cu2O, x=1.75~2 composite pyramid-like thin film |
| CN104475137A (en) * | 2014-11-04 | 2015-04-01 | 陕西科技大学 | In-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst and preparation method thereof |
| CN104495908A (en) * | 2014-12-31 | 2015-04-08 | 湖南稀土金属材料研究院 | Preparation method of cuprous sulfide powder, and cuprous sulfide powder |
| CN104689796A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Nano cuprous sulfide modified monolithic column material and preparation method thereof |
| CN105803500A (en) * | 2016-04-05 | 2016-07-27 | 华南师范大学 | Petal-shaped cuprous oxide and preparation method and application thereof |
-
2017
- 2017-01-23 CN CN201710050434.6A patent/CN106629814B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418130A (en) * | 2011-11-02 | 2012-04-18 | 西南交通大学 | Preparation method of grid CuxS/Cu2O, x=1.75~2 composite pyramid-like thin film |
| CN104689796A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Nano cuprous sulfide modified monolithic column material and preparation method thereof |
| CN104475137A (en) * | 2014-11-04 | 2015-04-01 | 陕西科技大学 | In-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst and preparation method thereof |
| CN104495908A (en) * | 2014-12-31 | 2015-04-08 | 湖南稀土金属材料研究院 | Preparation method of cuprous sulfide powder, and cuprous sulfide powder |
| CN105803500A (en) * | 2016-04-05 | 2016-07-27 | 华南师范大学 | Petal-shaped cuprous oxide and preparation method and application thereof |
Cited By (25)
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| CN111118537A (en) * | 2019-07-24 | 2020-05-08 | 天津大学 | Molybdenum disulfide modified carbon layer coated cuprous oxide nanowire material growing on surface of foam copper and preparation method and application thereof |
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| CN114892204B (en) * | 2022-04-02 | 2023-09-12 | 中国科学院化学研究所 | Anion-cation double-doped catalyst and preparation method and application thereof |
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| CN114657601B (en) * | 2022-05-10 | 2024-01-30 | 琼台师范学院 | Preparation method and application of nickel oxide-iridium nanocluster heterogeneous material |
| CN116143161A (en) * | 2023-01-17 | 2023-05-23 | 华南农业大学 | Copper sulfide composite material loaded with copper oxide self-supporting copper foam and preparation method and application thereof |
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