CN110479329A - A kind of preparation and application of phosphorus doping cobaltous telluride nano material - Google Patents
A kind of preparation and application of phosphorus doping cobaltous telluride nano material Download PDFInfo
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- CN110479329A CN110479329A CN201910788692.3A CN201910788692A CN110479329A CN 110479329 A CN110479329 A CN 110479329A CN 201910788692 A CN201910788692 A CN 201910788692A CN 110479329 A CN110479329 A CN 110479329A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 23
- 239000011574 phosphorus Substances 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 20
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 6
- -1 phosphorus Compound Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000004772 tellurides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic 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
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
It is cobalt hydroxide to be first made by hydro-thermal method using cobalt nitrate and urea as raw material, then Co is made through calcining the invention discloses a kind of preparation method of phosphorus doping cobaltous telluride nano material3O4Nanometer sheet, then by Co3O4It is calcined under an ar atmosphere after nanometer sheet and tellurium powder ground and mixed, obtains CoTe2Nanometer sheet；Finally by CoTe2Nanometer sheet is calcined under Ar gas with after sodium hypophosphite ground and mixed, obtains the CoTe of phosphorus doping2Nanometer particle material.The present invention changes CoTe around due to the doping of phosphorus2Cloud density, generate advantageous synergistic effect and improve HER activity, the P-CoTe of preparation2Nanoparticle shows porous structure, and specific surface area height, electric conductivity is high, has stable, efficient catalytic Hydrogen Evolution Performance under acid and alkaline environment, can be used as elctro-catalyst for hydrolyzing evolving hydrogen reaction.
Description
Technical field
The present invention relates to the preparation methods of consistent phosphorus doping cobaltous telluride nano material, can be used as catalyst and analyse for electro-catalysis
In hydrogen reaction, belong to composite material and preparation technical field and electrochemical technology field.
Background technique
With the use of fossil fuel, cause serious environmental pollution and energy crisis.Therefore, it is necessary to a kind of cleaning energy
Source replaces fossil energy, Hydrogen Energy as it is a kind of efficiently and friendly clean energy resource attracts attention.The source of Hydrogen Energy
Mode has very much, and electrolysis aquatic products hydrogen is a kind of efficient and free of contamination mode.But the consumption of electrolysis water Process Energy is more,
Therefore, efficient liberation of hydrogen (HER) catalyst is designed for accelerating kinetics and to substantially reduce overpotential most important.Platinum
It (Pt) is that the optimum catalyst of HER enables Pt to provide quick HER reaction since it has high stability and lower overpotential
Rate.But content is few and expensive on earth by Pt, extensive use is restricted.Therefore, there is an urgent need to find tool
There are high catalytic activity, the novel HER elctro-catalyst of good durability and low cost.
In recent years, many transition-metal catalysts have been widely studied, such as: transition metal oxide, sulfide, phosphorus
Compound, carbide, nitride, hydroxide etc..But these catalyst are counted by auto-catalytic activity area and active sites
The limitation of amount causes them to have biggish overpotential.Therefore, doping is drawn as a kind of effective raising electrocatalysis characteristic means
Researcher is played greatly to pay close attention to.Such as: Wang seminar is prepared for the CoS of Al doping2Nano wire shows good liberation of hydrogen
Can, when current density reaches 10 and 100 mA cm-2When, overpotential as low as 86 and 191 mV, and Tafel slope is 62.47
mV dec-1.(ACS Catal. 2019,9,1489 1502).Wei seminar is reported in the Ni of the S doping grown on carbon paper5P4
Nanometer plate array, S doping can not only inhibit S-Ni5P4NPA/CP surface oxidation in an acidic solution and dissolution, can be with
Reduce hydrogen adsorption free energy (Δ GH*), show the starting overpotential and 43.6mV dec of only 6mV-1Tafel slope (ACS
Appl. Mater. Interfaces 2018,10,26303 is 26311).
Tellurides material can be used as HER, oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and other electrochemical applications.Te
Compared with O, S and Se congeners, due to more obvious metallic character, so that the Te of good electronic conductivity helps to mention
High electrocatalytic active.But tellurides has biggish overpotential of hydrogen evolution, therefore, we are using the lesser P of atomic radius as yin
Ionic compartmentation occupies CoTe2Te a part in lattice, so as to improve the electro-catalysis HER performance of cobaltous telluride itself.
Summary of the invention
The purpose of the invention is to provide a kind of preparation methods of phosphorus doping cobaltous telluride nano material；
It is another object of the present invention to the electrocatalytic hydrogen evolution activity of the phosphorus doping cobaltous telluride nano material to above-mentioned preparation to grind
Study carefully and is applied to electro-catalysis hydrolysis evolving hydrogen reaction.
One, the preparation of phosphorus doping cobaltous telluride nano material
The method that the present invention prepares phosphorus doping cobaltous telluride nano material, comprising the following steps:
(1) it disperses cabaltous nitrate hexahydrate and urea in deionized water and stirs to after being completely dissolved, be lauched in 90 ~ 200 DEG C
Thermal response 5 ~ for 24 hours；Product is washed, dry, obtains cobalt hydroxide；Again by cobalt hydroxide in air atmosphere in 200 ~ 600 DEG C
2 ~ 8h is calcined, Co3O4 nanometer sheet is obtained；The mass ratio of cabaltous nitrate hexahydrate and urea is 1:0.25 ~ 1:4.
(2) by Co3O4 nanometer sheet with tellurium powder after ground mix, under an ar atmosphere in 400 ~ 800 DEG C of 2 ~ 8h of calcining, obtain
To CoTe2Nanometer sheet；The mass ratio of Co3O4 nanometer sheet and tellurium powder is 1:0.25 ~ 1:4.
(3) by CoTe2Nanometer sheet with sodium hypophosphite is ground mixes, then calcine 2 in 200 ~ 600 DEG C under an ar atmosphere
~8h；Obtained product is washed, dry, obtains the cobaltous telluride nano material of phosphorus doping, is labeled as P-CoTe2。CoTe2Nanometer
Piece and the mass ratio of sodium hypophosphite are 1:0.15 ~ 1:6, preferably 1:2 ~ 1:6.
Above-mentioned drying is 6 ~ 12h of vacuum drying at 60 ~ 80 DEG C.
Fig. 1 is P-CoTe prepared by the present invention2The X-ray powder diffraction pattern of nano material.From figure 1 it appears that
Form stable P-CoTe2Nanoparticle.
Fig. 2 is P-CoTe prepared by the present invention2The SEM of nano material schemes.Figure it is seen that P-CoTe2Nano material
Form the porous structure to be formed is accumulated similar to nanoparticle.This porous structure can expose more active sites, and mention
For more electronics transfer accesses to promote electrocatalysis characteristic.
Two, the chemical property of phosphorus doping cobaltous telluride nano material
Electrochemical measurement is completed on AUT84047 electrochemistry station by conventional three-electrode system.Working electrode is P-CoTe2
Nano-particle electrode (0.25 cm2), weigh 5 mg P-CoTe2Nano-particle catalyst sample is dissolved in 500 μ L water, 480 μ L
In ethyl alcohol and 20 μ LNafion solution (5wt%) mixed solutions, mixture is ultrasonically treated at least 30 minutes and is homogeneously urged with being formed
Agent ink.Then 10 μ L catalyst inks are added drop-wise on the glass-carbon electrode of 5 mm of diameter (catalyst loadings ~ 0.2mg/
cm2), it is carbon-point to electrode, reference electrode is the Ag/AgCl electrode for immersing saturation KCl.Use 0.5 MH2SO4And 1.0MKOH
Aqueous solution is made to test LSV polarization curve respectively as electrolyte.
Fig. 3 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2The LSV of nanoparticle and Pt/C in acid condition
Polarization curve.Fig. 3's the results show that P-CoTe2Nanoparticle shows a lower overpotential η in acidic environment10 =
64.62 mV dec of 159 mV and lesser Ta Feier-1。
Fig. 4 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2The LSV of nanoparticle and Pt/C under alkaline condition
Polarization curve.Fig. 4's the results show that P-CoTe2Nanoparticle overpotential in alkaline environment is η10=167 mV, Ta Feier
For 65.33 mV dec-1, Hydrogen Evolution Performance is better than other tellurides electrode materials reported in the literature.
Comparison diagram 3,4 is it is found that P-CoTe prepared by the present invention2Nanoparticle is in acidic environment (η10=159 mV) and alkali
(η in property environment10=167 mV) in show lower overpotential, there is excellent Hydrogen Evolution Performance, and be all far longer than
Prepared CoTe2Nanometer plate electrode and GC electrode, are more nearly Pt/C electrode, illustrate material prepared by the present invention in electro-catalysis
There is excellent performance in terms of liberation of hydrogen.Fig. 5 is GC, CoTe2Nanometer sheet, P-CoTe2Nanoparticle and Pt/C are in acid condition
Tafel slope curve, Fig. 6 GC, CoTe2Nanometer sheet, P-CoTe2The Tafel slope of nanoparticle and Pt/C under alkaline condition
Curve.Fig. 5,6 further explanations, P-CoTe2Nano-particle electrode shows excellent under alkaline condition and under acid condition
Electrocatalytic hydrogen evolution performance (slope of curve is smaller, illustrates that performance is better).
In conclusion compared with the prior art, the present invention has the following advantages:
1, the doping of phosphorus changes CoTe around2Cloud density, generate advantageous synergistic effect and improve HER activity；
2, the method for calcining is added to be prepared into P-CoTe by hydro-thermal2Nano material does not need any exacting terms, product knot
Structure can easily be accommodated, and batch wise differences are small, be suitble to large-scale production；
3、P-CoTe2Nanoparticle shows porous structure, and specific surface area is high, and electric conductivity is high, under acid and alkaline environment
With stabilization, efficient catalytic Hydrogen Evolution Performance.
Detailed description of the invention
Fig. 1 is P-CoTe prepared by the present invention2The X-ray powder diffraction pattern of nano material.
Fig. 2 is P-CoTe prepared by the present invention2The SEM of nano material schemes.
Fig. 3 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2The LSV of nanoparticle and Pt/C in acid condition
Polarization curve.
Fig. 4 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2The LSV of nanoparticle and Pt/C under alkaline condition
Polarization curve.
Fig. 5 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2Nanoparticle and Pt/C are in acid condition
Tafel slope curve.
Fig. 6 is GC, CoTe prepared by the present invention2Nanometer sheet, P-CoTe2Nanoparticle and Pt/C are under alkaline condition
Tafel slope curve.
Specific embodiment
In order to more preferably illustrate the contents of the present invention, combined with specific embodiments below to P-CoTe of the present invention2Nanometer liberation of hydrogen material
The preparation of material and performance are described further.Unless otherwise specified, each raw material used in following embodiment is commercially available production
Product.
Embodiment 1
(1) Co3O4The preparation of nanometer sheet: the Co (NO of 291 mg is taken3)2•6H2O and 300 mg urea are dissolved in the deionization of 35mL
It in water, stirs 30 minutes, forms homogeneous solution；Mixed solution is transferred to stainless steel high pressure of the 50mL containing polytetrafluoroethyllining lining
In kettle, hydro-thermal reaction 6 hours at 120 DEG C；Reaction kettle is cooled to room temperature after reaction, precipitated product deionized water and
It is lower 8 hours dry in 60 DEG C of vacuum drying ovens after ethanol washing 3 ~ 4 times；Finally desciccate is placed in tube furnace, in Ar atmosphere
It encloses, 250 DEG C (rate of heat addition is 2 DEG C of min-1) under calcine 2 hours, obtain Co3O4Nanometer sheet；
(2) CoTe2The preparation of nanometer sheet: the Co of above-mentioned synthesis is taken3O4Nanometer sheet 100mg is ground in mortar with 200 mgTe powder
Uniformly, with 5 DEG C of min-1Rate is warming up to 680 DEG C, calcines 2 hours, obtains CoTe2Nanometer sheet；
(3) P-CoTe2The preparation of nanoparticle: by 200 mgCoTe2Nanometer sheet is ground in mortar with 200 mg sodium hypophosphites
Mill uniformly, heats the sample to 300 DEG C of (2 DEG C of min of heating rate under an ar atmosphere-1) calcining 120 minutes；It is subsequently cooled to room
Temperature, product deionized water and ethyl alcohol are 4 hours dry in 60 DEG C of vacuum drying ovens by washing of precipitate 3 times, obtain P-CoTe2Nanometer
Particle；
(4) P-CoTe2Nano-particle electrode catalytic hydrogen evolution performance test: P-CoTe2Nanoparticle is shown in acidic environment
One lower overpotential η1064.62 mV dec of=159 mV and lesser Ta Feier-1；Overpotential is in alkaline environment
η10=167 mV, Ta Feier are 65.33 mV dec-1。
Embodiment 2
(1) Co3O4The preparation of nanometer sheet: with embodiment 1；
(2) CoTe2The preparation of nanometer sheet: with embodiment 1；
(3) P-CoTe2The preparation of nanoparticle: by 100 mg CoTe2Nanometer sheet is ground in mortar with 200 mg sodium hypophosphites
Mill uniformly, heats the sample to 300 DEG C of (2 DEG C of min of heating rate under an ar atmosphere-1) calcining 120 minutes；It is subsequently cooled to room
Temperature, product deionized water and ethyl alcohol are 4 hours dry in 60 DEG C of vacuum drying ovens by washing of precipitate 3 times, obtain P-CoTe2Nanometer
Particle；
(4) P-CoTe2Nano-particle electrode catalytic hydrogen evolution performance test: P-CoTe2Current density is 10 in acidic environment
mAcm-2, overpotential 192mV；Current density is 10 mAcm in alkaline condition-2, overpotential 198mV.
Embodiment 3
(1) Co3O4The preparation of nanometer sheet: with embodiment 1；
(2) CoTe2The preparation of nanometer sheet: with embodiment 1；
(3) P-CoTe2The preparation of nanoparticle: by 100 mg CoTe2Nanometer sheet is ground in mortar with 300 mg sodium hypophosphites
Mill uniformly, heats the sample to 300 DEG C of (2 DEG C of min of heating rate under an ar atmosphere-1) calcining 120 minutes；It is subsequently cooled to room
Temperature, product deionized water and ethyl alcohol are 4 hours dry in 60 DEG C of vacuum drying ovens by washing of precipitate 3 times, obtain P-CoTe2Nanometer
Particle；
(4) P-CoTe2Nano-particle electrode catalytic hydrogen evolution performance test: current density is 10 mAcm in acidic environment-2, mistake
Current potential is 210mV, and current density is 10 mAcm in alkaline condition-2, overpotential 218mV.
Embodiment 4
(1) Co3O4The preparation of nanometer sheet: with embodiment 1；
(2) CoTe2The preparation of nanometer sheet: with embodiment 1；
(3) P-CoTe2The preparation of nanoparticle: by 200 mg CoTe2Nanometer sheet is ground in mortar with 100 mg sodium hypophosphites
Mill uniformly, heats the sample to 300 DEG C of (2 DEG C of min of heating rate under an ar atmosphere-1) calcining 120 minutes；It is subsequently cooled to room
Temperature, product deionized water and ethyl alcohol are 4 hours dry in 60 DEG C of vacuum drying ovens by washing of precipitate 3 times, obtain P-CoTe2Nanometer
Particle；
(4) P-CoTe2Nano-particle electrode catalytic hydrogen evolution performance test: current density is 10mAcm in acidic environment-2, excessively electric
Position is 251mV, and current density is 10 mAcm in alkaline condition-2, overpotential 258mV.
Embodiment 5
(1) Co3O4The preparation of nanometer sheet: with embodiment 1；
(2) CoTe2The preparation of nanometer sheet: with embodiment 1；
(3) P-CoTe2The preparation of nanoparticle: by 300 mg CoTe2Nanometer sheet is ground in mortar with 100 mg sodium hypophosphites
Mill uniformly, heats the sample to 300 DEG C of (2 DEG C of min of heating rate under an ar atmosphere-1) calcining 120 minutes；It is subsequently cooled to room
Temperature, product deionized water and ethyl alcohol are 4 hours dry in 60 DEG C of vacuum drying ovens by washing of precipitate 3 times, obtain P-CoTe2Nanometer
Particle；
(4) P-CoTe2Nano-particle electrode catalytic hydrogen evolution performance test: current density is 10 mAcm in acidic environment-2, mistake
Current potential is 262mV, and current density is 10 mAcm in alkaline condition-2, overpotential 269mV.
Claims (6)
1. a kind of preparation method of phosphorus doping cobaltous telluride nano material, comprising the following steps:
(1) it disperses cabaltous nitrate hexahydrate and urea in deionized water and stirs to after being completely dissolved, be lauched in 90 ~ 200 DEG C
Thermal response 5 ~ for 24 hours；Product is washed, dry, obtains cobalt hydroxide；Again by cobalt hydroxide in air atmosphere in 200 ~ 600 DEG C
2 ~ 8h is calcined, Co3O4 nanometer sheet is obtained；
(2) by Co3O4 nanometer sheet with tellurium powder after ground mix, under an ar atmosphere in 400 ~ 800 DEG C of 2 ~ 8h of calcining, obtain
CoTe2Nanometer sheet；
(3) by CoTe2Nanometer sheet with sodium hypophosphite is ground mixes, then under an ar atmosphere in 200 ~ 600 DEG C of 2 ~ 8h of calcining；
Obtained product is washed, dry, obtains the cobaltous telluride nano material of phosphorus doping, is labeled as P-CoTe2。
2. the preparation method of phosphorus doping cobaltous telluride nano material as described in claim 1, it is characterised in that: cabaltous nitrate hexahydrate with
The mass ratio of urea is 1:0.25 ~ 1:4.
3. the preparation method of phosphorus doping cobaltous telluride nano material as described in claim 1, it is characterised in that: Co3O4 nanometer sheet with
The mass ratio of tellurium powder is 1:0.25 ~ 1:4.
4. the preparation method of phosphorus doping cobaltous telluride nano material as described in claim 1, it is characterised in that: CoTe2Nanometer sheet and time
The mass ratio of sodium phosphite is 1:0.15 ~ 1:6.
5. the preparation method of phosphorus doping cobaltous telluride nano material as described in claim 1, it is characterised in that: drying is 60 ~ 80
6 ~ 12h is dried in vacuo at DEG C.
6. the phosphorus doping cobaltous telluride nano material of method preparation as described in claim 1 is anti-for hydrolyzing liberation of hydrogen as elctro-catalyst
It answers.
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