CN110404562A - A kind of Co of richness defect3S4Ultra-thin porous nanometer sheet material and the preparation method and application thereof - Google Patents
A kind of Co of richness defect3S4Ultra-thin porous nanometer sheet material and the preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000007547 defect Effects 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 20
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 20
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 229960001124 trientine Drugs 0.000 claims description 16
- 230000036571 hydration Effects 0.000 claims description 15
- 238000006703 hydration reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000003851 corona treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000012044 organic layer Substances 0.000 abstract description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001786 chalcogen compounds Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- -1 chalcogenide compound Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of Co of rich defect3S4Ultra-thin porous nanometer sheet material and its preparation method and application, the ultra-thin porous two-dimensional nano sheet material of transition metal base richness defect that the dry removing of the alternately arranged inorganic-organic hybrid predecessor of inorganic organic layer prepares non-laminar structure is handled by using plasma technique, which has high stability, efficient electrocatalytic hydrogen evolution analysis oxygen performance and complete solution water activity in alkaline medium.
Description
Technical field
The present invention relates to transition metal base chalcogen compound technical field of nano material, and in particular to a kind of non-laminar crystal
The Co of the rich defect of structure3S4Ultra-thin porous nanometer sheet material and its preparation method and application.
Background technique
In recent years, the transient metal chalcogenide compound of non-laminar structure has been shown to have excellent electrocatalysis characteristic, but
It is that it still has and leads to problems such as catalyst mass activity lower because atom utilization is not high.In order to solve atom utilization
There is low problem porous or ultra-thin two-dimension structure nano material to receive the extensive concern of researchers in recent years, however
The accurate preparation simultaneously with porous and two structure features of ultra-thin two-dimension chalcogen compound nano materials is still synthesis chemistry
One significant challenge in field.
It is current studies have shown that suitable anion (O2‐, S2‐, Se2‐Deng) defect can effectively enhance transition metal
The electrolysis water performance of base catalyst.The presence of anion defect enhances the electron mobilities near fermi level, to enhance
The electric conductivity of catalyst.On the other hand, the charge density of region enhancing also subtracts the valence state reduction of metal ion and ligancy
It is small, thus the catalytic activity and the stability under high current density that further increase material.Plasma is mainly concentrated and is answered at present
With nanometer sheet processing with layer structure two-dimensional material synthesis on, the pervasive non-laminar structure of still rarely seen simplicity
The plasma synthesis method of the ultra-thin porous two-dimensional nano piece of transition metal base chalcogen compound richness defect.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Co of rich defect3S4Ultra-thin porous nanometer sheet
It is alternately arranged inorganic organic miscellaneous to handle inorganic organic layer by using plasma technique for material and its preparation method and application
Change the ultra-thin porous two-dimensional nano sheet material of transition metal base richness defect that the dry removing of predecessor prepares non-laminar structure, the nanometer sheet
Material has high stability, efficient electrocatalytic hydrogen evolution analysis oxygen performance and complete solution water activity in alkaline medium.
The present invention is achieved by the following technical solutions:
A kind of Co of richness defect3S4Ultra-thin porous nanometer sheet material has cavernous structure in nanometer sheet, in the nanometer sheet
Edge and hole in there are a large amount of electro catalytic activity site, which is the Co atom of low coordination, described
Nanometer sheet with a thickness of 0.5-3nm,
It prepares as steps described below:
Step 1, four hydration cobalt acetate (C are weighed4H6CoO4·4H2) and thioacetamide (C O2H5NS) in ice water bath environment
Under be dissolved in deionized water, until completely dissolved be added triethylene tetramine (TETA), wherein four hydration cobalt acetates, thioacetamide,
The mass volume ratio of deionized water and triethylene tetramine is (0.15-0.30): (0.05-0.08): (3.6-7.2): (7.2-
14.4), wherein four hydration cobalt acetates and thioacetamide dosage are quality, unit g, deionized water and triethylene tetramine
Dosage is volume, unit ml, is placed in hydrothermal reaction kettle from magnetic agitation 30min at 20-25 DEG C of room temperature to being uniformly dispersed,
15-20h is reacted under the conditions of 150-200 DEG C, is cooled to room temperature after being centrifugated product and is successively washed with deionized water and ethyl alcohol
It washs 3-5 times, is placed in a vacuum drying oven, dry 4-8h, obtains black reaction product Co under the conditions of 50-80 DEG C3S4/ TETA is miscellaneous
Change presoma；
Step 2, Co step 1 obtained3S4/ TETA hydridization presoma is put into porcelain boat to be handled with argon plasma, place
The reason time is 15-30min, power 250-400W, pressure 50-100Pa, and gas flow rate is 100-300mL min-1, will locate
The product obtained after reason ethanol washing and dry 6-10h obtains the Co of rich defect under the conditions of 30-60 DEG C3S4It is ultra-thin porous to receive
Rice sheet material (Co3S4PNSvac)。
In the above-mentioned technical solutions, the thickness of the nanometer sheet is preferably 1-1.5nm.
In the above-mentioned technical solutions, four hydration cobalt acetates, thioacetamide, deionized water and triethylene in the step 1
The mass volume ratio of tetramine is preferably (0.20-0.25): (0.06-0.07): (4.8-6): (9.6-12) is placed in hydrothermal reaction kettle
In reaction temperature be preferably 155-165 DEG C, the reaction time is preferably 16-18h, and the drying temperature being placed in a vacuum drying oven is excellent
It is selected as 60-70 DEG C, drying time is preferably 5-6h.
In the above-mentioned technical solutions, the time of the step 2 plasma processing is preferably 20-25min, and power is
300-350W, pressure 60-80Pa, gas flow rate are 150-200mL min-1, drying temperature is preferably 50-60 DEG C, when dry
Between preferably 6-8h.
On the other hand, a kind of Co of rich defect3S4The preparation method of ultra-thin porous nanometer sheet material, as steps described below into
Row:
Step 1, four hydration cobalt acetate (C are weighed4H6CoO4·4H2) and thioacetamide (C O2H5NS) in ice water bath environment
Under be dissolved in deionized water, until completely dissolved be added triethylene tetramine (TETA), wherein four hydration cobalt acetates, thioacetamide,
The mass volume ratio of deionized water and triethylene tetramine is (0.15-0.30): (0.05-0.08): (3.6-7.2): (7.2-
14.4) it, is placed in hydrothermal reaction kettle from magnetic agitation 30min at 20-25 DEG C of room temperature to being uniformly dispersed, in 150-200 DEG C of item
15-20h is reacted under part, is cooled to room temperature after being centrifugated product successively with deionized water and ethanol washing 3-5 times, is placed in true
In empty drying box, dry 4-8h, obtains black reaction product Co under the conditions of 50-80 DEG C3S4/ TETA hydridization presoma；
The mass volume ratio of four hydration cobalt acetates, thioacetamide, deionized water and triethylene tetramine is preferred in step 1
For (0.20-0.25): (0.06-0.07): (4.8-6): (9.6-12), the reaction temperature being placed in hydrothermal reaction kettle are preferably
155-165 DEG C, the reaction time is preferably 16-18h, and the drying temperature being placed in a vacuum drying oven is preferably 60-70 DEG C, when dry
Between preferably 5-6h；
Step 2, Co step 1 obtained3S4/ TETA hydridization presoma is put into porcelain boat to be handled with argon plasma, place
The reason time is 15-30min, power 250-400W, pressure 50-100Pa, and gas flow rate is 100-300mL min-1, will locate
The product obtained after reason ethanol washing and dry 6-10h obtains the Co of rich defect under the conditions of 30-60 DEG C3S4It is ultra-thin porous to receive
Rice sheet material (Co3S4PNSvac)；
The time of corona treatment is preferably 20-25min, power 300-350W, pressure 60- in step 2
80Pa, gas flow rate are 150-200mL min-1, drying temperature is preferably 50-60 DEG C, and drying time is preferably 6-8h.
On the other hand, a kind of Co of rich defect3S4Ultra-thin porous nanometer sheet material analyses oxygen and complete solution water side in electrocatalytic hydrogen evolution
The application in face, for alkaline medium evolving hydrogen reaction, in 10mA cm-1Current density under overpotential be only (60-70)
MV, and have up to (1000-1100) A g under the overpotential of (180-200) mV-1Mass activity；For oxygen evolution reaction
For, in 10mA cm-1Current density under overpotential be only (250-300) mV.
The advantages and benefits of the present invention are:
(1) present invention is using plasma to having in the cleaning action removal inorganic-organic hybrid predecessor of organic molecule
Machine layer obtains the inorganic ultra-thin two-dimension nanometer sheet of surface cleaning, avoids organic component in subsequent electro-chemical test to catalysis
Activity has an adverse effect.
(2) present invention generates anion defect and corrasion in ultrathin nanometer on piece using the reduction of plasma
Pore structure is formed, by controlling the experiment parameter (power, atmosphere, reaction time and temperature etc.) of plasma synthesis, is being synthesized
Realize that the defect density of ultra-thin porous two-dimension nano materials and pore size are adjustable while rich defect ultra-thin porous two-dimensional nano piece.
(3) the ultra-thin porous nanometer sheet material of rich defect of the invention has more active sites, and stable structure is porous
Structure and a large amount of sulphur defect can speed up the transfer and transmission of electronics, and performance is excellent in terms of electrocatalytic hydrogen evolution analyses oxygen and complete solution water
It is different.
Detailed description of the invention
Fig. 1 is the Co prepared through the invention3S4Scanning electron microscope (SEM) photo of/TETA hydridization presoma.
Fig. 2 is the Co prepared through the invention3S4PNSvacTransmission electron microscope (TEM) photo.
Fig. 3 is the Co prepared through the invention3S4PNSvacHigh resolution transmission electron microscopy (HRTEM) photo.
Fig. 4 is the Co prepared through the invention3S4PNSvacX-ray diffraction (XRD) figure.
Fig. 5 is the Co prepared through the invention3S4PNSvacElectrocatalytic hydrogen evolution linear sweep voltammetry curve.
Fig. 6 is the Co prepared through the invention3S4PNSvacElectro-catalysis analyse oxygen linear sweep voltammetry curve.
Fig. 7 is the Co prepared through the invention3S4PNSvacElectro-catalysis complete solution water linear scan volt-ampere curve.
Fig. 8 is the Co prepared through the invention3S4PNSvacElectrocatalytic hydrogen evolution time current curve.
Fig. 9 is the Co prepared through the invention3S4PNSvacElectro-catalysis analyse oxygen time current curve.
Figure 10 is the Co prepared through the invention3S4PNSvacElectro-catalysis complete solution water time current curve.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawing with specific embodiment into
One step illustrates technical solution of the present invention.It should be understood that following embodiments be it is illustrative, be not restrictive, cannot
It is limited the scope of protection of the present invention with following embodiments.Required raw material is commercially available in following embodiment, and used four
Being hydrated cobalt acetate, thioacetamide and triethylene tetramine is chemical analysis pure reagent.Hydrothermal reaction kettle described in step 1 uses
Using polytetrafluoroethylene (PTFE) as the stainless steel cauldron of liner.
Embodiment one
Step 1: weighing the clean conical flask that 0.25g tetra- is hydrated cobalt acetate and 0.07g thioacetamide is placed in 200mL
In, the deionized water that 6mL is added into conical flask in the environment of ice-water bath is complete by four hydration cobalt acetates and thioacetamide
Dissolution；
Step 2: the triethylene tetramine of 12mL is slowly added into the solution that step 1 obtains, at room temperature magnetic agitation 30
Minute is placed in 50mL hydrothermal reaction kettle, 16h is reacted under the conditions of 160 DEG C, after being cooled to room temperature by product from reaction kettle
Be transferred to centrifuge tube to be centrifuged, and washed respectively 3 times with deionized water and ethyl alcohol, be put into vacuum oven later in
Dry 6h, obtains the Co of black under the conditions of 60 DEG C3S4/ TETA hydridization presoma is simultaneously ground into powdered；
Step 3: weighing the Co that 100mg step 2 obtains3S4/ TETA hydridization presoma, is put into porcelain boat, uses argon plasma
Body handles 20min, and wherein power used by corona treatment is 300W, pressure 70Pa, gas flow rate 200mL
min-1；
Step 4: will by step 3 treated after sample is cooled to room temperature with ethanol washing and under the conditions of 60 DEG C it is dry
6h obtains the Co of rich defect3S4Ultra-thin porous nanometer sheet material (Co3S4PNSvac)。
Embodiment two
Step 1: weighing the clean conical flask that 0.25g tetra- is hydrated cobalt acetate and 0.07g thioacetamide is placed in 200mL
In, the deionized water that 6mL is added into conical flask in the environment of ice-water bath is complete by four hydration cobalt acetates and thioacetamide
Dissolution；
Step 2: the triethylene tetramine of 12mL is slowly added into the solution that step 1 obtains, at room temperature magnetic agitation 30
Minute is placed in 50mL hydrothermal reaction kettle, 16h is reacted under the conditions of 150 DEG C, after being cooled to room temperature by product from reaction kettle
Be transferred to centrifuge tube to be centrifuged, and washed respectively 3 times with deionized water and ethyl alcohol, be put into vacuum oven later in
Dry 6h, obtains the Co of black under the conditions of 60 DEG C3S4/ TETA hydridization presoma is simultaneously ground into powdered；
Step 3: weighing the Co that 100mg step 2 obtains3S4/ TETA hydridization presoma, is put into porcelain boat, uses argon plasma
Body handles 20min, and wherein power used by corona treatment is 300W, pressure 70Pa, gas flow rate 200mL
min-1；
Step 4: will by step 3 treated after sample is cooled to room temperature with ethanol washing and under the conditions of 60 DEG C it is dry
6h obtains the Co of rich defect3S4Ultra-thin porous nanometer sheet material (Co3S4PNSvac)。
Embodiment three
Step 1: weighing the clean conical flask that 0.25g tetra- is hydrated cobalt acetate and 0.07g thioacetamide is placed in 200mL
In, the deionized water that 6mL is added into conical flask in the environment of ice-water bath is complete by four hydration cobalt acetates and thioacetamide
Dissolution；
Step 2: the triethylene tetramine of 12mL is slowly added into the solution that step 1 obtains, at room temperature magnetic agitation 30
Minute is placed in 50mL hydrothermal reaction kettle, 20h is reacted under the conditions of 160 DEG C, after being cooled to room temperature by product from reaction kettle
Be transferred to centrifuge tube to be centrifuged, and washed respectively 3 times with deionized water and ethyl alcohol, be put into vacuum oven later in
Dry 6h, obtains the Co of black under the conditions of 60 DEG C3S4/ TETA hydridization presoma is simultaneously ground into powdered；
Step 3: weighing the Co that 100mg step 2 obtains3S4/ TETA hydridization presoma, is put into porcelain boat, uses argon plasma
Body handles 20min, and wherein power used by corona treatment is 300W, pressure 70Pa, gas flow rate 200mL
min-1；
Step 4: will by step 3 treated after sample is cooled to room temperature with ethanol washing and under the conditions of 60 DEG C it is dry
6h obtains the Co of rich defect3S4Ultra-thin porous nanometer sheet material (Co3S4PNSvac)。
Example IV
With example one, difference is in step 3 using the power that argon plasma is handled to be 350W, other reactions step
Condition remains unchanged, and acquired results are close to 1 acquired results of example.
Embodiment five
Step is as in the first embodiment, difference is in step 3 using the gas flow that argon plasma is handled to be 150mL
min-1, other reaction conditions remain unchanged, and acquired results are close to 1 acquired results of example.
By Fig. 1 Co prepared by the present invention3S4Scanning electron microscope (SEM) photo of/TETA hydridization presoma can be clear
Find out that the nano material has the pattern of two-dimensional sheet in ground.
By Fig. 2 Co prepared by the present invention3S4PNSvacTransmission electron microscope (TEM) photo can significantly find out it is described
The sheet porous structural of nanometer sheet material.
By Fig. 3 Co prepared by the present invention3S4PNSvacHigh resolution transmission electron microscopy (HRTEM) photo can be seen that crystalline substance
Compartment is away from for 0.33nm, corresponding Co3S4(- 220) crystal face of crystal, it was demonstrated that synthesized material is strictly Co3S4PNSvac。。
By Fig. 4 Co prepared by the present invention3S4PNSvacX-ray diffraction (XRD) figure can be seen that resulting diffraction maximum can be with
The Co that card number is JCPDS:19-03673S4Crystal corresponds, it was demonstrated that synthesized material is strictly Co3S4。。
Fig. 5 is the Co prepared through the invention3S4PNSvacElectrocatalytic hydrogen evolution linear sweep voltammetry curve, wherein Co3S4
Ultrathin nanometer piece (is denoted as Co3S4It NS is prepared referring to method of the invention, specifically, Co3S4NS is that the product of step 1 passes through
Ultrasonic treatment obtains；Co3S4Nano particle (is denoted as Co3S4NP) the preparation method is as follows: weighing a certain proportion of cobalt powder and sulphur powder
It is mixed in quartz boat, for 24 hours in the lower 600 DEG C of calcinations of argon atmosphere, heating rate is 3 DEG C of min-1, ethyl alcohol is used after being cooled to room temperature
For several times, and in 60 DEG C of dry 6h with deionized water washing, Co can be obtained3S4NP；It can be seen that Co3S4PNSvacLiberation of hydrogen starting
Current potential is 18mV, and is 10mA cm in current density-1When overpotential be only 63mV, with Co3S4NS and Co3S4NP compares performance
Excellent is more.
By Fig. 6 Co prepared by the present invention3S4PNSvacElectro-catalysis analyse oxygen linear sweep voltammetry curve, it can be seen that
Co3S4PNSvacIt is 10mA cm in current density-1When overpotential be only 290mV, with Co3S4NS、Co3S4NP and ruthenic oxide (note
Make RuO2) more compared to haveing excellent performance.
By Fig. 7 Co prepared by the present invention3S4PNSvacElectro-catalysis complete solution water linear scan volt-ampere curve, it can be seen that
Co3S4PNSvacEqually show the aqueous energy of excellent complete solution.
By Co prepared by the present invention3S4PNSvacElectrocatalytic hydrogen evolution time current curve (Fig. 8), electro-catalysis analysis oxygen when it is m-
Current curve (Fig. 9) and electro-catalysis complete solution water time current curve (Figure 10) are it can be seen that Co3S4PNSvacIt all has high
Stability.
Using Co prepared by the present invention3S4PNSvacThe test equipment that material use when electro-catalysis test is model
The electrochemical workstation of CHI660D, the specific steps are as follows: by the Co of 4mg3S4PNSvacIt is logical with 5% Nafion solution of 20 μ L
It crosses ultrasound to be evenly dispersed in the deionized water of 1mL, the homogeneous dispersion of 5 μ L is taken to drip on the glass-carbon electrode that diameter is 3mm,
Working electrode is used as after drying at room temperature.Wherein, reference electrode is Hg/HgO electrode, is glass-carbon electrode to electrode, and electrolyte is
Concentration is the KOH solution of 1M.It carries out being passed through H into electrolyte respectively before electrocatalytic hydrogen evolution and analysis oxygen2And O2, make up to full
With.
Although above example combination attached drawing compares detailed description to the invention, the invention is not limited to
The Co of rich defect can be achieved according to the adjustment that summary of the invention carries out technological parameter for the specific embodiment stated3S4It is ultra-thin porous to receive
The preparation of rice sheet material, and show the performance almost the same with above-described embodiment.It should be noted that not departing from the present invention
Core in the case where, it is any it is simple deformation, modification or the present invention enlightenment under creative work can not be spent to make
Various forms of transformation each fall within protection scope of the present invention.
Claims (10)
1. a kind of Co of richness defect3S4Ultra-thin porous nanometer sheet material, it is characterised in that: there is cavernous structure, in institute in nanometer sheet
It states there are a large amount of electro catalytic activity site in the edge and hole of nanometer sheet, which is that the Co of low coordination is former
Son, the nanometer sheet with a thickness of 0.5-3nm；It prepares as steps described below:
Step 1, four hydration cobalt acetates are weighed and thioacetamide is dissolved in deionized water under ice water bath environment, until completely dissolved
Triethylene tetramine is added, wherein four hydration cobalt acetates, thioacetamide, deionized water and triethylene tetramine mass volume ratio be
(0.15-0.30): (0.05-0.08): (3.6-7.2): (7.2-14.4) extremely divides from magnetic agitation 30min at 20-25 DEG C of room temperature
It dissipates and is uniformly placed in hydrothermal reaction kettle, react 15-20h under the conditions of 150-200 DEG C, be cooled to room temperature and be centrifugated product
Deionized water and ethanol washing 3-5 times are successively used afterwards, is placed in a vacuum drying oven, and dry 4-8h, obtains under the conditions of 50-80 DEG C
Black reaction product Co3S4/ TETA hydridization presoma；
Step 2, Co step 1 obtained3S4/ TETA hydridization presoma is put into porcelain boat to be handled with argon plasma, when processing
Between be 15-30min, power 250-400W, pressure 50-100Pa, gas flow rate be 100-300mL min-1, after processing
Obtained product ethanol washing and dry 6-10h obtains the Co of rich defect under the conditions of 30-60 DEG C3S4Ultra-thin porous nanometer sheet
Material.
2. a kind of Co of rich defect according to claim 13S4Ultra-thin porous nanometer sheet material, it is characterised in that: described to receive
The thickness of rice piece is preferably 1-1.5nm.
3. a kind of Co of rich defect according to claim 13S4Ultra-thin porous nanometer sheet material, it is characterised in that: the step
Four mass volume ratios for being hydrated cobalt acetates, thioacetamide, deionized water and triethylene tetramine are preferably (0.20- in rapid 1
0.25): (0.06-0.07): (4.8-6): (9.6-12), the reaction temperature being placed in hydrothermal reaction kettle are preferably 155-165 DEG C,
Reaction time is preferably 16-18h, and the drying temperature being placed in a vacuum drying oven is preferably 60-70 DEG C, and drying time is preferably 5-
6h。
4. a kind of Co of rich defect according to claim 13S4Ultra-thin porous nanometer sheet material, it is characterised in that: the step
The time of rapid 2 plasma processing is preferably 20-25min, power 300-350W, pressure 60-80Pa, and gas flow rate is
150-200mL min-1, drying temperature is preferably 50-60 DEG C, and drying time is preferably 6-8h.
5. a kind of Co of richness defect3S4The preparation method of ultra-thin porous nanometer sheet material, it is characterised in that: as steps described below into
Row:
Step 1, four hydration cobalt acetates are weighed and thioacetamide is dissolved in deionized water under ice water bath environment, until completely dissolved
Triethylene tetramine is added, wherein four hydration cobalt acetates, thioacetamide, deionized water and triethylene tetramine mass volume ratio be
(0.15-0.30): (0.05-0.08): (3.6-7.2): (7.2-14.4) extremely divides from magnetic agitation 30min at 20-25 DEG C of room temperature
It dissipates and is uniformly placed in hydrothermal reaction kettle, react 15-20h under the conditions of 150-200 DEG C, be cooled to room temperature and be centrifugated product
Deionized water and ethanol washing 3-5 times are successively used afterwards, is placed in a vacuum drying oven, and dry 4-8h, obtains under the conditions of 50-80 DEG C
Black reaction product Co3S4/ TETA hydridization presoma；
Step 2, Co step 1 obtained3S4/ TETA hydridization presoma is put into porcelain boat to be handled with argon plasma, when processing
Between be 15-30min, power 250-400W, pressure 50-100Pa, gas flow rate be 100-300mL min-1, after processing
Obtained product ethanol washing and dry 6-10h obtains the Co of rich defect under the conditions of 30-60 DEG C3S4Ultra-thin porous nanometer sheet
Material.
6. preparation method according to claim 5, it is characterised in that: four hydration cobalt acetate, thioacetyl in step 1
The mass volume ratio of amine, deionized water and triethylene tetramine is preferably (0.20-0.25): (0.06-0.07): (4.8-6):
(9.6-12), the reaction temperature being placed in hydrothermal reaction kettle are preferably 155-165 DEG C, and the reaction time is preferably 16-18h, are placed in
Drying temperature in vacuum oven is preferably 60-70 DEG C, and drying time is preferably 5-6h.
7. preparation method according to claim 5, it is characterised in that: the time of corona treatment is preferred in step 2
For 20-25min, power 300-350W, pressure 60-80Pa, gas flow rate is 150-200mL min-1, drying temperature is preferred
It is 50-60 DEG C, drying time is preferably 6-8h.
8. a kind of Co of rich defect as described in claim 13S4Ultra-thin porous nanometer sheet material is in electrocatalytic hydrogen evolution analysis oxygen and entirely
Application in terms of Xie Shui.
9. application according to claim 8, it is characterised in that: for alkaline medium evolving hydrogen reaction, in 10mA cm-1Current density under overpotential be (60-70) mV, and have up to (1000-1100) under the overpotential of (180-200) mV
A g-1Mass activity.
10. application according to claim 8, it is characterised in that: for oxygen evolution reaction, in 10mA cm-1Electric current
Overpotential is (250-300) mV under density.
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