CN110075870A - The application of the preparation method of the pointed cadmium sulfide of spininess and its electro-catalysis reduction carbon dioxide - Google Patents
The application of the preparation method of the pointed cadmium sulfide of spininess and its electro-catalysis reduction carbon dioxide Download PDFInfo
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- CN110075870A CN110075870A CN201910470056.6A CN201910470056A CN110075870A CN 110075870 A CN110075870 A CN 110075870A CN 201910470056 A CN201910470056 A CN 201910470056A CN 110075870 A CN110075870 A CN 110075870A
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- cadmium
- spininess
- pointed
- preparation
- cadmium sulfide
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 84
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 title claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001661 cadmium Chemical class 0.000 claims abstract description 24
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 49
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical group [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 16
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 10
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 229960004424 carbon dioxide Drugs 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000012456 homogeneous solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- AHFZDLKCVOOKKC-UHFFFAOYSA-N C(=O)=[Cd] Chemical compound C(=O)=[Cd] AHFZDLKCVOOKKC-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal bicarbonate Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- 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
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/341—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 electric or magnetic fields, wave energy or particle radiation
- B01J37/344—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 electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—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 electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The present invention provides a kind of preparation methods of the pointed cadmium sulfide of spininess, comprising: mixes cadmium salt, thiocarbamide with water, is heated to 150 DEG C~180 DEG C and is reacted, obtain the pointed cadmium sulfide of spininess；The molar ratio of the cadmium salt and thiocarbamide is 1:(0.25~1).Compared with prior art, the present invention realizes the adjusting to cadmium sulfide pattern by adjusting the straightforward procedure of reactant ratio, and the tip curvature of the obtained pointed cadmium sulfide of spininess is bigger than the pure noble metal that most of electro-deposition obtain, therefore it is with fabulous carbon dioxide electrocatalysis characteristic, carbon monoxide faradic efficiency with higher and current density.
Description
Technical field
The invention belongs to carbon dioxide electroreduction technical field more particularly to a kind of preparation methods of the pointed cadmium sulfide of spininess
And its application of electro-catalysis reduction carbon dioxide.
Background technique
In recent years, a large amount of consumption of fossil fuel cause carbon dioxide (CO2) excessive emissions, accelerate global climate change
It is warm, so as to cause Global Environmental Problems such as the rising on sea level and a series of extreme weathers.It therefore need to be by carbon dioxide conversion
A kind of environment protection method is provided for valuable carbon products to cope with these challenges.
In existing carbon dioxide conversion technology, electrochemical carbon dioxide reduction technique because have reaction condition it is mild,
The advantages that reacting easily controllable and being easy to modularization is the hot technology of the current area research.In be reduced carbon dioxide
Product in, such as carbon monoxide (CO), methane (CH4), ethylene (C2H4), formates (HCOO-), acetate (CH3COO-), ethyl alcohol
(CH3CH2) and normal propyl alcohol (CH OH3CH2CH2OH in), carbon monoxide has selectivity height, the advantages of easily separation with electrolyte, together
When also can be used as chemical raw material and directly participate in commercial synthesis.Although in exploitation for being an oxidation by Carbon dioxide electrochemical reduction
A series of breakthroughs are achieved in terms of the catalyst of carbon, but in real operation, large-scale industrial application still suffers from many challenges,
Such as catalyst cost is excessively high, the problems such as product selectivity and bad long-time stability.
The activity that Carbon dioxide electrochemical reduction produces carbon monoxide used catalyst is special by several controlled morphologies and structure
The influence of sign, including high preferred orientation, particle size, element doping, crystal boundary introduce, bimetallic alloy, defect and vacancy.Its
In, the curvature adjustment of nanocatalyst is to control the common and effective mode of form, and higher curvature can lead to the concentration of electric field,
Referred to as point discharge can directly affect mass transfer and reaction process in solution.But up to the present, most of document reports make
The method that carbon dioxide electroreduction is controlled with curvature control strategy all concentrates on noble metal field, such as Au, Ag, In and Pd, and
Synthetic method used is electro-deposition mostly, and catalyst cost and electrode size are very limited.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of pointed cadmium sulfide of spininess preparation method and
Its electro-catalysis restores the application of carbon dioxide, and the Nano cadmium sulphide of this method preparation has spininess pointed, and with higher two
Carbonoxide electrocatalysis characteristic.
The present invention provides a kind of preparation methods of the pointed cadmium sulfide of spininess, comprising:
Cadmium salt, thiocarbamide are mixed with water, 150 DEG C~180 DEG C is heated to and is reacted, obtain the pointed cadmium sulfide of spininess；Institute
The molar ratio for stating cadmium salt and thiocarbamide is 1:(0.25~1).
Preferably, the cadmium salt is selected from one of cadmium sulfate, caddy and cadmium nitrate or a variety of.
Preferably, the ratio of the cadmium salt and water is 1mmol:(10~30) ml.
Preferably, the temperature of the heating is 180 DEG C；The time of the reaction is 0.5~3h.
Preferably, the heating rate of the heating is 15~20 DEG C/min.
Preferably, after reaction, 40 DEG C~60 DEG C are cooled to, is centrifuged, washing obtains Nano cadmium sulphide.
Preferably, the molar ratio of the cadmium salt and thiocarbamide is 1:0.5.
Preferably, described to be heated to be microwave heating.
Preferably, the pattern of the pointed cadmium sulfide of the spininess is that spininess is pointed, and the pointed spininess includes main needle and secondary needle
Point；The pair needle point is distributed on the needle shaft of main needle.
The present invention also provides application of the above-mentioned pointed cadmium sulfide of prepared spininess in electro-catalysis reduction carbon dioxide.
The present invention provides a kind of preparation methods of the pointed cadmium sulfide of spininess, comprising: mixes cadmium salt, thiocarbamide with water, adds
Heat is reacted to 150 DEG C~180 DEG C, and the pointed cadmium sulfide of spininess is obtained；The molar ratio of the cadmium salt and thiocarbamide be 1:(0.25~
1).Compared with prior art, the present invention realizes the adjusting to cadmium sulfide pattern by adjusting the straightforward procedure of reactant ratio,
And the tip curvature of the obtained pointed cadmium sulfide of spininess is bigger than the pure noble metal that most of electro-deposition obtain, therefore it is with pole
Good carbon dioxide electrocatalysis characteristic, carbon monoxide faradic efficiency with higher and current density.
Experiment shows that the pointed Nano cadmium sulphide of spininess prepared by the present invention has fabulous carbon dioxide electrocatalysis characteristic,
In the case that carbon monoxide faradic efficiency maintains 95% or more, carbon monoxide partial current density is up to 210mA/cm2。
Detailed description of the invention
Fig. 1 is the stereoscan photograph of the pointed Nano cadmium sulphide of spininess obtained in the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 1 obtain the pointed Nano cadmium sulphide of spininess, the vulcanization of nanometer obtained in comparative example 1~2
The X-ray crystal diffraction spectrogram of cadmium；
Fig. 3 be the embodiment of the present invention 1 obtain the pointed Nano cadmium sulphide of spininess, the vulcanization of nanometer obtained in comparative example 1~2
Cadmium carbon monoxide faradic efficiency figure under different voltages；
Fig. 4 is that the pointed Nano cadmium sulphide of spininess obtained in the embodiment of the present invention 1 uses channel electrode in various concentration
In potassium hydroxide, relative under reversible hydrogen electrode -1.2V, carbon monoxide faradic efficiency and carbon monoxide partial current density
Figure；
Fig. 5 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 2；
Fig. 6 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 3；
Fig. 7 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 4；
Fig. 8 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 5；
Fig. 9 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 6；
Figure 10 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 7；
Figure 11 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 8；
Figure 12 is the stereoscan photograph of Nano cadmium sulphide obtained in the embodiment of the present invention 9；
Figure 13 is the stereoscan photograph of Nano cadmium sulphide obtained in comparative example 1 of the present invention；
Figure 14 is the stereoscan photograph of Nano cadmium sulphide obtained in comparative example 2 of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of the pointed cadmium sulfide of spininess, comprising: mixes cadmium salt, thiocarbamide with water, adds
Heat is reacted to 150 DEG C~180 DEG C, and the pointed cadmium sulfide of spininess is obtained；The molar ratio of the cadmium salt and thiocarbamide be 1:(0.25~
1)。
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
Cadmium salt, thiocarbamide are mixed with water；The cadmium salt is preferably soluble inorganic cadmium salt, more preferably cadmium sulfate, chlorination
One of cadmium and cadmium nitrate are a variety of；The molar ratio of the cadmium salt and thiocarbamide is preferably 1:(0.25~1), more preferably 1:
(0.3~0.8) is further preferably 1:(0.4~0.6), most preferably 1:0.5；The ratio of the cadmium salt and water is preferably 1mmol:
(10~30) ml, more preferably 1mmol:(15~25) ml is further preferably 1mmol:20ml；The water is preferably deionized water.
After mixing, preferably ultrasonic disperse is uniform；The time of the ultrasound is preferably 10~50min, more preferably 20~
40min is further preferably 30min.
150 DEG C~180 DEG C are then heated to be reacted；The temperature of the heating is preferably 160 DEG C~180 DEG C, more excellent
170 DEG C~180 DEG C are selected as, is further preferably 180 DEG C；The heating rate of the heating is preferably 15~20 DEG C/min, more preferably
16~19 DEG C/min, be further preferably 18~19 DEG C/min；In the present invention, it is preferred to from room temperature to anti-in in 5~10min
Temperature is answered, from room temperature to reaction temperature more preferably in 6~9min, further preferably in 7~8min from room temperature to anti-
Temperature is answered, most preferably in 8min from room temperature to reaction temperature；The heating is preferably microwave heating；The device of the reaction
Preferably microwave reactor or hydrothermal reaction kettle；The reaction carries out in confined conditions in the present invention；The time of the reaction
Preferably 0.5~3h, more preferably 1~3h are further preferably 2~3h.Reaction time is uneven compared with the cadmium sulfide pattern being so short that,
Reaction time, which reaches 2h, can be obtained the more uniform cadmium sulfide of pattern.
After reaction, 40 DEG C~60 DEG C are preferably cooled to, 50 DEG C~60 DEG C is more preferably cooled to, is further preferably cooled to 55
DEG C, it is centrifuged, washing；The washing, which is preferably first adopted, to be washed with deionized, and then uses ethanol washing again；The deionized water washing
Number be preferably 2~4 times, more preferable 3 times；The number of the ethanol washing is preferably 2~4 times, and more preferably 3 times.
It after washing, is preferably dried in vacuo, obtains the pointed cadmium sulfide of spininess；The pattern of the pointed cadmium sulfide of spininess is preferably
Spininess is pointed, and the pointed spininess includes main needle and secondary needle point；The pair needle point is distributed on the needle shaft of main needle.
When the ratio of cadmium salt and thiocarbamide is lower (cadmium salt content is high), the cadmium sulfide of synthesis tends to form nanorod shaped
Looks；When the ratio of cadmium salt and thiocarbamide is higher, the cadmium sulfide of synthesis tends to form nano particle pattern；And work as cadmium salt and thiocarbamide
Ratio where appropriate, the Nano cadmium sulphide of the pointed pattern of spininess can be synthesized, the temperature and time of simultaneous reactions can also influence
The nanotopography of gained cadmium sulfide.
The present invention realizes the adjusting to cadmium sulfide pattern by adjusting the straightforward procedure of reactant ratio, and obtains more
The tip curvature of tip-like cadmium sulfide is bigger than the pure noble metal that most of electro-deposition obtain, therefore it is with fabulous titanium dioxide
Carbon electrocatalysis characteristic.
The present invention also provides the pointed cadmium sulfide of spininess of above method preparation answering in electro-catalysis reduction carbon dioxide
With the pointed cadmium sulfide of spininess is as carbon dioxide electro-reduction reaction catalyst wherein；Carbon dioxide reduction in the present invention
Electrolyte is preferably bicarbonate solution, more preferably alkali metal bicarbonate solution, is further preferably potassium bicarbonate solution；It is described
The concentration of bicarbonate solution is preferably 0.1~5mol/L；The product of the carbon dioxide electro-catalysis reduction is preferably an oxidation
Carbon.
In order to further illustrate the present invention, with reference to embodiments to a kind of pointed cadmium sulfide of spininess provided by the invention
The application of preparation method and its electro-catalysis reduction carbon dioxide is described in detail.
Reagent used in following embodiment is commercially available；Examples and Comparative Examples reaction carries out in confined conditions.
Embodiment 1
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
2h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain the pointed Nano cadmium sulphide of spininess.
Nano cadmium sulphide obtained in embodiment 1 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 1.
Nano cadmium sulphide obtained in embodiment 1 is analyzed using X-ray diffraction, obtains its X-ray crystal diffraction
Map, as shown in Figure 2.
The pointed Nano cadmium sulphide of 1mg spininess and 4mg carbon black are weighed, 1mL isopropanol is added, is then added the 5% of 20 μ L
Nafion solution ultrasound is evenly dispersed to catalyst, and 200 μ L dispersion liquids are sprayed on the porous carbon paper of 1cm × 0.5cm, are obtained
Electrode slice.
Electrode slice is assembled into working electrode with electrode holder, and carries out the test of carbon dioxide electroreduction in H-type electrolytic cell,
Test electrolyte is 0.1MKHCO3Solution obtains carbon monoxide faradic efficiency figure under its different voltages, as shown in Figure 3.By scheming
3 it is found that the pointed cadmium sulfide catalyst entirety carbon monoxide faradic efficiency of spininess is higher, the carbon monoxide at -1.0V vs.RHE
Faradic efficiency reaches highest 91.1 ± 2.8%.
Electrode slice is assembled into working electrode with electrode holder, and carries out the test of carbon dioxide electroreduction in H-type electrolytic cell,
Using the KHCO of various concentration3Solution is test electrolyte, obtains it relative under reversible hydrogen electrode -1.2V, carbon monoxide method
Efficiency and carbon monoxide partial current density figure are drawn, as shown in figure 4, wherein carbon monoxide electric current corresponding to column diagram is close
It spends, is then carbon monoxide faradic efficiency corresponding to point above.
Embodiment 2
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 150 DEG C is heated to from room temperature within 8 minutes, at 150 DEG C
2h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in embodiment 2 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 5.
Embodiment 3
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 160 DEG C is heated to from room temperature within 8 minutes, at 160 DEG C
2h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in embodiment 4 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 6.
Embodiment 4
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 170 DEG C is heated to from room temperature within 8 minutes, at 170 DEG C
2h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in embodiment 4 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 7.
Embodiment 5
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
0.5h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol washes 3 times, vacuum
It is dried to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in embodiment 5 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 8.
Embodiment 6
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
1h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in embodiment 6 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 9.
Embodiment 7
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.5mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
3h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain the pointed Nano cadmium sulphide of spininess.
The pointed Nano cadmium sulphide of spininess obtained in embodiment 7 is analyzed using scanning electron microscope, obtains it
Stereoscan photograph, as shown in Figure 10.
Embodiment 8
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.25mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Homogeneous solution is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
2h is reacted, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, and vacuum is dry
It is dry to obtain Nano cadmium sulphide powder.
Nano cadmium sulphide obtained in embodiment 8 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in figure 11.
Embodiment 9
First the thiocarbamide of the cadmium sulfate of 1mmol and 1mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Even solution is subsequently placed into microwave reactor (Monowave 450), is heated to 180 DEG C from room temperature within 8 minutes, anti-at 180 DEG C
2h is answered, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, vacuum drying
Obtain Nano cadmium sulphide powder.
Nano cadmium sulphide obtained in embodiment 9 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in figure 12.
Comparative example 1
First the thiocarbamide of the cadmium sulfate of 1mmol and 10mmol is dissolved in 20mL deionized water, is obtained after ultrasonic 30min
Even solution is subsequently placed into microwave reactor (Monowave 450), is heated to 180 DEG C from room temperature within 8 minutes, anti-at 180 DEG C
2h is answered, is then cooled to 55 DEG C, obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol is washed 3 times, vacuum drying
Obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in comparative example 1 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in figure 13.As shown in Figure 13, when cadmium sulfate and thiocarbamide molar ratio are 1:10, obtained Nano cadmium sulphide is inclined to
In nano particle pattern.
Nano cadmium sulphide obtained in comparative example 1 is analyzed using X-ray diffraction, obtains its X-ray crystal diffraction
Spectrogram, as shown in Figure 2.
Nano cadmium sulphide obtained in 1mg comparative example 1 and 4mg carbon black are weighed, 1mL isopropanol is added, 20 μ L are then added
5%Nafion solution ultrasound it is evenly dispersed to catalyst, 200 μ L dispersion liquids are sprayed on to the porous carbon paper of 1cm × 0.5cm
On, obtain electrode slice.
Electrode slice is assembled into working electrode with electrode holder, and carries out the test of carbon dioxide electroreduction in H-type electrolytic cell,
Test electrolyte is 0.1MKHCO3Solution obtains carbon monoxide faradic efficiency figure under its different voltages, as shown in Figure 3.
Comparative example 2
First the thiocarbamide of the cadmium sulfate of 1mmol and 0.125mmol is dissolved in 20mL deionized water, after ultrasonic 30min
It to homogeneous solution, is subsequently placed into microwave reactor (Monowave 450), 180 DEG C is heated to from room temperature within 8 minutes, at 180 DEG C
Lower reaction 2h, is then cooled to 55 DEG C, and obtained product is centrifuged, then makes to be washed with deionized water 3 times, ethyl alcohol washes 3 times, vacuum
It is dried to obtain Nano cadmium sulphide.
Nano cadmium sulphide obtained in comparative example 2 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in figure 14.As shown in Figure 14, when cadmium sulfate and thiocarbamide molar ratio are 1:0.125, obtained Nano cadmium sulphide inclines
To in nanometer rods pattern.
Nano cadmium sulphide obtained in comparative example 2 is analyzed using X-ray diffraction, obtains its X-ray crystal diffraction
Spectrogram, as shown in Figure 2.
Nano cadmium sulphide obtained in 1mg comparative example 2 and 4mg carbon black are weighed, 1mL isopropanol is added, 20 μ L are then added
5%Nafion solution ultrasound it is evenly dispersed to catalyst, 200 μ L dispersion liquids are sprayed on to the porous carbon paper of 1cm × 0.5cm
On, obtain electrode slice.
Electrode slice is assembled into working electrode with electrode holder, and carries out the test of carbon dioxide electroreduction in H-type electrolytic cell,
Test electrolyte is 0.1MKHCO3Solution obtains carbon monoxide faradic efficiency figure under its different voltages, as shown in Figure 3.
Claims (10)
1. a kind of preparation method of the pointed cadmium sulfide of spininess characterized by comprising
Cadmium salt, thiocarbamide are mixed with water, 150 DEG C~180 DEG C is heated to and is reacted, obtain the pointed cadmium sulfide of spininess；The cadmium
The molar ratio of salt and thiocarbamide is 1:(0.25~1).
2. preparation method according to claim 1, which is characterized in that the cadmium salt is selected from cadmium sulfate, caddy and nitric acid
One of cadmium is a variety of.
3. preparation method according to claim 1, which is characterized in that the ratio of the cadmium salt and water be 1mmol:(10~
30)ml。
4. preparation method according to claim 1, which is characterized in that the temperature of the heating is 180 DEG C；The reaction
Time is 0.5~3h.
5. preparation method according to claim 1, which is characterized in that the heating rate of the heating be 15~20 DEG C/
min。
6. preparation method according to claim 1, which is characterized in that after reaction, 40 DEG C~60 DEG C are cooled to, from
The heart, washing, obtains Nano cadmium sulphide.
7. preparation method according to claim 1, which is characterized in that the molar ratio of the cadmium salt and thiocarbamide is 1:0.5.
8. preparation method according to claim 1, which is characterized in that described to be heated to be microwave heating.
9. preparation method according to claim 1, which is characterized in that the pattern of the pointed cadmium sulfide of spininess is Multi-tip
Shape, the pointed spininess includes main needle and secondary needle point；The pair needle point is distributed on the needle shaft of main needle.
10. the pointed cadmium sulfide of spininess prepared by claim 1~9 any one answering in electro-catalysis reduction carbon dioxide
With.
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