CN109759120A - A kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application - Google Patents
A kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application Download PDFInfo
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- CN109759120A CN109759120A CN201910171517.XA CN201910171517A CN109759120A CN 109759120 A CN109759120 A CN 109759120A CN 201910171517 A CN201910171517 A CN 201910171517A CN 109759120 A CN109759120 A CN 109759120A
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- cobaltous selenide
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 246
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 126
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 120
- -1 cobaltous selenide Chemical class 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 52
- 239000010941 cobalt Substances 0.000 claims abstract description 52
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011669 selenium Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 40
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 19
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 229940091258 selenium supplement Drugs 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical group [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 8
- 229960001471 sodium selenite Drugs 0.000 claims description 8
- 235000015921 sodium selenite Nutrition 0.000 claims description 8
- 239000011781 sodium selenite Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 235000013495 cobalt Nutrition 0.000 description 46
- 239000000047 product Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- 239000007787 solid Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application, belong to water electrolysis hydrogen production catalyst technical field.Preparation method provided by the invention includes the following steps: that (1) mixes cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine, carries out solvent thermal reaction, obtains nitrogen, nickel co-doped selenizing cobalt precursor；(2) nitrogen, nickel co-doped selenizing cobalt precursor are washed and is dried, obtain nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece.The above method does not need to reduce costs using noble metal, and preparation process is simply easy to implement.The experimental results showed that above-mentioned preparation method obtain nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece in 1M KOH solution during water electrolysis hydrogen production, when current density is 10mAcm‑2When, overvoltage 220mV, hence it is evident that adulterate cobaltous selenide lower than cobaltous selenide, N doping cobaltous selenide and nickel, there is excellent electrocatalysis characteristic.
Description
Technical field
The present invention relates to water electrolysis hydrogen production catalyst technical field more particularly to a kind of nitrogen, nickel co-doped cobaltous selenide are ultra-thin
Nanometer sheet and its preparation method and application.
Background technique
Fossil energy problem is more and more severeer since 21 century, since fossil fuel reserves are limited, as the mankind do not turn off
Utilization is adopted, the exhaustion of fossil energy will be inevitable.In view of the above problem, seek the novel cleaning of one kind, renewable energy
It is the direction of energy development from now on.Since water resource is quite abundant on the earth, people gradually pay attention to the research in hydrolysis field, lead to
Crossing water decomposition is hydrogen and oxygen, the energy of light or electric form can be converted to chemical energy and stored.Electrochemical decomposition
Water without other by-products because generate in the whole process, and clean and environmental protection is pollution-free, therefore water electrolysis hydrogen production has obtained greatly
Concern, and existing a large amount of research.Water electrolysis hydrogen production is needed using catalyst, i.e. the evolving hydrogen reaction catalyst and anode of cathode
Oxygen evolution reaction catalysts, performance is preferably at present and the catalyst that is most widely used is that platinum (Pt), iridium (Ir), ruthenium (Ru) etc. are expensive
Metallic catalyst, but this kind of catalyst is expensive, scarcity of resources, thus find it is a kind of efficiently, stablize, be cheap alternative
Electrocatalysis material is particularly important for being electrolysed aqueous systems on a large scale.
Transition-metal dichalcogenide (TMCs) is resourceful because its is at low cost, HER performance relatively preferably increasingly by
The concern of researcher.As typical TMC material, cobaltous selenide can promote charge because it is with excellent metallicity
Quickly transmitted on the surface of electrode and catalyst, and be considered as enrich, inexpensively, efficiently Electrocatalytic Activity for Hydrogen Evolution Reaction agent.Currently, having very
More researchers have done correlative study to the preparation of cobaltous selenide and electrocatalysis characteristic, and research focuses primarily upon the doping to cobaltous selenide.
For example, (the 0.85 Se and N-doped carbon via one- of In situ coupling of Co such as Tao Meng
step selenization of metal–organic frameworks as a trifunctional catalyst for
Overall water splitting and Zn-air batteries [J], Meng T, Qin J, Wang S, et al.,
Journal of Materials Chemistry A, 2017,5 (15)) it is prepared for compound selenizing cobalt nanocrystal body and N- doping
Carbon, improve cobaltous selenide electro catalytic activity to a certain extent, but this method process is many and diverse, be not suitable for industrialized production and answering
With；(the Engineering the Electrical Conductivity of Lamellar Silver-Doped such as Zhao X
Cobalt (II) Selenide Nanobelts for Enhanced Oxygen Evolution [J], Zhao X, Zhang H,
Yan Y, et al, Angewandte Chemie, 2017,56 (1)) based on two-dimensional layer cobaltous selenide nanobelt, by from
Sub- exchange process introduces micro silver ion, has obtained the cobaltous selenide nanocatalyst of silver ion doping, and this method also can be improved selenium
Change cobalt electro catalytic activity, but this method is doped with metallic silver, expensive, higher cost, be also not suitable for industrialized production and
Using.
Summary of the invention
The object of the present invention is to provide a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and preparation method thereof and answer
With nitrogen that preparation method provided by the invention obtains, nickel co-doped cobaltous selenide ultrathin nanometer piece have that electro catalytic activity is high, cost
Cheap advantage, and the preparation method is easily operated, is suitble to industrialized production and application.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides the preparation methods of a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece, include the following steps:
(1) cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine are mixed, carries out solvent thermal reaction, obtains nitrogen, nickel
Codope selenizing cobalt precursor；
(2) nitrogen, nickel co-doped selenizing cobalt precursor are washed and is dried, obtain nitrogen, nickel co-doped cobaltous selenide
Ultrathin nanometer piece.
Preferably, the solvent thermal reaction is carried out in confined condition；The temperature of the solvent thermal reaction is 160~220 DEG C,
Time be 12~for 24 hours.
Preferably, according to cobalt atom, selenium atom, nickle atom and nitrogen-atoms meter, the cobalt source, selenium source, nickel source and nitrogen source
Molar ratio is 0.8~0.9:1:0.1~0.2:1~3.
Preferably, the amount of the substance of selenium atom and the volume of water, the volume ratio of diethylenetriamine are 1mol in the selenium source:
10~15mL:20~30mL.
Preferably, the washing includes that the alcohol successively carried out is washed and washed.
Preferably, the nickel source is at least one of nickel nitrate, nickel chloride and nickel acetate.
Preferably, the nitrogen source is at least one of dicyanodiamine and urea.
Preferably, the selenium source is sodium selenite；The cobalt source is four acetate hydrate cobalts.
Nitrogen, the nickel co-doped cobaltous selenide obtained the present invention also provides preparation method described in a kind of above-mentioned technical proposal is super
Thin nanometer sheet, the nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece lamellar spacing be less than 10nm.
The nitrogen that obtains the present invention also provides the preparation method described in above-mentioned technical proposal, nickel co-doped cobaltous selenide is ultra-thin receives
Nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece answering as water electrolysis hydrogen production catalyst described in rice piece or above-mentioned technical proposal
With.
The present invention provides the preparation methods of a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece, include the following steps:
(1) cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine are mixed, carries out solvent thermal reaction, obtains nitrogen, nickel co-doped selenium
Change cobalt precursor；(2) nitrogen, nickel co-doped selenizing cobalt precursor are washed and is dried, obtain nitrogen, nickel co-doped selenizing
Cobalt ultrathin nanometer piece.The present invention obtains nitrogen, nickel co-doped selenizing cobalt precursor by solvent thermal reaction, in solvent thermal reaction process
In, cobalt source, selenium source reaction generate cobaltous selenide, and the nickle atom in nickel source replaces the cobalt atom in the cobaltous selenide of part, the nitrogen in nitrogen source
Atom replaces the selenium atom in the cobaltous selenide of part, and the amino guidance metal cobaltous selenide in diethylenetriamine is arranged as lamellar structure；
The present invention is by the anionic impurity and diethylenetriamine in nitrogen, the washed removal presoma of nickel co-doped selenizing cobalt precursor, so
After dry, nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece can be obtained.The above method does not need to reduce into using noble metal
This, and preparation process is simply easy to implement.The experimental results showed that nitrogen, the nickel co-doped cobaltous selenide that above-mentioned preparation method obtains are super
Thin nanometer sheet is in 1M KOH solution during water electrolysis hydrogen production, when current density is 10mAcm-2When, overvoltage is
220mV, hence it is evident that adulterate cobaltous selenide lower than cobaltous selenide, N doping cobaltous selenide and nickel, there is excellent electrocatalysis characteristic.
Detailed description of the invention
The XRD diagram of 1 gained nitrogen of Fig. 1 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The SEM figure and TEM figure of 1 gained nitrogen of Fig. 2 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The SEM figure and TEM figure of 2 gained nitrogen of Fig. 3 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The XPS figure of 2 gained nitrogen of Fig. 4 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The SEM figure and TEM figure of 3 gained nitrogen of Fig. 5 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The SEM figure and TEM figure of 4 gained nitrogen of Fig. 6 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The SEM figure and TEM figure of 5 gained nitrogen of Fig. 7 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The AC impedance figure of 1 products obtained therefrom of Fig. 8 embodiment 5 and comparative example；
The polarization curve of Fig. 9 embodiment 5 and 1~3 products obtained therefrom of the comparative example water electrolysis hydrogen production in 1M KOH solution；
The cyclical stability test chart of 5 gained nitrogen of Figure 10 embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece；
The cyclic voltammetric of Figure 11 embodiment 5 and 1~3 products obtained therefrom of the comparative example water electrolysis hydrogen production in 1M KOH solution is bent
Line；
Figure 12 embodiment 5 and 1~3 products obtained therefrom of comparative example in 1M KOH solution the capacitance current of water electrolysis hydrogen production with sweep
The relational graph of speed.
Specific embodiment
The present invention provides the preparation methods of a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece, include the following steps:
(1) cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine are mixed, carries out solvent thermal reaction, obtains nitrogen, nickel
Codope selenizing cobalt precursor；
(2) nitrogen, nickel co-doped selenizing cobalt precursor are washed and is dried, obtain nitrogen, nickel co-doped cobaltous selenide
Ultrathin nanometer piece.
The present invention by cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine mix, carry out solvent thermal reaction, obtain nitrogen,
Nickel co-doped selenizing cobalt precursor.In the present invention, during solvent thermal reaction, cobalt source, selenium source reaction generate cobaltous selenide, nickel source
In nickle atom replace the cobalt atom in the cobaltous selenide of part, the nitrogen-atoms in nitrogen source replaces the selenium atom in the cobaltous selenide of part, two
Amino guidance metal cobaltous selenide in ethylene triamine is arranged as lamellar structure, plays the role of soft template.
In the present invention, the selenium source is preferably sodium selenite；The cobalt source is preferably four acetate hydrate cobalts；The nickel source
Preferably at least one of nickel nitrate, nickel chloride and nickel acetate；The nitrogen source be preferably in dicyanodiamine and urea at least
It is a kind of.
In the present invention, according to cobalt atom, selenium atom, nickle atom and nitrogen-atoms meter, the cobalt source, selenium source, nickel source and nitrogen
The molar ratio in source is preferably 0.8~0.9:1:0.1~0.2:1~3.
In the present invention, the amount of the substance of selenium atom and the volume of water, the volume ratio of diethylenetriamine are excellent in the selenium source
It is selected as 1mol:10~15mL:20~30mL.
The present invention is not particularly limited the order by merging of the cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine,
It can obtain uniformly mixed feed liquid.In embodiments of the present invention, cobalt source, selenium source, nickel source, nitrogen source are preferably dissolved in water
In, diethylenetriamine is then added and is uniformly mixed；The mode of the dissolution preferably stirs assisting ultrasonic, the mixed mode
Preferably stir.
In the present invention, the solvent thermal reaction is preferably carried out in confined condition；The temperature of the solvent thermal reaction is preferred
It is 160~220 DEG C, more preferably 180~220 DEG C；The time of the solvent thermal reaction is preferably 12~for 24 hours, more preferably 15
~20h.
After the completion of solvent thermal reaction, feed liquid obtained by solvent thermal reaction is preferably cooled to room temperature by the present invention, then solid-liquid point
From obtaining nitrogen, nickel co-doped selenizing cobalt precursor.
The present invention is not particularly limited the mode of the separation of solid and liquid, can separate solid.In this hair
In bright embodiment, after the feed liquid stratification for preferably obtaining solvent thermal reaction, supernatant liquid is poured out, obtains solid, i.e. nitrogen, nickel
Codope selenizing cobalt precursor.
After obtaining nitrogen, nickel co-doped selenizing cobalt precursor, the present invention carries out the nitrogen, nickel co-doped selenizing cobalt precursor
Washing and drying, obtain nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece.
In the present invention, the washing includes that the alcohol successively carried out is washed and washed；The mode that the alcohol is washed and washed is preferred
For centrifuge washing.In the present invention, the alcohol, which is washed, can remove diethylenetriamine；The washing can remove water-solubility impurity
(such as unreacted selenium source, nickel source and cobalt source).
In the present invention, it is preferably dehydrated alcohol that the alcohol, which washes washing lotion used,；Washing lotion used in the washing is preferably distilled
Water；The number that the alcohol is washed and washed independently is 3~8 times.
The dosage that the present invention washed and washed washing lotion used to the alcohol is not particularly limited, and can submerge nitrogen, nickel co-doped
Selenizing cobalt precursor.
In the present invention, the drying is preferably dried in vacuo；The temperature of the drying is preferably 60~100 DEG C, more excellent
It is selected as 75~85 DEG C；The time of the drying is preferably 6~for 24 hours, more preferably 12~20h.
Nitrogen, the nickel co-doped cobaltous selenide obtained the present invention also provides preparation method described in a kind of above-mentioned technical proposal is super
Thin nanometer sheet, the nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece lamellar spacing be less than 10nm.
Nitrogen, the nickel co-doped cobaltous selenide obtained the present invention also provides preparation method described in a kind of above-mentioned technical proposal is super
Nitrogen described in thin nanometer sheet or above-mentioned technical proposal, nickel co-doped cobaltous selenide ultrathin nanometer piece are as water electrolysis hydrogen production catalyst
Using.
The present invention is not particularly limited the specific method of the application, according to the side of conventional water electrolysis hydrogen production catalyst
Method use.
Below with reference to embodiment to a kind of nitrogen provided by the invention, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation side
Method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Tetra- acetate hydrate cobalt of 0.200g, 0.173g sodium selenite, 0.037g nickel nitrate and 0.84g dicyanodiamine are successively added
Enter into beaker, add 10mL water, after being completely dissolved to solid particle, 20mL diethylenetriamine, magnetic is added in ultrasonic 5min
Power stirs 20min, is subsequently poured into the reaction kettle of 50mL and seals, reaction kettle is placed in crucible furnace, the isothermal reaction at 160 DEG C
12h；After the reaction was completed, reaction kettle is naturally cooled into room temperature, pours out supernatant liquid, obtain solid；The solid is successively used
Dehydrated alcohol and distilled water centrifuge washing 3 times, be subsequently placed in vacuum oven 60 DEG C of vacuum drying for 24 hours, it is total to obtain nitrogen, nickel
Adulterate cobaltous selenide ultrathin nanometer piece.
The XRD diagram of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is tested, as a result as shown in Figure 1.Fig. 1
In 2 angles θ be 33.264 °, 44.736 °, 50.562 °, 60.387 °, 61.866 ° and 69.919 ° of position, respectively correspond
Co0.85The characteristic diffraction peak of (101), (102), (110), (103), (112) and (202) crystal face of Se, and the spectrogram compared with
Co0.85The standard card of Se offsets by the right certain angle, illustrates that catalyst obtained by the present embodiment is Ni, N-Co0.85Se is (i.e.
Nitrogen, nickel co-doped cobaltous selenide), and due to the doping of Ni and N, so that peak corresponding to cobaltous selenide after doping has occurred partially
It moves.
The pattern of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is characterized, as a result such as Fig. 2 institute
Show, left side a is SEM figure, and right side b is TEM figure.As shown in Figure 2, the present embodiment products therefrom is flaky nanometer structure and nanometer sheet
Very thin, through measuring, the nanometer sheet lamellar spacing of the present embodiment products therefrom is less than 10nm.
The x-ray photon energy spectrum analysis of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece obtained by the present embodiment is tested, as a result table
There are the characteristic peaks of nickel, nitrogen, selenium and cobalt in bright product, it was demonstrated that nickel, nitrogen are successfully doped in cobaltous selenide.
Embodiment 2
Successively by tetra- acetate hydrate cobalt of 0.224g, 0.173g sodium selenite, 0.018g nickel nitrate and 0.168g dicyanodiamine
It being added in beaker, adds 13mL water, after being completely dissolved to solid particle, 26mL diethylenetriamine is added in ultrasonic 5min,
Magnetic agitation 25min, is subsequently poured into the reaction kettle of 50mL and seals, and reaction kettle is placed in crucible furnace, and constant temperature is anti-at 200 DEG C
Answer 18h；After the reaction was completed, reaction kettle is naturally cooled into room temperature, pours out supernatant liquid, obtain solid；Successively by the solid
With dehydrated alcohol and distilled water centrifuge washing 5 times, it is subsequently placed in vacuum oven in 80 DEG C of vacuum drying 12h, obtains nitrogen, nickel
Codope cobaltous selenide ultrathin nanometer piece.
The XRD diagram of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is tested, it is as a result consistent with Fig. 1.
The pattern of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is characterized, as a result such as Fig. 3 institute
Show, left side a is SEM figure, and right side b is TEM figure.From the figure 3, it may be seen that the present embodiment products therefrom is flaky nanometer structure and nanometer sheet
Very thin, through measuring, the nanometer sheet lamellar spacing of the present embodiment products therefrom is less than 10nm.
The x-ray photon energy spectrum analysis of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece obtained by the present embodiment is tested, as a result such as
Shown in Fig. 4, wherein a is nitrogen spectrogram, and b is nickel spectrogram, and c is cobalt spectrogram, and d is selenium spectrogram.The combination of N1s known to from figure a nitrogen spectrum
It can be 399.4eV；Scheming b is XPS spectrum corresponding to Ni2p, respectively corresponds Ni2p in conjunction with energy 856.0eV and 873.6eV3/2With
Ni2p1/2Signal peak, corresponding Ni element valence is respectively Ni2+And Ni3+；The cobalt spectrum of figure c corresponds to Co2p3/2And Co2p1/2(d) it is
Diffraction maximum at the XPS spectrum figure of Co2p, 780.9eV and 797.2eV corresponds to the signal peak of Co2p1/2,778.5eV and
793.5eV corresponds to Co2p3/2Signal peak, show Ni, N-Co0.85Se catalyst had not only contained the cobalt of positive divalent, but also contained positive three
The cobalt of valence, this shows nitrogen phosphorus codope cobaltous selenide (N, Ni-Co0.85Se Co is existed simultaneously in)2+And Co3+Two kinds of valence states；Scheming d is selenium
Spectrogram, the corresponding combination of Se3d can be 54.5eV, show that there are Se in catalyst2-.By above- mentioned information it is found that existing in product
Nickel, nitrogen, selenium and cobalt characteristic peak, it was demonstrated that nickel, nitrogen are successfully doped in cobaltous selenide.
Embodiment 3
Tetra- acetate hydrate cobalt of 0.200g, 0.173g sodium selenite, 0.05g nickel acetate and 0.180g urea are added sequentially to
In beaker, 20mL water is added, after being completely dissolved to solid particle, 30mL diethylenetriamine, magnetic force is added in ultrasonic 10min
30min is stirred, is subsequently poured into the reaction kettle of 50mL and seals, reaction kettle is placed in crucible furnace, the isothermal reaction at 220 DEG C
24h；After the reaction was completed, reaction kettle is naturally cooled into room temperature, pours out supernatant liquid, obtain solid；The solid is successively used
Dehydrated alcohol and distilled water centrifuge washing 6 times, are subsequently placed in vacuum oven in 70 DEG C of vacuum drying 6h, it is total to obtain nitrogen, nickel
Adulterate cobaltous selenide ultrathin nanometer piece.
The XRD diagram of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is tested, it is as a result consistent with Fig. 1.
The pattern of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is characterized, as a result such as Fig. 5 institute
Show, wherein left side a is SEM figure, and right side b is TEM figure, and through measuring, the nanometer sheet lamellar spacing of the present embodiment products therefrom is less than
10nm。
Test the present embodiment obtained by nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece x-ray photon energy spectrum analysis, as a result with
Fig. 4 is consistent, shows that there are the characteristic peaks of nickel, nitrogen, selenium and cobalt in product, it was demonstrated that nickel, nitrogen are successfully doped in cobaltous selenide.
Embodiment 4
Tetra- acetate hydrate cobalt of 0.224g, 0.173g sodium selenite, 0.02g nickel nitrate and 0.084g dicyanodiamine are successively added
Entering into beaker, adds 13mL water, after being completely dissolved to solid particle, 26mL diethylenetriamine is added in ultrasonic 10min,
Magnetic agitation 30min, is subsequently poured into the reaction kettle of 50mL and seals, and reaction kettle is placed in crucible furnace, and constant temperature is anti-at 220 DEG C
Answer 16h；After the reaction was completed, reaction kettle is naturally cooled into room temperature, pours out supernatant liquid, obtain solid；Successively by the solid
With dehydrated alcohol and distilled water centrifuge washing 6 times, it is subsequently placed in vacuum oven in 70 DEG C of vacuum drying 12h, obtains nitrogen, nickel
Codope cobaltous selenide ultrathin nanometer piece.
The XRD diagram of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is tested, it is as a result consistent with Fig. 1.
The pattern of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is characterized, as a result such as Fig. 6 institute
Show, wherein left side a is SEM figure, and right side b is TEM figure, and through measuring, the nanometer sheet lamellar spacing of the present embodiment products therefrom is less than
10nm。
Test the present embodiment obtained by nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece x-ray photon energy spectrum analysis, as a result with
Fig. 4 is consistent, shows that there are the characteristic peaks of nickel, nitrogen, selenium and cobalt in product, it was demonstrated that nickel, nitrogen are successfully doped in cobaltous selenide.
Embodiment 5
Successively by tetra- acetate hydrate cobalt of 0.224g, 0.173g sodium selenite, 0.026g nickel chloride and 0.168g dicyanodiamine
It is added in beaker, adds 13mL water, after being completely dissolved to solid particle, 26mL divinyl three is added in ultrasonic 15min
Amine, magnetic agitation 30min, is subsequently poured into the reaction kettle of 50mL and seals, and reaction kettle is placed in crucible furnace, permanent at 220 DEG C
Temperature reaction 16h；After the reaction was completed, reaction kettle is naturally cooled into room temperature, pours out supernatant liquid, obtain solid；By the solid
Dehydrated alcohol and distilled water centrifuge washing 6 times are successively used, is subsequently placed in vacuum oven in 70 DEG C of vacuum drying 12h, obtains
Nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece.
The XRD diagram of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is tested, it is as a result consistent with Fig. 1.
The pattern of nitrogen obtained by the present embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece is characterized, as a result such as Fig. 7 institute
Show, wherein left side a is SEM figure, and right side b is TEM figure, and through measuring, the nanometer sheet lamellar spacing of the present embodiment products therefrom is small
In 10nm.
Test the present embodiment obtained by nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece x-ray photon energy spectrum analysis, as a result with
Fig. 4 is consistent, shows that there are the characteristic peaks of nickel, nitrogen, selenium and cobalt in product, it was demonstrated that nickel, nitrogen are successfully doped in cobaltous selenide.
Comparative example 1
According to the preparation method of embodiment 5, it is added without nickel chloride and dicyanodiamine, prepares cobaltous selenide.
Comparative example 2
According to the preparation method of embodiment 5, it is added without dicyanodiamine, prepares the cobaltous selenide of nickel doping.
Comparative example 3
According to the preparation method of embodiment 5, it is added without nickel chloride, prepares the cobaltous selenide of N doping.
Testing impedance is carried out in 1M KOH solution to embodiment 5 and 1 products obtained therefrom of comparative example, as a result as shown in figure 8, its
Middle Co0.85Se is 1 gained cobaltous selenide of comparative example, N, Ni-Co0.85Se, which is 5 gained nitrogen of embodiment, nickel co-doped cobaltous selenide is ultra-thin receives
Rice piece.Curve by high frequency region semicircle and low frequency range rectilinear(-al), respectively correspond load transfer and mass transport process, comparison diagram medium-high frequency
The size of half circular diameter in area, hence it is evident that be Ni, N-Co0.85Se<Co0.85Se illustrates that the load transfer resistance after doping is significantly less than not
Doping, it was demonstrated that improve the electron conduction of cobaltous selenide after doping nickel and nitrogen really.
Detect embodiment 5 and 1~3 products obtained therefrom of comparative example as cathod catalyst the water electrolysis hydrogen production in 1M KOH solution
Polarization curve, as a result as shown in Figure 9.When current density is 10mAcm-2When undoped cobaltous selenide (Co0.85Se is compared
1 products therefrom of example), the mono- cobaltous selenide (Ni-Co adulterated of Ni0.85Se, i.e. 2 products therefrom of comparative example), the mono- cobaltous selenide adulterated of N
(N-Co0.85Se, i.e. 3 products therefrom of comparative example) and Ni, N codope cobaltous selenide (Ni, N-Co0.85Se is produced obtained by embodiment 5
Object) corresponding overvoltage is respectively 340mV, 255mV, 260mV, 220mV, nitrogen, nickel co-doped cobaltous selenide (Ni, N-
Co0.85Se the electrochemistry overpotential of hydrogen evolution corresponding to) is significantly less than other samples, illustrates nitrogen, the electricity of nickel co-doped cobaltous selenide is urged
It is more excellent to change activity.
The cyclical stability for detecting 5 gained nitrogen of embodiment, nickel co-doped cobaltous selenide ultrathin nanometer piece, as a result such as Figure 10 institute
Show.By 1000 circle cyclic voltammetric stability tests after, nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece polarization curve not
There is too apparent variation, when current density is 10mAcm-2When, before and after loop test needed for voltage only increase 5mV, explanation
Nitrogen provided by the invention, nickel co-doped cobaltous selenide ultrathin nanometer piece have excellent stability.
Detection embodiment 5 and 1~3 products obtained therefrom of the comparative example different cyclic voltammetry curves swept under speed in 1M KOH solution
(sweeping speed is 20,40,60,80,100,120,140,160mV/s), as shown in figure 11, wherein a is following for 1 products obtained therefrom of comparative example
Ring volt-ampere curve, b are the cyclic voltammetry curve of 2 products obtained therefrom of comparative example, and c is the cyclic voltammetry curve of 3 products obtained therefrom of comparative example,
D is the cyclic voltammetry curve of 5 products obtained therefrom of embodiment.The capacitor of 1~3 products obtained therefrom of embodiment 5 and comparative example is obtained by Figure 11
Electric current and the relationship for sweeping speed, as shown in figure 12, wherein Co0.85Se is 1 products therefrom of comparative example, Ni-Co0.85Se is 2 institute of comparative example
Obtain product, N-Co0.85Se is 3 products therefrom of comparative example, Ni, N-Co0.85Se is 5 products therefrom of embodiment.Current density and scanning
Rate is in a linear relationship, and slope is electric double layer capacitance, therefore, as shown in Figure 12,5 > comparative example of embodiment, 2 > comparative example, 3 >
Comparative example 1.Since electric double layer capacitance is proportional to the specific surface area active of elctro-catalyst, nickel nitrogen is total from the above results
The specific surface area active of the cobaltous selenide ultrathin nanometer piece of doping mixes than cobaltous selenide, the nitrogen list that undoped cobaltous selenide, nickel list adulterate
Miscellaneous cobaltous selenide is bigger, can preferably utilize active site, is conducive to enhance electro catalytic activity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece, which comprises the steps of:
(1) cobalt source, selenium source, nickel source, nitrogen source, water and diethylenetriamine are mixed, carries out solvent thermal reaction, obtains nitrogen, nickel is co-doped with
Miscellaneous selenizing cobalt precursor；
(2) nitrogen, nickel co-doped selenizing cobalt precursor are washed and is dried, it is ultra-thin to obtain nitrogen, nickel co-doped cobaltous selenide
Nanometer sheet.
2. preparation method as described in claim 1, which is characterized in that the solvent thermal reaction is carried out in confined condition；It is described
The temperature of solvent thermal reaction be 160~220 DEG C, the time be 12~for 24 hours.
3. preparation method as described in claim 1, which is characterized in that according to cobalt atom, selenium atom, nickle atom and nitrogen-atoms
Meter, the cobalt source, selenium source, nickel source and nitrogen source molar ratio be 0.8~0.9:1:0.1~0.2:1~3.
4. preparation method as claimed in claim 1 or 3, which is characterized in that the amount and water of the substance of selenium atom in the selenium source
Volume, the volume ratio of diethylenetriamine be 1mol:10~15mL:20~30mL.
5. preparation method as described in claim 1, which is characterized in that the washing includes that the alcohol successively carried out is washed and washed.
6. preparation method as described in claim 1, which is characterized in that the nickel source is in nickel nitrate, nickel chloride and nickel acetate
At least one.
7. preparation method as described in claim 1, which is characterized in that the nitrogen source is at least one in dicyanodiamine and urea
Kind.
8. preparation method as described in claim 1, which is characterized in that the selenium source is sodium selenite；The cobalt source is four water
Close cobalt acetate.
9. a kind of nitrogen that preparation method according to any one of claims 1 to 8 obtains, nickel co-doped cobaltous selenide ultrathin nanometer piece,
The nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece lamellar spacing be less than 10nm.
10. the nitrogen that preparation method according to any one of claims 1 to 8 obtains, nickel co-doped cobaltous selenide ultrathin nanometer piece or power
Benefit require 9 described in the application of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece as water electrolysis hydrogen production catalyst.
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