CN108380229B - A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent - Google Patents
A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent Download PDFInfo
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- CN108380229B CN108380229B CN201810380491.5A CN201810380491A CN108380229B CN 108380229 B CN108380229 B CN 108380229B CN 201810380491 A CN201810380491 A CN 201810380491A CN 108380229 B CN108380229 B CN 108380229B
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- cobalt molybdate
- molybdate
- cobalt
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- hydrogen evolution
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- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 46
- 239000011574 phosphorus Substances 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims abstract description 23
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 14
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000008240 homogeneous mixture Substances 0.000 claims abstract description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000010348 incorporation Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 8
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- GCFSKCZBSOKYLJ-UHFFFAOYSA-N [Na].O[PH2]=O Chemical group [Na].O[PH2]=O GCFSKCZBSOKYLJ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910015421 Mo2N Inorganic materials 0.000 description 1
- 229910003218 Ni3N Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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 the preparation methods and product of a kind of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent, belong to electrocatalytic hydrogen evolution technical field, this method comprises the following steps: (1) cobalt chloride hexahydrate, Ammonium Molybdate Tetrahydrate and urea being added separately in deionized water, stirring forms homogeneous mixture solotion；(2) solution prepared by step (1) is transferred in reaction kettle, conductive substrates is added, hydro-thermal reaction obtains β phase cobalt molybdate persursor material；(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, obtains β phase cobalt molybdate；(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is sodium hypophosphite, obtains the phosphorus doping cobalt molybdate.This method is by the amount and pyrolysis time of control sodium hypophosphite, and successfully by the lattice of P elements incorporation cobalt molybdate, the catalyst of preparation shows efficient liberation of hydrogen ability in alkaline solution.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution technical fields, more particularly, to a kind of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction
Preparation method of agent and products thereof.
Background technique
Growing energy demand and the natural environment constantly deteriorated make the mankind, and there is an urgent need to not depending on of one kind
The source of the physical efficiency containing energy of stone fuel, rich reserves.Hydrogen energy density with higher (140MJ kg-1), excellent combustibility,
The advantages that cleanliness without any pollution, it is considered to be ideal energy carrier.Electrolysis method is a kind of cleaning, efficient big using water as raw material
The method that scale prepares high-purity hydrogen, however the 4% of the total hydrogen manufacturing amount of hydrogen Zhan prepared at present by this method.Restrict the skill
One key problem of art large-scale application is that the dynamics of hydrogen evolution reaction is slow, therefore usually needs the yin in electrolytic cell
Catalyst is added with the quick progress of driving a reaction in pole.A large amount of experiment and theoretical calculation confirm most effective Electrocatalytic Activity for Hydrogen Evolution Reaction
Agent is noble metal platinum (Pt), but its fancy price and low amount of storage limit such catalyst and lead in electrolysis water hydrogen manufacturing
In domain practical application (see Xing Cheng, Yonghe Li, Lirong Zheng, et al., Highly active,
stable oxidized platinum clusters as electrocatalysts for the hydrogen
evolution reaction,Energy&Environmental Science,2017,10,2450).In conclusion to push
Electrolysis method becomes mainstream hydrogen producing technology, and exploitation design is efficient, the base metal elctro-catalyst of high stability is extremely urgent.
Develop by last decade, there are various base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent to be mined out, such as transition
Metal phosphide (CoP, FeP, NiP etc.), sulfide (MoS2, CoS, NiS etc.), carbide (Mo2C, VC, WC etc.), nitride
(WN、Mo2N、Ni3N etc.), boride (Co2B、FeB2, NiB etc.) etc. (see Isolda Roger, Michael A.Shipman,
Mark D.Symes,Earth-abundant catalysts for electrochemical and
photoelectrochemical water splitting,Nature Reviews Chemistry,2017,1,0003).To the greatest extent
It manages these materials and shows inspirer catalytic effect, but preparation process is relative complex, is also unavoidably had using various
Malicious harmful substance is not suitable for large-scale industrial production.Transition metal oxide, as above-mentioned phosphide, sulfide, carbonization
The persursor material of object, nitride, boride etc., since the advantages that abundant raw materials, preparation simplicity has been applied to various energy
In source conversion and memory device, such as lithium ion battery, supercapacitor, solar battery, but directly it is applied to electricity
Catalyzing manufacturing of hydrogen rarely has report.The liberation of hydrogen ability of transition metal oxide is weaker, and overpotential of hydrogen evolution is generally wanted in alkaline solution
More than 250mV, with noble metal platinum at a distance of too big.Its weaker catalytic activity for hydrogen evolution is mainly as caused by two aspect reasons one
Be transition metal oxide electric conductivity it is poor, second is that adsorption capacity of the hydrogen atom on transition metal oxide surface is weaker, because
This intrinsic catalytic activity is very low.Although people have developed the liberation of hydrogen that various control measures attempt to be promoted transition metal oxide
Can, such as pattern variation, the introducing of Lacking oxygen, lithium ion insertion, it is unfortunately, most of all unsuccessfully to accuse
Eventually.
In this context, develop new method to go to change the electronic structure of transition metal oxide, it is intended to improve it and lead
Electrical property and latent active, and then realize its efficient precipitation hydrogen, it will the very big extensive use for pushing electrolysis method in hydrogen preparation field.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of phosphorus doping cobalt molybdate liberation of hydrogen electricity to urge
The preparation method of agent, by reducing sodium hypophosphite dosage and shortening phosphating time, successfully by P elements incorporation cobalt molybdate
In lattice, significant increase catalytic hydrogen evolution performance of the cobalt molybdate in alkaline solution, overpotential of hydrogen evolution is only than precious metals pt/C
Small 100mV, therefore can effectively reduce electrolysis water hydrogen manufacturing cost.
To achieve the above object, according to one aspect of the present invention, a kind of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction is provided
The preparation method of agent, this method comprises the following steps: (1) being separately added into cobalt chloride hexahydrate, Ammonium Molybdate Tetrahydrate and urea
Into deionized water, stirring forms homogeneous mixture solotion；(2) solution prepared by step (1) is transferred in reaction kettle, addition is led
Electric substrate carries out hydro-thermal reaction, obtains β phase cobalt molybdate persursor material；(3) sample prepared by step (2) is placed in tube furnace
In, high-temperature heat treatment is carried out under nitrogen atmosphere, obtains β phase cobalt molybdate；(4) by β phase cobalt molybdate sample prepared by step (3)
Carry out phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is sodium hypophosphite, and phosphatization temperature is 250 DEG C~350 DEG C, when phosphatization
Between be 0.5~1.5 hour, obtain phosphorus doping cobalt molybdate, wherein phosphorus doping cobalt molybdate refer to P elements incorporation cobalt molybdate lattice
In, rather than form phosphide.
Preferably, the mass concentration of the cobalt chloride hexahydrate and the urea in the homogeneous mixture solotion is respectively
6mg/ml~7mg/ml and 8mg/ml~8.5mg/ml, the cobalt element of the cobalt chloride hexahydrate and the Ammonium Molybdate Tetrahydrate
The molar ratio of molybdenum element is 1:2.
Preferably, the conductive substrates are titanium sheet and nickel foam.
Preferably, the hydrothermal temperature is 120~140 DEG C, and the hydro-thermal reaction time is 8~10 hours.
Preferably, the high-temperature heat treatment temperature is 400~500 DEG C, and the high-temperature heat treatment time is 1~3 hour.
Preferably, the dosage of the sodium hypophosphite is 50~100mg.
The second aspect according to the invention also provides a kind of phosphorus doping cobalt molybdate liberation of hydrogen electricity according to method as above preparation
Catalyst.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, have below beneficial to effect
Fruit:
1, it is capable of the electronic structure of Effective Regulation cobalt molybdate by phosphorus doping, to change its electric conductivity and intrinsic electricity is urged
Change activity, this method can be extended to other transition metal oxides, to open up an activated transition metal oxide
New approaches.
2, the cobalt molybdate of phosphorus doping shows efficient Hydrogen Evolution Performance in alkaline solution, when liberation of hydrogen current density is 10mA
cm-2, overpotential is only 140mV.Compared with the cobalt molybdate not adulterated (overpotential 280mV), catalytic performance, which has, greatly to be mentioned
It is high；Compared with noble metal platinum, overpotential differs only by 80mV.Therefore the use that noble metal platinum can be abandoned completely, to effectively drop
Low electrolysis water hydrogen manufacturing cost.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present invention；
(a), (b) are the X-ray of β phase cobalt molybdate and phosphorus doping cobalt molybdate prepared by the embodiment of the present invention 1 respectively in Fig. 2
Diffraction pattern and Raman spectrogram；
Fig. 3 is the x-ray photoelectron spectroscopy figure of phosphorus doping cobalt molybdate prepared by the embodiment of the present invention 1；
Fig. 4 is β phase cobalt molybdate, phosphorus doping cobalt molybdate and precious metals pt/C linear scan prepared by the embodiment of the present invention 1
Curve.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Fig. 1 is the flow chart of the preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present invention, as seen from the figure, the present invention
The preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent a kind of include the following steps:
(1) cobalt chloride hexahydrate, Ammonium Molybdate Tetrahydrate and urea are added separately in deionized water, stirring forms uniform
Mixed solution；
(2) solution prepared by step (1) is transferred in reaction kettle, conductive substrates is added, carried out hydro-thermal reaction, obtain β
Phase cobalt molybdate persursor material；
(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, obtains β phase
Cobalt molybdate；
(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is hypophosphorous acid
Sodium, phosphatization temperature are 250 DEG C~350 DEG C, and phosphating time is 0.5~1.5 hour, it is preferable that phosphatization temperature is 300 DEG C, phosphatization
Time is 1 hour, obtains the phosphorus doping cobalt molybdate.Wherein, phosphorus doping cobalt molybdate refers to the crystalline substance of P elements incorporation cobalt molybdate
In lattice, rather than form phosphide.
Specifically, the mass concentration of the cobalt chloride hexahydrate and the urea in the homogeneous mixture solotion is respectively
6mg/ml~7mg/ml and 8mg/ml~8.5mg/ml, the cobalt element of the cobalt chloride hexahydrate and the Ammonium Molybdate Tetrahydrate
The molar ratio of molybdenum element is 1:2.
Specifically, the conductive substrates are titanium sheet and nickel foam.
Specifically, the hydrothermal temperature is 120~140 DEG C, and the hydro-thermal reaction time is 8~10 hours.
Specifically, the high-temperature heat treatment temperature is 400~500 DEG C, and the high-temperature heat treatment time is 1~3 hour.
Specifically, the dosage of the sodium hypophosphite is 50~100mg.
The principle of the above inventive concept are as follows: sodium hypophosphite can produce PH between 250 DEG C~350 DEG C3Gas, the gas
It is reacted with β phase cobalt molybdate, will lead to P elements and replace part oxygen element, to form the cobalt molybdate of phosphorus doping.If PH3Gas
Excessively or reaction temperature is too high, will lead to whole oxygen elements and all reacts away, to form phosphide.Therefore control hypophosphorous acid
The amount and reaction temperature of sodium are the key that the cobalt molybdates for obtaining phosphorus doping.
In order to enable those skilled in the art to better understand the present invention, combined with specific embodiments below to a kind of phosphorus of the invention
The preparation method of doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent is described in detail.
Embodiment 1
A kind of preparation method of the phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present embodiment, comprising the following steps:
(1) by 476mg cobalt chloride hexahydrate, 706.4mg Ammonium Molybdate Tetrahydrate and 600mg urea be added to 72ml go from
In sub- water, stirring forms homogeneous mixture solotion, wherein the cobalt chloride hexahydrate and the urea are in the homogeneous mixture solotion
In mass concentration be respectively 6.6mg/ml and 8.3mg/ml, cobalt element and four molybdic acid hydrate in the cobalt chloride hexahydrate
The molar ratio of the molybdenum element of ammonium is 1:2；
(2) by step (1) prepare solution be transferred in reaction kettle, be added titanium sheet, 120 DEG C hydro-thermal reaction 8 hours, obtain
To β phase cobalt molybdate；
(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, at high temperature
Managing temperature is 450 DEG C, and the high-temperature process time is 2 hours, obtains β phase cobalt molybdate；
(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is hypophosphorous acid
Sodium, the amount of sodium hypophosphite are 75mg, and phosphatization temperature is 250 DEG C, and phosphating time is 1 hour, obtain the phosphorus doping cobalt molybdate.
Catalyst obtained is tested for the property as follows:
Electro-chemical test carries out on CHI 660D electrochemical workstation, using the phosphorus doping cobalt molybdate of above-mentioned preparation as work
Make electrode, carbon-point is used as to electrode, and saturated calomel electrode is as reference electrode；With 2mV s in 1MKOH solution-1Sweep fast survey
Measure the linear scan curve of the catalyst.
Precious metals pt/C and β phase cobalt molybdate is also tested for the property according to the above method, details are not described herein.
Fig. 2 (a), (b) are the x-ray diffraction patterns of β phase cobalt molybdate prepared by the embodiment of the present invention 1 and phosphorus doping cobalt molybdate
And Raman spectrogram, the x-ray photoelectron spectroscopy figure of phosphorus doping cobalt molybdate prepared by Fig. 3 embodiment of the present invention 1.Such as Fig. 2 institute
Show, phosphorating treatment will not change the crystal phase of β phase cobalt molybdate, will not influence the vibration of the various keys of β phase cobalt molybdate, illustrate at phosphatization
Reason does not form phosphide.From figure 3, it can be seen that there is the presence of P elements in β phase cobalt molybdate, in conjunction with Fig. 2, phosphorus member may infer that
Element has been incorporated into the lattice of cobalt molybdate.Fig. 4 is β phase cobalt molybdate, phosphorus doping cobalt molybdate and expensive prepared by the embodiment of the present invention 1
Pt metal/C linear scan curve.As shown in figure 4, when current density is 10mA cm-2, β phase cobalt molybdate, phosphorus doping cobalt molybdate
It is respectively 283mV, 138mV, 54mV with precious metals pt/C overpotential, shows the β phase cobalt molybdate of the embodiment of the present invention by phosphorus
After change processing, catalytic hydrogen evolution ability is remarkably reinforced, and is slightly weaker than precious metals pt/C.
Embodiment 2
A kind of preparation method of the phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present embodiment, comprising the following steps:
(1) by 432mg cobalt chloride hexahydrate, 641.1mg Ammonium Molybdate Tetrahydrate and 576mg urea be added to 72ml go from
In sub- water, stirring forms homogeneous mixture solotion；The cobalt chloride hexahydrate and the urea are in the homogeneous mixture solotion
Mass concentration is respectively 6mg/ml and 8mg/ml, the molybdenum of cobalt element and Ammonium Molybdate Tetrahydrate member in the cobalt chloride hexahydrate
The molar ratio of element is 1:2；
(2) by step (1) prepare solution be transferred in reaction kettle, be added titanium sheet, 140 DEG C hydro-thermal reaction 9 hours, obtain
To β phase cobalt molybdate；
(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, at high temperature
Managing temperature is 400 DEG C, and the high-temperature process time is 3 hours, obtains β phase cobalt molybdate；
(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is hypophosphorous acid
Sodium, the amount of sodium hypophosphite are 50mg, and phosphatization temperature is 300 DEG C, and phosphating time is 1.5 hours, obtain the phosphorus doping molybdic acid
Cobalt.
The catalyst is tested for the property with method same as Example 1.
Embodiment 3
A kind of preparation method of the phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present embodiment, comprising the following steps:
(1) 504mg cobalt chloride hexahydrate, 748mg Ammonium Molybdate Tetrahydrate and 612mg urea are added to 72ml deionization
In water, stirring forms homogeneous mixture solotion；The matter of the cobalt chloride hexahydrate and the urea in the homogeneous mixture solotion
Amount concentration is respectively 7mg/ml and 8.5mg/ml, the molybdenum of cobalt element and Ammonium Molybdate Tetrahydrate member in the cobalt chloride hexahydrate
The molar ratio of element is 1:2；
(2) by step (1) prepare solution be transferred in reaction kettle, be added titanium sheet, 130 DEG C hydro-thermal reaction 10 hours,
Obtain β phase cobalt molybdate；
(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, at high temperature
Managing temperature is 500 DEG C, and the high-temperature process time is 1 hour, obtains β phase cobalt molybdate；
(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is hypophosphorous acid
Sodium, the amount of sodium hypophosphite are 100mg, and phosphatization temperature is 350 DEG C, and phosphating time is 0.5 hour, obtain the phosphorus doping molybdic acid
Cobalt.
The catalyst is tested for the property with method same as Example 1.
Embodiment 4
A kind of preparation method of the phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent of the present embodiment, comprising the following steps:
(1) by 468mg cobalt chloride hexahydrate, 694.5mg Ammonium Molybdate Tetrahydrate and 576mg urea be added to 72ml go from
In sub- water, stirring forms homogeneous mixture solotion；The cobalt chloride hexahydrate and the urea are in the homogeneous mixture solotion
Mass concentration is respectively 6.5mg/ml and 8mg/ml, the molybdenum of cobalt element and the Ammonium Molybdate Tetrahydrate in the cobalt chloride hexahydrate
The molar ratio of element is 1:2；
(2) by step (1) prepare solution be transferred in reaction kettle, be added titanium sheet, 130 DEG C hydro-thermal reaction 10 hours,
Obtain β phase cobalt molybdate；
(3) sample prepared by step (2) is placed in tube furnace, carries out high-temperature heat treatment under nitrogen atmosphere, at high temperature
Managing temperature is 500 DEG C, and the high-temperature process time is 1 hour, obtains β phase cobalt molybdate；
(4) sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is hypophosphorous acid
Sodium, the amount of sodium hypophosphite are 75mg, and phosphatization temperature is 300 DEG C, and phosphating time is 0.5 hour, obtain the phosphorus doping molybdic acid
Cobalt.
The catalyst is tested for the property with method same as Example 1.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent, which comprises the steps of:
(1) cobalt chloride hexahydrate, Ammonium Molybdate Tetrahydrate and urea are add to deionized water, stirring formation uniformly mixes molten
Liquid, wherein the mass concentration of the cobalt chloride hexahydrate and the urea in the homogeneous mixture solotion is respectively 6mg/ml
~7mg/ml and 8mg/ml~8.5mg/ml, the molybdenum element of the cobalt element of the cobalt chloride hexahydrate and the Ammonium Molybdate Tetrahydrate
Molar ratio be 1:2；
(2) solution prepared by step (1) is transferred in reaction kettle, conductive substrates is added, carried out hydro-thermal reaction, obtain β phase molybdenum
Sour cobalt precursor material；
(3) β phase cobalt molybdate persursor material prepared by step (2) is placed in tube furnace, carries out high warm under nitrogen atmosphere
Processing, obtains β phase cobalt molybdate；
(4) β phase cobalt molybdate sample prepared by step (3) is subjected to phosphorating treatment under nitrogen atmosphere, phosphatization agents useful for same is
Sodium hypophosphite, phosphatization temperature are 250 DEG C~350 DEG C, and phosphating time is 0.5~1.5 hour, obtain phosphorus doping cobalt molybdate, wherein
Phosphorus doping cobalt molybdate refers in the lattice of P elements incorporation cobalt molybdate, rather than forms phosphide.
2. a kind of preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent as described in claim 1, which is characterized in that described
Conductive substrates are titanium sheet and nickel foam.
3. a kind of preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent as claimed in claim 2, which is characterized in that described
Hydrothermal temperature is 120 DEG C~140 DEG C, and the hydro-thermal reaction time is 8~10 hours.
4. a kind of preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent as claimed in claim 3, which is characterized in that described
High-temperature heat treatment temperature is 400 DEG C~500 DEG C, and the high-temperature heat treatment time is 1~3 hour.
5. a kind of preparation method of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent as claimed in claim 4, which is characterized in that described
The dosage of sodium hypophosphite is 50mg~100mg.
6. the phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent prepared according to one of claim 1-5 as above the method.
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| CN112108149A (en) * | 2019-06-21 | 2020-12-22 | 南京大学昆山创新研究院 | Preparation method of electrocatalytic material, corresponding material and use method |
| CN110195235A (en) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | A kind of phosphorus doping cobalt acid nickel/foam nickel electrode and its preparation method and application |
| CN110342586A (en) * | 2019-08-30 | 2019-10-18 | 济南大学 | A kind of defective phosphorus doping CoFe of tool2O4The preparation and electro-catalysis application of nano-powder |
| CN110404577A (en) * | 2019-08-30 | 2019-11-05 | 安徽理工大学 | A kind of carbon-based phosphating sludge nano particle Electrocatalytic Activity for Hydrogen Evolution Reaction agent, preparation method and application |
| CN110624593A (en) * | 2019-09-30 | 2019-12-31 | 陕西科技大学 | Preparation method of VN @ Co electrocatalyst |
| CN110773210B (en) * | 2019-11-27 | 2022-06-17 | 哈尔滨师范大学 | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof |
| CN111068694A (en) * | 2019-12-03 | 2020-04-28 | 上海工程技术大学 | Cobalt-molybdenum composite/carbon fiber composite material of nano array and preparation method thereof |
| CN111701595B (en) * | 2020-05-20 | 2022-11-15 | 上海应用技术大学 | Mo-La/NF hydrogen evolution material and preparation method and application thereof |
| CN112371119B (en) * | 2020-11-13 | 2023-07-07 | 中南大学深圳研究院 | Preparation method and application of multi-metal pairing alkaline catalyst |
| CN112701304B (en) * | 2021-01-07 | 2021-12-14 | 淮北德昇科技有限公司 | Sea urchin-shaped P-doped ZrMo2O8Preparation method of nano catalyst |
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