CN108889331A - A kind of electrocatalytic hydrogen evolution material and preparation method thereof - Google Patents
A kind of electrocatalytic hydrogen evolution material and preparation method thereof Download PDFInfo
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- CN108889331A CN108889331A CN201810906511.8A CN201810906511A CN108889331A CN 108889331 A CN108889331 A CN 108889331A CN 201810906511 A CN201810906511 A CN 201810906511A CN 108889331 A CN108889331 A CN 108889331A
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- ruthenium
- hydrogen evolution
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- electrocatalytic hydrogen
- catalyst
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 15
- UYVDBJBSAPKNAN-UHFFFAOYSA-N 5,6-dihydroxycyclohex-5-ene-1,2,3,4-tetrone;sodium Chemical compound [Na].[Na].OC1=C(O)C(=O)C(=O)C(=O)C1=O UYVDBJBSAPKNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000005253 cladding Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- -1 0.25mmol Chemical compound 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- WCJLIWFWHPOTAC-UHFFFAOYSA-N rhodizonic acid Chemical compound OC1=C(O)C(=O)C(=O)C(=O)C1=O WCJLIWFWHPOTAC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- HMYQBFAEJWGUMD-UHFFFAOYSA-N cyclohexene-1,2-diol Chemical compound OC1=C(O)CCCC1 HMYQBFAEJWGUMD-UHFFFAOYSA-N 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000012300 argon atmosphere Substances 0.000 description 6
- MGWNCZWPMHBQNV-UHFFFAOYSA-N methanol;1-methylpyrrolidin-2-one Chemical compound OC.CN1CCCC1=O MGWNCZWPMHBQNV-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 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
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 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
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to catalyst to synthesize field, more specifically, it is related to a kind of synthesis of nitrogen-doped carbon cladding efficient liberation of hydrogen catalyst of ruthenium, catalyst is by ruthenium trichloride, 3, 3', 4, 4'- biphenyl tetramine, 5, 6- dihydroxy -5- cyclohexene -1, 2, 3, 4- tetrone disodium salt and N-Methyl pyrrolidone are made, a kind of nitrogen-doped carbon cladding efficient liberation of hydrogen catalyst of ruthenium provided by the invention and preparation method thereof, platinum based catalyst is substituted with ruthenium-based catalyst, it is high to efficiently solve the generally existing overpotential of electrolysis hydrogen catalyst, preparation condition is harsh, the disadvantages of stability is poor, preparation process is simple, yield is high, it is good using the thermostabilization and chemical stability of the nitrogen-doped carbon cladding efficient liberation of hydrogen catalyst material of ruthenium of this method preparation, its catalytic hydrogen evolution performance is much higher than platinum carbon material in acid condition.
Description
Technical field
The present invention relates to catalyst preparation technical fields, more specifically, are related to a kind of electrocatalytic hydrogen evolution material and its system
Preparation Method.
Background technique
Hydrogen energy source is one of most promising clear energy sources, this, which is primarily due to it, has environmental-friendly, energy density height
The characteristics of.Ideal electrocatalytic hydrogen evolution catalyst is platinum and its composite material.But the resource scarcity of platinum, it is at high price, be difficult by
Make the selection of heavy industrialization application.It is in recent years, like a raging fire in terms of non-platinum class electrocatalytic hydrogen evolution catalyst research,
Such as sulfide of molybdenum disulfide, tungsten sulfide, carbide, defect nickel oxide, phosphatization cobalt, nickel phosphide, iron-cobalt-nickel.In addition, ruthenium and
Its composite material has also obtained people's attention as liberation of hydrogen material, this is primarily due to ruthenium composite material and often has connect with platinum carbon
Close plays spike potential and overpotential, and performance is brilliant.
Summary of the invention
In the presence of overcoming the shortcomings of the prior art, the present invention provides a kind of electrocatalytic hydrogen evolution material and its preparation side
Method solves the features such as existing electrolysis hydrogen catalyst overpotential is high, preparation process is complicated, condition is harsh, stability is poor.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows：
A kind of electrocatalytic hydrogen evolution material, by ruthenium trichloride, 3,3', 4,4'- biphenyl tetramines, 5,6- dihydroxy -5- cyclohexene -1,2,
3,4- tetrone disodium salt and N-Methyl pyrrolidone are made.
The ruthenium trichloride can also be ruthenium trichloride hydrate.
Mole of the 3,3', 4,4'- biphenyl tetramine and 5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salt
Than being 1：1.
A kind of preparation method of electrocatalytic hydrogen evolution material, includes the following steps：
S1, by the ruthenium trichloride of 10 ~ 100mg or the 3,3' of ruthenium trichloride hydrate, 0.25mmol, 4,4'- biphenyl tetramine and
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone the disodium salt of 0.25mmol be dissolved in the N-Methyl pyrrolidone of 10mL with
Methanol（NMP-MeOH）In mixed solution, stir evenly；
S2, mixed solution in S1 is transferred in water heating kettle, 200 degrees Celsius are reacted 24 hours, and grey black solid is obtained；
S3, by grey black solid in S2 in nitrogen atmosphere, 800 ~ 1000 degree of temperature lower calcinations obtain nitrogen-doped carbon cladding ruthenium
The catalyst of efficient liberation of hydrogen.
The volume ratio of N-Methyl pyrrolidone and N-Methyl pyrrolidone in methanol mixed solution and methanol is in the S1
4:1。
Nitrogen can also be argon gas in the S3.
A kind of preparation method of electrocatalytic hydrogen evolution material, includes the following steps：
S1, by the ruthenium trichloride of 10 ~ 100mg or the 3,3' of ruthenium trichloride hydrate, 0.25mmol, 4,4'- biphenyl tetramine and
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone the disodium salt of 0.25mmol is dissolved in the N-Methyl pyrrolidone of 10mL
（NMP）In, it stirs evenly；
S2, mixed solution in S1 is stirred at reflux reaction 18 hours for 180 degrees Celsius under nitrogen protection, be cooled to after completion of the reaction
Room temperature；
S3, the N-Methyl pyrrolidone solution that 4mL is added flow back 8 hours, cooling, and grey black solid is obtained by filtration；
S4, by grey black solid in S3 in nitrogen atmosphere, 800 ~ 1000 degree of temperature lower calcinations obtain nitrogen-doped carbon cladding ruthenium
The catalyst of efficient liberation of hydrogen.
The sodium borohydride for being 40% containing mass fraction in N-Methyl pyrrolidone solution in the S3（NaBH4）.
Nitrogen can also be argon gas in the S4.
Compared with prior art, the advantageous effect of present invention is that：
A kind of electrocatalytic hydrogen evolution material provided by the invention and preparation method thereof, to substitute platinum based catalyst with non-platinum catalyst,
Efficiently solve the generally existing overpotential height of electrolysis hydrogen catalyst, preparation process complexity, preparation condition harshness, stability difference etc.
Disadvantage, the preparation have many advantages, such as simply, reproducible, reaction condition is mild, yield is high, the N doping prepared using this method
The thermostabilization of the efficient liberation of hydrogen catalyst material of carbon coating ruthenium and chemical stability are good, its catalytic hydrogen evolution performance is remote in acid condition
Higher than platinum carbon material.
Detailed description of the invention
Fig. 1 is electrocatalytic hydrogen evolution material prepared by the present invention in 0.5M H2SO4Polarization curve in solution；
Fig. 2 is electrocatalytic hydrogen evolution material prepared by the present invention in 0.5M H2SO4Ta Feier in solution（Tafel）Curve；
Fig. 3 is polarization curve of the electrocatalytic hydrogen evolution material prepared by the present invention in 1M KOH solution；
Fig. 4 is electrocatalytic hydrogen evolution material prepared by the present invention in 0.5M H2SO4In solution, through 10000 front and backs are recycled
Polarization curve.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
S1, by 10mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 13,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mL NMP-MeOH, wherein N- in mixed solution
The volume ratio of methyl pyrrolidone and methanol is 4:1, it stirs evenly；
S2, mixed solution in S1 is transferred in water heating kettle, 200 degrees Celsius are reacted 24 hours, are obtained after completion of the reaction greyish black
Color solid, the yield based on ruthenium are 81%；
S3, by grey black solid in S2,800 degree of calcinings obtain black powder, as electrocatalytic hydrogen evolution under nitrogen or argon atmosphere
Catalyst.
Embodiment 2
S1, by 54mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 3,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mL NMP-MeOH, wherein N- in mixed solution
The volume ratio of methyl pyrrolidone and methanol is 4:1, it stirs evenly；
S2, mixed solution in S1 is transferred in water heating kettle, 200 degrees Celsius are reacted 24 hours, are obtained after completion of the reaction greyish black
Color solid, the yield based on ruthenium are 80%；
S3, by grey black solid in S2,900 degree of calcinings obtain black powder, as electrocatalytic hydrogen evolution under nitrogen or argon atmosphere
Catalyst.
Embodiment 3
S1, by 100mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 3,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mL NMP-MeOH, wherein N- in mixed solution
The volume ratio of methyl pyrrolidone and methanol is 4:1, it stirs evenly；
S2, mixed solution in S1 is transferred in water heating kettle, 200 degrees Celsius are reacted 24 hours, are obtained after completion of the reaction greyish black
Color solid, the yield based on ruthenium are 79%；
S3, by grey black solid in S2,1000 degree of calcinings obtain black powder under nitrogen or argon atmosphere, and as electro-catalysis is analysed
Hydrogen catalyst.
Embodiment 4
S1, by 10mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 3,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mLNMP, stir evenly；
S2, mixing liquid in S1 is stirred at reflux reaction 18 hours for 180 degrees Celsius under nitrogen protection, be cooled to after completion of the reaction
Room temperature；
S3,4mL nmp solution is added, the NaBH for being wherein 40% containing mass fraction in nmp solution4,Reflux 8 hours, it is cooling,
Grey black solid is obtained by filtration, the yield based on ruthenium is 80%；
S4, by grey black solid in S3 in nitrogen or argon atmosphere, be electrocatalytic hydrogen evolution in 800 degree of temperature lower calcinations.
Embodiment 5
S1, by 54mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 3,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mLNMP, stir evenly；
S2, mixing liquid in S1 is stirred at reflux reaction 18 hours for 180 degrees Celsius under nitrogen protection, be cooled to after completion of the reaction
Room temperature；
S3,4mL nmp solution is added, the NaBH for being wherein 40% containing mass fraction in nmp solution4, it flows back 8 hours, it is cooling,
Grey black solid is obtained by filtration, the yield based on ruthenium is 82%；
S4, by grey black solid in S3 in nitrogen or argon atmosphere, be electrocatalytic hydrogen evolution in 900 degree of temperature lower calcinations.
Embodiment 6
S1, by 10mg ruthenium trichloride or ruthenium trichloride hydrate, 0.25mmol 3,3', 4,4'- biphenyl tetramine and 0.25mmol
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salts are dissolved in 10mLNMP, stir evenly；
S2, mixing liquid in S1 is stirred at reflux reaction 18 hours for 180 degrees Celsius under nitrogen protection, be cooled to after completion of the reaction
Room temperature；
S3,4mL nmp solution is added, the NaBH for being wherein 40% containing mass fraction in nmp solution4, it flows back 8 hours, it is cooling,
Grey black solid is obtained by filtration, the yield based on ruthenium is 78%；
S4, by grey black solid in S3 in nitrogen or argon atmosphere, be electrocatalytic hydrogen evolution in 1000 degree of temperature lower calcinations.
As shown in Fig. 1 ~ 4, electrocatalytic hydrogen evolution material prepared in the above embodiments is subjected to electro-chemical test, electro-chemical test
Condition is：
Linear sweep voltammetry test condition is：2.5 milligrams of samples are taken, 250 microlitres of solvents are dispersed in（170 microlitres+80 microlitres of water different
Propyl alcohol）In, add 8 microlitre 5% of perfluorinated sulfonic resin, ultrasonic disperse half an hour obtains ink shape suspension.Take 4 microlitres of suspensions
It drips in drying and can test on the glass-carbon electrode of 3 mm dias.Test is to electrode with graphite, and Ag/AgCl is reference electrode, if
Setting scanning speed is 0.001 Vs-1。
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment,
Within the knowledge of a person skilled in the art, it can also make without departing from the purpose of the present invention each
Kind variation, various change should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of electrocatalytic hydrogen evolution material, it is characterised in that：By ruthenium trichloride, 3,3', 4,4'- biphenyl tetramine, 5,6- dihydroxy-
5- cyclohexene -1,2,3,4- tetrone disodium salt and N-Methyl pyrrolidone are made.
2. a kind of electrocatalytic hydrogen evolution material according to claim 1, it is characterised in that：The ruthenium trichloride can also be three
Ruthenium chloride hydrate.
3. a kind of electrocatalytic hydrogen evolution material according to claim 1, it is characterised in that：The 3,3', 4,4'- biphenyl tetramine
Molar ratio with 5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone disodium salt is 1：1.
4. a kind of preparation method of electrocatalytic hydrogen evolution material, which is characterized in that include the following steps：
S1, by the ruthenium trichloride of 10 ~ 100mg or the 3,3' of ruthenium trichloride hydrate, 0.25mmol, 4,4'- biphenyl tetramine and
5,6- dihydroxy -5- cyclohexene -1,2,3,4- tetrone the disodium salt of 0.25mmol be dissolved in the N-Methyl pyrrolidone of 10mL with
In methanol mixed solution, stir evenly；
S2, mixed solution in S1 is transferred in water heating kettle, 200 degrees Celsius are reacted 24 hours, and grey black solid is obtained；
S3, by grey black solid in S2 in nitrogen atmosphere, 800 ~ 1000 degree of temperature lower calcinations obtain nitrogen-doped carbon cladding ruthenium
The catalyst of efficient liberation of hydrogen.
5. a kind of preparation method of electrocatalytic hydrogen evolution material according to claim 4, it is characterised in that：N- first in the S1
The volume ratio of N-Methyl pyrrolidone and methanol is 4 in base pyrrolidones and methanol mixed solution:1.
6. a kind of preparation method of electrocatalytic hydrogen evolution material according to claim 4, it is characterised in that：Nitrogen in the S3
It can also be argon gas.
7. a kind of preparation method of electrocatalytic hydrogen evolution material, which is characterized in that include the following steps：
S1, by the ruthenium trichloride of 10 ~ 100mg or the 3,3' of ruthenium trichloride hydrate, 0.25mmol, 4,4'- biphenyl tetramine and
5,6- dihydroxy -5- cyclohexene -1,2 of 0.25mmol, 3,4- tetrone disodium salts are dissolved in the N-Methyl pyrrolidone of 10mL,
It stirs evenly；
S2, mixed solution in S1 is stirred at reflux reaction 18 hours for 180 degrees Celsius under nitrogen protection, be cooled to after completion of the reaction
Room temperature；
S3, the N-Methyl pyrrolidone solution that 4mL is added flow back 8 hours, cooling, and grey black solid is obtained by filtration；
S4, by grey black solid in S3 in nitrogen atmosphere, 800 ~ 1000 degree of temperature lower calcinations obtain nitrogen-doped carbon cladding ruthenium
The catalyst of efficient liberation of hydrogen.
8. a kind of preparation method of electrocatalytic hydrogen evolution material according to claim 7, it is characterised in that：N- first in the S3
The sodium borohydride for being 40% containing mass fraction in base pyrrolidone solution.
9. a kind of preparation method of electrocatalytic hydrogen evolution material according to claim 7, it is characterised in that：Nitrogen in the S4
It can also be argon gas.
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| CN111266109A (en) * | 2018-12-04 | 2020-06-12 | 中国科学院上海硅酸盐研究所 | Ru-WOxNanowire HER catalyst and preparation method thereof |
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