CN109569651A - A kind of bifunctional catalyst RuCo@HCSs and its preparation method and application - Google Patents
A kind of bifunctional catalyst RuCo@HCSs and its preparation method and application Download PDFInfo
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- CN109569651A CN109569651A CN201811383321.9A CN201811383321A CN109569651A CN 109569651 A CN109569651 A CN 109569651A CN 201811383321 A CN201811383321 A CN 201811383321A CN 109569651 A CN109569651 A CN 109569651A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- -1 aldehyde compound Chemical class 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical class O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- HHZQLQREDATOBM-CODXZCKSSA-M Hydrocortisone Sodium Succinate Chemical compound [Na+].O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)COC(=O)CCC([O-])=O)[C@@H]4[C@@H]3CCC2=C1 HHZQLQREDATOBM-CODXZCKSSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000001851 hypotonia-cystinuria syndrome Diseases 0.000 description 1
- 238000002952 image-based readout Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B01J35/33—
-
- B01J35/51—
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to catalyst preparation technical field, a kind of bifunctional catalyst RuCo@HCSs and its preparation method and application is disclosed.Using hollow carbon sphere as carrier, RuCo alloy nano particle is covered by between hollow carbon sphere wall the bifunctional catalyst [email protected] is prepared using St ber method2Nanosphere；By SiO obtained2In the mixed solvent is added in nanosphere, sequentially adds ethyl orthosilicate, phenolic compound and cetyl trimethylammonium bromide, and the aqueous solution of aldehyde compound is added under stiring, then stirs, and separates, dry, and SiO is made2@phenolic resin；By SiO2@phenolic resin roasts under an inert atmosphere, and SiO is made2@C；By SiO2Metal precursor cobalt nitrate and ruthenium trichloride is added by the method for incipient impregnation in@C, then dries, and SiO is made2@C@RuCo；By SiO2@C@RuCo is roasted under an inert atmosphere, then with HF solution corrosion to get bifunctional catalyst [email protected] catalyst RuCo@HCSs of the present invention releases the application of hydrogen catalyst as electrolysis water liberation of hydrogen or ammonia borane hydrolysis.
Description
Technical field
The invention belongs to electrolysis water liberations of hydrogen and ammonia borane hydrolysis to release hydrogen catalyst preparation technical field, and in particular to Yi Zhongshuan
Function catalyst RuCo@HCSs and its preparation method and application.
Background technique
With the shortage of non-renewable resources (such as coal, oil and natural gas), the environmental pollutions such as global warming are asked
Topic is increasingly sharpened, and exploitation green regenerative energy sources are increasingly urgent.In numerous new energy, Hydrogen Energy, as a kind of cleaning, low-carbon
The energy and receive significant attention.Wherein, electrolysis water prepare hydrogen and ammonia borane hydrolysis to release hydrogen be most economical effective conversion and storage
The method for depositing hydrogen.Releasing the dominant catalyst of hydrogen currently used for electrolysis aquatic products hydrogen (HER) and ammonia borane hydrolysis is Pt base catalyst.Pt
Base catalyst activity is high, stability is good, but the drawback limited there are expensive, reserves, it is hindered to apply and develop.
Although tool has great advantage in terms of cost, catalytic activity needs to improve base metal (Co, Ni etc.).
Carbon material has the advantages such as specific surface area is high, electric conductivity is good and is studied extensively by scientific research person.Carbon nanotube, carbon
Nanosphere, carbon nano-fiber research are increasingly mature, there is larger application potential in the catalyst.However the catalytic activity of carbon material with
There is very big gap in metal phase ratio, some researchs are dedicated to adulterating electronics transfer of the hetero atoms such as N, S to regulate and control carbon material, produce effects
It is little.Therefore, more efficient, more stable and low-cost New-type bifunctional catalyst is prepared to be of great significance.
Summary of the invention
In place of overcoming the shortcomings of the prior art, the purpose of the present invention is to provide a kind of bifunctional catalysts
RuCo@HCSs and its preparation method and application.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of bifunctional catalyst RuCo@HCSs, the bifunctional catalyst RuCo@HCSs is using hollow carbon sphere as carrier, RuCo
Alloy nano particle is covered by between hollow carbon sphere wall.
Preparation method, steps are as follows:
(a), SiO is prepared using St ber method2Nanosphere；
(b), by SiO obtained2In the mixed solvent is added in nanosphere, sequentially adds ethyl orthosilicate, phenolic compound and 16
The aqueous solution of aldehyde compound is added under stiring, then stirs for alkyl trimethyl ammonium bromide, separates, dry, and intermediate is made
I is labeled as SiO2@phenolic resin；The mixed solvent 1: 1 ~ 5 is made of by volume dehydrated alcohol and water；
(c), by SiO obtained2@phenolic resin roasts under an inert atmosphere, and intermediate II is made, and is labeled as SiO2@C；
(d), by SiO obtained2Metal precursor cobalt nitrate and ruthenium trichloride is added by the method for incipient impregnation in@C, then
It is dry, intermediate III is made, is labeled as SiO2@C@RuCo；
(e), by SiO obtained2@C@RuCo is roasted under an inert atmosphere, then with HF solution corrosion to get double-function catalyzing
Agent is labeled as RuCo@HCSs.
Preferably, in step (b), the phenolic compound is resorcinol, and the aqueous solution of the aldehyde compound is matter
Measure the formalin of concentration 35 ~ 40%.
Preferably, in step (b), in terms of mass volume ratio, SiO2Nanosphere: mixed solvent: ethyl orthosilicate: isophthalic two
Phenol: cetyl trimethylammonium bromide: mg: 50 ~ 70 mL: 0.2 ~ 0.4 mL: 0.25 ~ 0.3 g of formalin=200 ~ 500
:0.3~0.4 g:0.6~0.8 mL；15 ~ 24 h are stirred after formalin is added.
Preferably, in step (c), calcination process is carried out under an argon atmosphere, and heating rate is 2 ~ 10 DEG C/min, roasting
Burning temperature is 650 ~ 850 DEG C, and calcining time is 2 ~ 6 h.
Preferably, in step (d), the amount ratio of cobalt nitrate and ruthenium trichloride guarantees the quality of Ru and Co in metal precursor
Than being 1 ~ 3: 50.
Preferably, in step (e), calcination process is carried out under an argon atmosphere, and heating rate is 1 ~ 10 DEG C/min, roasting
Temperature is 450 ~ 650 DEG C, and calcining time is 1 ~ 6 h.
The bifunctional catalyst RuCo@HCSs releases answering for hydrogen catalyst as electrolysis water liberation of hydrogen or ammonia borane hydrolysis
With.
Compared with prior art, the present invention has the following beneficial effects:
Noble metal Ru and transition metal Co is formed alloy and received by bifunctional catalyst RuCo@HCSs prepared by the method for the present invention
Rice corpuscles not only reduces the concerted catalysis that cost has also given full play between metal and acts on；In addition using hollow carbon sphere as carrier,
Hollow carbon sphere has porous, huge specific surface area and good electric conductivity, and RuCo alloy nano particle can be made in hollow carbon sphere
It is evenly dispersed between wall, be conducive to mass transport process；Between RuCo alloy nano particle is supported on hollow carbon sphere wall, metal is made full use of
Difunctional effect between particle and hollow carbon sphere, the catalytic activity and stability of the bifunctional catalyst are far superior to monometallic
The catalyst of load or single function catalysis.Preparation method of the present invention, simple process, raw material are easy to get, are at low cost, are suitble to commercialization
Production.
Detailed description of the invention
Fig. 1: the XRD spectrum of RuCo@HCSs catalyst prepared by embodiment 1；
Fig. 2: the TEM figure of RuCo@HCSs catalyst prepared by embodiment 1；
Fig. 3: the N of RuCo@HCSs catalyst prepared by embodiment 12Adsorption-desorption curve and graph of pore diameter distribution；
Fig. 4: the XPS figure of RuCo@HCSs catalyst prepared by embodiment 1；
Fig. 5: RuCo HCSs catalyst and contrast sample Pt/C catalyst prepared by upper behavior embodiment 1 ~ 7 is respectively in 0.5 M
H2SO4, liberation of hydrogen polarization curve in 1 M PBS and 1 M KOH；RuCo@HCSs catalyst prepared by middle behavior embodiment 1 and right
Than sample P t/C catalyst respectively in 0.5 M H2SO4, Tafel slope in 1 M PBS and 1 M KOH；Lower behavior embodiment 1
The RuCo@HCSs catalyst and contrast sample Pt/C catalyst of preparation are respectively in 0.5 M H2SO4, in 1 M PBS and 1 M KOH
The liberation of hydrogen polarization curve of 10000 circle front and back of circulation；
Fig. 6 :(a) the ammonia borane hydrolysis of RuCo@HCSs catalyst and contrast sample Pt/C catalyst prepared by embodiment 1 releases hydrogen speed
Rate figure；(b) TOF under RuCo@HCSs catalyst different temperatures prepared by embodiment 1；(c) RuCo@HCSs prepared by embodiment 1
Ammonia borane hydrolysis under catalyst different temperatures releases hydrogen rate diagram；(d) the ammonia borane hydrolysis for recycling 7 times releases hydrogen rate diagram；
Fig. 7: the activation energy figure of RuCo@HCSs catalyst prepared by embodiment 1.
Specific embodiment
To keep the present invention clearer, clear, technical solution of the present invention is further described below.It should manage
Solution, the specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
Embodiment 1
The preparation method of bifunctional catalyst RuCo@HCSs:
(a), SiO is prepared using St ber method2Nanosphere；
(b), by SiO obtained2300 mg of nanosphere addition, 60 mL in the mixed solvents (dehydrated alcohol: water=1: 5, volume ratio),
0.3 mL ethyl orthosilicate, 0.27 g Resorcino and 0.33 g cetyl trimethylammonium bromide are sequentially added, under stiring
The formalin of 0.75 mL mass concentration 40% is added, then stirs 22 h, centrifuge washing at room temperature, 500 rpm of revolving speed
(revolving speed is 7000 rpm, 3 min), intermediate compound I is made in 60 DEG C of 6 h of vacuum drying, is labeled as SiO2@phenolic resin；
(c), by SiO obtained2@phenolic resin is warming up to 750 DEG C of roastings under an argon atmosphere with the heating rate of 3 DEG C/min
Intermediate II is made in 2 h, is labeled as SiO2@C；
(d), by 400 mg SiO2@C is placed in beaker, and metal precursor six is added by the method for incipient impregnation and is hydrated nitre
(amount ratio of cabaltous nitrate hexahydrate and three hydrate ruthenium trichlorides guarantees that the mass ratio of Ru and Co is for sour cobalt and three hydrate ruthenium trichlorides
2: 50, cabaltous nitrate hexahydrate and three hydrate ruthenium trichlorides are codissolved in 700 μ L water, and while earthquake, beaker is added dropwise
In), then 60 DEG C of 8 h of drying, are made intermediate III, are labeled as SiO2@C@RuCo。
(e), by SiO obtained2@C@RuCo is warming up to 550 DEG C of roastings under an argon atmosphere with the heating rate of 3 DEG C/min
2 h are burnt, the HF solution corrosion of 5 % of mass concentration is then used, obtains bifunctional catalyst, are labeled as RuCo@HCSs.
Embodiment 2
Difference from example 1 is that: in step (d), guarantee that the dosage of cabaltous nitrate hexahydrate is constant, three hydration three of change
The dosage of ruthenic chloride guarantees that Ru and Co mass ratio is 1: 50, other with embodiment 1.
Embodiment 3
Difference from example 1 is that: in step (d), guarantee that the dosage of cabaltous nitrate hexahydrate is constant, three hydration three of change
The dosage of ruthenic chloride guarantees that Ru and Co mass ratio is changed to 3: 50, other with embodiment 1.
Embodiment 4
Difference from example 1 is that: in step (e), maturing temperature is changed to 450 DEG C, other with embodiment 1.
Embodiment 5
Difference from example 1 is that: in step (e), maturing temperature is changed to 650 DEG C, other with embodiment 1.
Embodiment 6
Difference from example 1 is that: in step (e), calcining time is changed to 1 h, other with embodiment 1.
Embodiment 7
Difference from example 1 is that: in step (e), calcining time is changed to 6 h, other with embodiment 1.
Catalyst structure characterization
Fig. 1 is the XRD diagram of RuCo@HCSs catalyst prepared by the embodiment of the present invention 1.Fig. 1 can prove that armorphous carbon and
The presence of RuCo alloy.
Fig. 2 is the transmission electron microscope picture of RuCo@HCSs catalyst prepared by the embodiment of the present invention 1.As can be seen from Figure 2:
RuCo alloy nano particle is evenly distributed between hollow carbon sphere wall, and partial size is about 2 ~ 10 nm.
Fig. 3 is the N of RuCo@HCSs catalyst prepared by the embodiment of the present invention 12Adsorption-desorption curve and pore-size distribution
Figure.As can be seen from Figure 3: RuCo@HCSs catalyst is porous structure, and specific surface area is 1262 m2 g-1, pore volume is 1.17 cm3
g−1, pore-size distribution has a mesoporous peak at 3.3 nm.
Fig. 4 is the XPS figure of RuCo@HCSs catalyst prepared by the embodiment of the present invention 1.The score from figure it can be seen that
The presence of Ru, Co and C.
Catalyst performance test
(1) evolving hydrogen reaction
Circulation volt is carried out using Pt/C catalyst of the three-electrode system to catalyst prepared by the present invention and commercialized 20 wt%
Peace test, three-electrode system are divided into working electrode, reference electrode and to electrodes, and wherein saturated calomel electrode is reference electrode, carbon
Stick is used as to electrode, and evolving hydrogen reaction is respectively in 0.5 M H2SO4, test in 1M PBS and 1 M KOH solution.
According to following preparation method preparation work electrode: weighing the catalyst sample that 3 mg have been prepared first and be added 300
In mL dehydrated alcohol, 50 μ L, 5 wt % Nafion solution is then added, it is suspended to measure 10 μ L with liquid-transfering gun by 30 min of ultrasound
Drop is dried at room temperature on the glass-carbon electrode of 4 mm of diameter.
Liberation of hydrogen test condition: test temperature: room temperature (25 ~ 28 DEG C)；Linear sweep rate: 2 mv/s；0.5 M H2SO4
Middle LSV test voltage range: -0.8 ~ -1.5 mV；LSV test voltage range in 1M PBS: -0.4 ~ -1.1 mV；In 1M KOH
LSV test voltage range: 0 ~ -0.65 mV；0.5 M H2SO4Middle 10000 circle voltage range of CV circulation: 0.25 ~ -0.35
V；10000 circle voltage range of CV circulation in 1M PBS: 0.7 ~ -0.8 V；10000 circle voltage range of CV circulation in 1M KOH:
1.1~ -1.0 V；10000 circle sweep speed of CV circulation: 50 mv/s.
Fig. 5 is RuCo@HCSs catalyst and contrast sample prepared by the embodiment of the present invention 1 ~ 7 -- commercialization Pt/C catalysis
Agent is respectively in 0.5 M H2SO4, 1 M PBS and liberation of hydrogen polarization curve in 1 M KOH solution, Tafel slope and circulation 10000
Enclose the liberation of hydrogen polarization curve of front and back；As can be seen from the figure: RuCo@HCSs catalyst prepared by embodiment 1 is in 1 M KOH and 1
Overpotential in M PBS solution is (in 10 mA cm of current density-2When, similarly hereinafter) it is 20 mV and 41 mV respectively, better than commercialization
Pt/C catalyst and other embodiments preparation catalyst；RuCo@HCSs catalyst prepared by embodiment 1 is in 0.5 M H2SO4
Overpotential in solution is 57 mV, close to commercialized Pt/C catalyst and better than the catalyst of other embodiments preparation；Implement
RuCo@HCSs catalyst prepared by example 1 is in 1 M KOH, 1 M PBS and 0.5 M H2SO4Tafel slope difference in solution
It is 30 mv/dec, 55 mv/dec and 46 mv/dec；RuCo@HCSs catalyst prepared by embodiment 1 is in 1 M KOH and 0.5
M H2SO4In solution after 10000 circle of CV circulation, overpotential has increased separately 4mV and 8mV, better than commercialization Pt/C catalyst；
RuCo@HCSs catalyst prepared by embodiment 1 is in 1 M PBS solution, and after 10000 circle of CV circulation, overpotential is increased
12mV presents good stability close to commercialization Pt/C catalyst (8mV).
(2) ammonia borane hydrolysis releases hydrogen reaction
Ammonia borane hydrolysis releases hydrogen test condition: 45 mg of ammonia borine, and 10 mg of catalyst tests solution: 0.5 M NaOH solution 10
mL；Test temperature: 298K, 308K, 318K and 328K.
Fig. 6 (a) is RuCo@HCSs catalyst and contrast sample prepared by the embodiment of the present invention 1 ~ 7 -- commercialization Pt/C
Ammonia borane hydrolysis of catalyst at a temperature of 298K releases hydrogen rate diagram；(b) the RuCo@HCSs catalyst that prepared by embodiment 1 is different
At a temperature of TOF；(c) ammonia borane hydrolysis releases hydrogen rate diagram under RuCo@HCSs catalyst different temperatures prepared by embodiment 1；(d)
The ammonia borane hydrolysis that RuCo@HCSs catalyst prepared by embodiment 1 recycles every time at 298K releases hydrogen rate diagram.It can from Fig. 6 (a)
To find out: RuCo@HCSs catalyst prepared by embodiment 1 has best ammonia borane hydrolysis ice thaw characteristics.It can be with from Fig. 6 (b)
Find out: as temperature increases, TOF is become larger；From Fig. 6 (d) it can be seen that RuCo@HCSs catalyst prepared by embodiment 1 follows
The activity that 81% is still kept after ring 7 times, shows fabulous stability.
Fig. 7 is the activation energy figure of RuCo@HCSs catalyst prepared by embodiment 1.As seen from the figure: the activation energy of catalyst is
19.11 KJ/mol。
Above-described embodiment elaborates the present invention.Certainly, foregoing invention is not limitation of the present invention, the present invention
Also not only limit and above-mentioned example, related technical personnel within the essential scope of the present invention made variation, retrofit, add and add deduct
It is few, also belong to protection scope of the present invention.
Claims (8)
1. a kind of bifunctional catalyst RuCo@HCSs, it is characterised in that: the bifunctional catalyst RuCo@HCSs is with hollow carbon
Ball is carrier, and RuCo alloy nano particle is covered by between hollow carbon sphere wall.
2. a kind of preparation method of bifunctional catalyst RuCo@HCSs as described in claim 1, which is characterized in that step is such as
Under:
(a), SiO is prepared using St ber method2Nanosphere；
(b), by SiO obtained2In the mixed solvent is added in nanosphere, sequentially adds ethyl orthosilicate, phenolic compound and hexadecane
The aqueous solution of aldehyde compound is added under stiring, then stirs for base trimethylammonium bromide, separates, dry, and intermediate compound I is made,
Labeled as SiO2@phenolic resin；The mixed solvent 1: 1 ~ 5 is made of by volume dehydrated alcohol and water；
(c), by SiO obtained2@phenolic resin roasts under an inert atmosphere, and intermediate II is made, and is labeled as SiO2@C；
(d), by SiO obtained2Metal precursor cobalt nitrate and ruthenium trichloride is added by the method for incipient impregnation in@C, then
It is dry, intermediate III is made, is labeled as SiO2@C@RuCo；
(e), by SiO obtained2@C@RuCo is roasted under an inert atmosphere, then with HF solution corrosion to get bifunctional catalyst,
Labeled as RuCo@HCSs.
3. preparation method as claimed in claim 2, it is characterised in that: in step (b), the phenolic compound is isophthalic two
Phenol, the aqueous solution of the aldehyde compound are the formalin of mass concentration 35 ~ 40%.
4. preparation method as claimed in claim 3, it is characterised in that: in step (b), in terms of mass volume ratio, SiO2Nanosphere
: mixed solvent: ethyl orthosilicate: resorcinol: cetyl trimethylammonium bromide: formalin=200 ~ 500 mg: 50 ~
70 mL:0.2~0.4 mL:0.25~ 0.3 g:0.3~0.4 g:0.6~0.8 mL；15 ~ 24 are stirred after formalin is added
h。
5. preparation method as claimed in claim 2, it is characterised in that: in step (c), carry out at roasting under an argon atmosphere
Reason, heating rate are 2 ~ 10 DEG C/min, and maturing temperature is 650 ~ 850 DEG C, and calcining time is 2 ~ 6 h.
6. preparation method as claimed in claim 2, it is characterised in that: in step (d), cobalt nitrate and trichlorine in metal precursor
The amount ratio for changing ruthenium guarantees that the mass ratio of Ru and Co is 1 ~ 3: 50.
7. preparation method as claimed in claim 2, it is characterised in that: in step (e), carry out at roasting under an argon atmosphere
Reason, heating rate are 1 ~ 10 DEG C/min, and maturing temperature is 450 ~ 650 DEG C, and calcining time is 1 ~ 6 h.
8. bifunctional catalyst RuCo@HCSs as described in claim 1 releases hydrogen as electrolysis water liberation of hydrogen or ammonia borane hydrolysis and urges
The application of agent.
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