CN109569651B - Dual-function catalyst RuCo @ HCSs and preparation method and application thereof - Google Patents
Dual-function catalyst RuCo @ HCSs and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 12
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- 238000001035 drying Methods 0.000 claims abstract description 8
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- 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
- 239000002243 precursor Substances 0.000 claims abstract description 6
- -1 aldehyde compound Chemical class 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
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 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
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 229920000557 Nafion® Polymers 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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 the technical field of catalyst preparation, and discloses a bifunctional catalyst RuCo @ HCSs as well as a preparation method and application thereof. The dual-function catalyst RuCo @ HCSs takes hollow carbon spheres as carriers, and RuCo alloy nano particles are coated between the walls of the hollow carbon spheres. Preparation of SiO by utilizing baby method2Nanospheres; the prepared SiO2Adding the nanosphere into the mixed solvent, sequentially adding ethyl orthosilicate, phenolic compound and hexadecyl trimethyl ammonium bromide, adding aqueous solution of aldehyde compound under stirring, separating, and drying to obtain SiO2@ phenolic resin; mixing SiO2Baking the @ phenolic resin in inert atmosphere to prepare SiO2@ C; mixing SiO2@ C adding metal precursors of cobalt nitrate and ruthenium trichloride by an isovolumetric impregnation method, and then drying to prepare SiO2@ C @ RuCo; mixing SiO2@ C @ RuCo is roasted in inert atmosphere and then corroded by HF solution, and the dual-function catalyst RuCo @ HCSs is obtained. The invention discloses application of a bifunctional catalyst RuCo @ HCSs as a catalyst for hydrogen evolution by electrolyzing water or hydrogen release by ammonia borane hydrolysis.
Description
Technical Field
The invention belongs to the technical field of preparation of catalysts for hydrogen evolution by electrolyzed water and hydrogen release by ammonia borane hydrolysis, and particularly relates to a bifunctional catalyst RuCo @ HCSs and a preparation method and application thereof.
Background
With the shortage of non-renewable resources (such as coal, petroleum, natural gas and the like), the problem of environmental pollution such as global warming is increasingly aggravated, and the development of green renewable energy sources is increasingly urgent. Among many new energy sources, hydrogen energy has received much attention as a clean, low-carbon energy source. Among them, the electrolysis of water to produce hydrogen and the hydrolysis of ammonia borane to release hydrogen are the most economical and efficient methods for converting and storing hydrogen. The main catalysts currently used for hydrogen production by electrolysis of water (HER) and hydrogen release by hydrolysis of ammonia borane are Pt-based catalysts. The Pt-based catalyst has high catalytic activity and good stability, but has the defects of high price and limited storage capacity, thus hindering the application and development of the Pt-based catalyst. Non-noble metals (Co, Ni, etc.) have a great advantage in terms of cost, but the catalytic activity needs to be improved.
Carbon materials have the advantages of high specific surface area, good electrical conductivity and the like, and are widely researched by researchers. The research of the carbon nano tube, the carbon nano sphere and the carbon nano fiber is mature day by day, and the carbon nano fiber has larger application potential in the catalyst. However, the catalytic activity of the carbon material is far from that of the metal, and some researches are focused on doping N, S and other heteroatoms to regulate the electron transfer of the carbon material, which has little effect. Therefore, it is of great significance to prepare novel bifunctional catalysts that are more efficient, more stable and less costly.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a bifunctional catalyst RuCo @ HCSs and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the dual-function catalyst RuCo @ HCSs take hollow carbon spheres as carriers, and RuCo alloy nano particles are coated between the walls of the hollow carbon spheres.
The preparation method comprises the following steps:
(a) preparation of SiO by the mini-barber method2Nanospheres;
(b) SiO to be obtained2Adding nanosphere into mixed solvent, sequentially adding ethyl orthosilicate, phenolic compound and hexadecyl trimethyl ammonium bromide, adding aqueous solution of aldehyde compound under stirring, separating, and drying to obtain intermediate I marked as SiO2@ phenolic resin; the mixed solvent consists of absolute ethyl alcohol and water according to the volume ratio of 1: 1-5;
(c) SiO to be obtained2@ phenolic resin in inertnessRoasting in atmosphere to obtain intermediate II marked as SiO2@C；
(d) SiO to be obtained2@ C adding metal precursors of cobalt nitrate and ruthenium trichloride by an isovolumetric impregnation method, and then drying to prepare an intermediate III which is marked as SiO2@C@RuCo；
(e) SiO to be obtained2@ C @ RuCo is roasted in inert atmosphere and then corroded by HF solution to obtain the bifunctional catalyst, which is marked as RuCo @ HCSs.
Preferably, in the step (b), the phenolic compound is resorcinol, and the aqueous solution of the aldehyde compound is a 35-40% by mass aqueous formaldehyde solution.
Preferably, in step (b), SiO is present in a mass to volume ratio2Nanospheres, mixed solvent, ethyl orthosilicate, resorcinol, cetyltrimethylammonium bromide and 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; adding a formaldehyde aqueous solution and stirring for 15-24 h.
Preferably, in the step (c), roasting treatment is carried out in an argon atmosphere, the heating rate is 2-10 ℃/min, the roasting temperature is 650-850 ℃, and the roasting time is 2-6 h.
Preferably, in the step (d), the mass ratio of the cobalt nitrate to the ruthenium trichloride in the metal precursor is ensured to be 1-3: 50.
Preferably, in the step (e), roasting treatment is carried out in an argon atmosphere, the heating rate is 1-10 ℃/min, the roasting temperature is 450-650 ℃, and the roasting time is 1-6 h.
The dual-function catalyst RuCo @ HCSs is applied to a catalyst for hydrogen evolution by electrolysis of water or hydrogen release by hydrolysis of ammonia borane.
Compared with the prior art, the invention has the following beneficial effects:
the bifunctional catalyst RuCo @ HCSs prepared by the method form alloy nanoparticles by using the noble metal Ru and the transition metal Co, so that the cost is reduced, and the synergistic catalytic action among the metals is fully exerted; in addition, the hollow carbon spheres are used as carriers, have porous and large specific surface area and good conductivity, can uniformly disperse RuCo alloy nanoparticles among the walls of the hollow carbon spheres and are beneficial to the mass transfer process; the RuCo alloy nano particles are loaded between the walls of the hollow carbon spheres, the dual-function between the metal particles and the hollow carbon spheres is fully utilized, and the catalytic activity and the stability of the dual-function catalyst are far superior to those of a single metal loaded or single-function catalyzed catalyst. The preparation method has the advantages of simple process, easily obtained raw materials and low cost, and is suitable for commercial production.
Drawings
FIG. 1: XRD spectrum of the RuCo @ HCSs catalyst prepared in example 1;
FIG. 2: TEM image of RuCo @ HCSs catalyst prepared in example 1;
FIG. 3: n of RuCo @ HCSs catalyst prepared in example 12Adsorption-desorption curves and pore size distribution maps;
FIG. 4: XPS plots of RuCo @ HCSs catalyst prepared in example 1;
FIG. 5: the RuCo @ HCSs catalysts prepared in the above behaviors in examples 1-7 and the Pt/C catalysts of the comparative samples are respectively 0.5M H2SO4Hydrogen evolution polarization curves in 1M PBS and 1M KOH; the RuCo @ HCSs catalyst prepared in the Medium behavior example 1 and the comparative sample Pt/C catalyst were respectively at 0.5M H2SO4Tafel slopes in 1M PBS and 1M KOH; the RuCo @ HCSs catalyst prepared in example 1 and the comparative sample Pt/C catalyst were each at 0.5M H2SO4Hydrogen evolution polarization curves before and after 10000 cycles of circulation in 1M PBS and 1M KOH;
FIG. 6: (a) graph of ammonia borane hydrolysis hydrogen release rate for RuCo @ HCSs catalyst prepared in example 1 and comparative sample Pt/C catalyst; (b) TOF of RuCo @ HCSs catalyst prepared in example 1 at different temperatures; (c) graph of ammonia borane hydrolysis hydrogen release rate at different temperatures for RuCo @ HCSs catalysts prepared in example 1; (d) ammonia borane hydrolysis hydrogen release rate chart circulating 7 times;
FIG. 7: activation energy profiles for RuCo @ HCSs catalysts prepared in example 1.
Detailed Description
In order to make the present invention clearer and clearer, the technical scheme of the present invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the bifunctional catalyst RuCo @ HCSs comprises the following steps:
(a) preparation of SiO by the mini-barber method2Nanospheres;
(b) SiO to be obtained2Adding 300 mg of nanosphere into 60 mL of mixed solvent (absolute ethyl alcohol: water = 1: 5, volume ratio), sequentially adding 0.3 mL of ethyl orthosilicate, 0.27 g of m-diphenol and 0.33 g of hexadecyl trimethyl ammonium bromide, adding 0.75 mL of 40% formaldehyde aqueous solution with stirring, stirring at room temperature and 500 rpm for 22 h, centrifugally washing (7000 rpm, 3 min), and drying in vacuum at 60 ℃ for 6 h to obtain intermediate I marked as SiO2@ phenolic resin;
(c) SiO to be obtained2@ phenolic resin is heated to 750 ℃ at the heating rate of 3 ℃/min under the argon atmosphere and is roasted for 2 h to prepare an intermediate II which is marked as SiO2@C；
(d) 400 mg of SiO2@ C is placed in a beaker, metal precursors of cobalt nitrate hexahydrate and ruthenium trichloride trihydrate are added by an isovolumetric impregnation method (the mass ratio of the cobalt nitrate hexahydrate to the ruthenium trichloride trihydrate ensures that the mass ratio of Ru to Co is 2: 50, the cobalt nitrate hexahydrate and the ruthenium trichloride trihydrate are dissolved in 700 mu L of water together, and are added into the beaker dropwise while shaking), and then the mixture is dried for 8 hours at 60 ℃ to prepare an intermediate III which is marked as SiO2@C@RuCo。
(e) SiO to be obtained2@ C @ RuCo is heated to 550 ℃ at the heating rate of 3 ℃/min under the argon atmosphere and is roasted for 2 h, and then, HF solution with the mass concentration of 5% is used for corrosion, so that the bifunctional catalyst is obtained and is marked as RuCo @ HCSs.
Example 2
The difference from example 1 is that: in the step (d), the amount of cobalt nitrate hexahydrate is kept unchanged, and the amount of ruthenium trichloride trihydrate is changed to ensure that the mass ratio of Ru to Co is 1: 50, and the rest is the same as in the example 1.
Example 3
The difference from example 1 is that: in the step (d), the amount of cobalt nitrate hexahydrate is kept unchanged, the amount of ruthenium trichloride trihydrate is changed, and the mass ratio of Ru to Co is changed to 3: 50, and the rest is the same as in the example 1.
Example 4
The difference from example 1 is that: in the step (e), the calcination temperature was changed to 450 ℃ and the procedure was otherwise the same as in example 1.
Example 5
The difference from example 1 is that: in the step (e), the calcination temperature was changed to 650 ℃ and the procedure was otherwise the same as in example 1.
Example 6
The difference from example 1 is that: in the step (e), the calcination time was changed to 1 hour, and the procedure was otherwise the same as in example 1.
Example 7
The difference from example 1 is that: in the step (e), the calcination time was changed to 6 hours, and the procedure was otherwise the same as in example 1.
Catalyst structural characterization
FIG. 1 is an XRD pattern of RuCo @ HCSs catalyst prepared in example 1 of the present invention. Fig. 1 can prove that: amorphous carbon and RuCo alloys.
FIG. 2 is a transmission electron micrograph of RuCo @ HCSs catalyst prepared in example 1 of the present invention. As can be seen from fig. 2: the RuCo alloy nano particles are uniformly distributed among the walls of the hollow carbon spheres, and the particle size is about 2-10 nm.
FIG. 3 is a N of RuCo @ HCSs catalyst prepared in example 1 of the present invention2Adsorption-desorption curve and aperture distribution diagram. As can be seen from fig. 3: the RuCo @ HCSs catalyst is of a porous structure and has a specific surface area of 1262 m2 g-1Pore volume of 1.17 cm3g−1The pore size distribution has a mesoporous peak at 3.3 nm.
FIG. 4 is an XPS plot of RuCo @ HCSs catalyst prepared in example 1 of the present invention. From the summary spectrum in the figure it can be seen that: the presence of Ru, Co and C.
Testing of catalyst Performance
(I) hydrogen evolution reaction
The catalyst prepared by the invention and a commercial 20 wt% Pt/C catalyst are subjected to cyclic voltammetry by adopting a three-electrode system, wherein the three-electrode system is divided into a working electrode, a reference electrode and a counter electrode, a saturated calomel electrode is used as the reference electrode, a carbon rod is used as the counter electrode, and hydrogen evolution reactions are respectively carried out at 0.5M H2SO41M PBS and 1M KOH solutions.
The working electrode was prepared according to the following preparation method: firstly, 3 mg of prepared catalyst sample is weighed and added into 300 mL of absolute ethyl alcohol, then 50 mu L of 5 wt% Nafion solution is added, ultrasonic treatment is carried out for 30 min, 10 mu L of suspension liquid is weighed by a liquid transfer gun and dropped on a glassy carbon electrode with the diameter of 4 mm, and drying is carried out at room temperature.
Hydrogen evolution test conditions: and (3) testing temperature: room temperature (25-28 ℃); linear scan rate: 2 mv/s; 0.5M H2SO4Medium LSV test voltage range: -0.8 to-1.5 mV; LSV test voltage range in 1M PBS: -0.4 to-1.1 mV; LSV test voltage range in 1M KOH: 0 to-0.65 mV; 0.5M H2SO4Medium CV cycle 10000 cycles voltage range: ‒ 0.25.25 to-0.35V; CV cycle 10000 cycles in 1M PBS voltage range: ‒ 0.7.7 to-0.8V; CV cycle 10000 cycles voltage range in 1M KOH: ‒ 1.1.1 to-1.0V; CV cycle 10000 cycles scan rate: 50 mv/s.
FIG. 5 shows that the RuCo @ HCSs catalysts prepared in examples 1-7 of the present invention and the commercial Pt/C catalyst of the comparative sample are respectively 0.5M H2SO4Hydrogen evolution polarization curves in 1M PBS and 1M KOH solution, tafel slope and hydrogen evolution polarization curves before and after 10000 cycles of circulation; as can be seen from the figure: overpotential (at current density of 10 mA cm) of RuCo @ HCSs catalyst prepared in example 1 in 1M KOH and 1M PBS solution-2The same applies hereinafter) were 20 mV and 41 mV, respectively, which are superior to the commercial Pt/C catalyst and the catalysts prepared in the other examples; the RuCo @ HCSs catalyst prepared in example 1 was at 0.5M H2SO4The overpotential in the solution was 57 mV, close to the commercial Pt/C catalyst and better than the catalysts prepared in the other examples; RuCo @ HCSs prepared in example 1The catalyst was in 1M KOH, 1M PBS and 0.5M H2SO4The Taffel slopes in the solution were 30 mv/dec, 55 mv/dec and 46 mv/dec, respectively; RuCo @ HCSs catalyst prepared in example 1 was prepared at 1M KOH and 0.5M H2SO4After the CV in the solution circulates 10000 circles, the overpotential is respectively increased by 4mV and 8mV, which is superior to the commercialized Pt/C catalyst; the RuCo @ HCSs catalyst prepared in example 1 showed good stability with an increase in overpotential of 12mV, approaching that of a commercial Pt/C catalyst (8 mV), in 1M PBS solution after 10000 CV cycles.
Hydrolytic hydrogen releasing reaction of (di) ammonia borane
Ammonia borane hydrolysis hydrogen release test conditions: ammonia borane 45 mg, catalyst 10 mg, test solution: 10 mL of 0.5M NaOH solution; and (3) testing temperature: 298K, 308K, 318K and 328K.
FIG. 6 (a) is a graph of the rate of ammonia borane hydrolysis hydrogen release at a temperature of 298K for RuCo @ HCSs catalysts prepared in examples 1-7 of the present invention and for a comparative sample, commercial Pt/C catalyst; (b) TOF of RuCo @ HCSs catalyst prepared in example 1 at different temperatures; (c) graph of ammonia borane hydrolysis hydrogen release rate at different temperatures for RuCo @ HCSs catalysts prepared in example 1; (d) graph of ammonia borane hydrolysis hydrogen release rate per cycle at 298K for RuCo @ HCSs catalyst prepared in example 1. As can be seen from fig. 6 (a): the RuCo @ HCSs catalyst prepared in example 1 has the best ammonia borane hydrolytic hydrogen release performance. As can be seen from fig. 6 (b): as the temperature increases, TOF gradually becomes larger; as can be seen from fig. 6 (d): the RuCo @ HCSs catalyst prepared in example 1 still maintained 81% of activity after 7 cycles, and showed excellent stability.
FIG. 7 is a graph of the activation energy of RuCo @ HCSs catalyst prepared in example 1. As can be seen from the figure: the activation energy of the catalyst was 19.11 KJ/mol.
The above examples illustrate the present invention in detail. It is to be understood that the above-described embodiments are not intended to limit the present invention, and the present invention is not limited to the above-described embodiments, and that various changes, modifications, additions and subtractions within the spirit and scope of the present invention may be made by those skilled in the art.
Claims (5)
1. A preparation method of a dual-function catalyst RuCo @ HCSs is characterized in that the dual-function catalyst RuCo @ HCSs takes hollow carbon spheres as carriers, RuCo alloy nano particles are coated between the walls of the hollow carbon spheres, and the preparation method comprises the following steps:
(a) preparation of SiO by the mini-barber method2Nanospheres;
(b) SiO to be obtained2Adding nanosphere into mixed solvent, sequentially adding ethyl orthosilicate, phenolic compound and hexadecyl trimethyl ammonium bromide, adding aqueous solution of aldehyde compound under stirring, separating, and drying to obtain intermediate I marked as SiO2@ phenolic resin; the mixed solvent consists of absolute ethyl alcohol and water according to the volume ratio of 1: 1-5;
(c) SiO to be obtained2The @ phenolic resin is roasted under inert atmosphere to prepare an intermediate II which is marked as SiO2@C；
(d) SiO to be obtained2@ C adding metal precursors of cobalt nitrate and ruthenium trichloride by an isovolumetric impregnation method, and then drying to prepare an intermediate III which is marked as SiO2@C@RuCo；
(e) SiO to be obtained2@ C @ RuCo is roasted in an inert atmosphere and then corroded by HF solution to obtain the bifunctional catalyst, and the bifunctional catalyst is marked as RuCo @ HCSs;
in the step (d), the dosage ratio of cobalt nitrate and ruthenium trichloride in the metal precursor ensures that the mass ratio of Ru to Co is 2: 50; in the step (e), roasting is carried out in an argon atmosphere, the heating rate is 3 ℃/min, the roasting temperature is 550 ℃, and the roasting time is 2 h.
2. The method of claim 1, wherein: in the step (b), the phenolic compound is resorcinol, and the aqueous solution of the aldehyde compound is 35-40% of formaldehyde aqueous solution.
3. The method of claim 1, wherein: in step (b), SiO is present in a mass/volume ratio2Nanospheres, mixed solvent, ethyl orthosilicate, resorcinol, cetyltrimethylammonium bromide and 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; adding a formaldehyde aqueous solution and stirring for 15-24 h.
4. The method of claim 1, wherein: in the step (c), roasting is carried out in an argon atmosphere, the heating rate is 2-10 ℃/min, the roasting temperature is 650-850 ℃, and the roasting time is 2-6 h.
5. The use of the bifunctional catalyst RuCo @ HCSs prepared by the preparation method as described in claim 1 as a catalyst for hydrogen release in ammonia borane hydrolysis.
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| CN111939930B (en) * | 2020-09-14 | 2023-04-21 | 郑州大学 | Carbon quantum dot supported cobalt-ruthenium alloy composite material and preparation method and application thereof |
| CN113649004B (en) * | 2021-07-07 | 2023-10-13 | 中国科学院合肥物质科学研究院 | Hollow carbon sphere supported metal particle catalyst and preparation method and application thereof |
| CN113755881A (en) * | 2021-09-10 | 2021-12-07 | 西北有色金属研究院 | Preparation method of carbon nano tube supported ruthenium-cobalt hydrogen evolution catalyst |
| CN114045522A (en) * | 2021-11-29 | 2022-02-15 | 中国石油大学(华东) | NiMo6-S @ HCS nano composite material, preparation method and application in electrocatalytic hydrogen production |
| CN114959771B (en) * | 2022-04-19 | 2023-10-20 | 南京信息工程大学 | Nickel-based electrocatalyst and hydrogen production synergistic formaldehyde wastewater degradation electrolytic cell |
| CN115770589A (en) * | 2022-11-24 | 2023-03-10 | 中国科学院深圳先进技术研究院 | Ultra-small stable platinum-cobalt nanoparticle catalyst, preparation method thereof and application thereof in selective hydrogenation |
| CN117045823B (en) * | 2023-10-11 | 2023-12-19 | 四川美文鑫彩新材料科技有限公司 | Mesoporous hollow copper single-atom carbon sphere, preparation method and application |
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