CN108531932A - A kind of hollow carbon sphere encapsulation Ru nano particle electrolysis water catalyst and preparation method thereof - Google Patents
A kind of hollow carbon sphere encapsulation Ru nano particle electrolysis water catalyst and preparation method thereof Download PDFInfo
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- CN108531932A CN108531932A CN201810320972.7A CN201810320972A CN108531932A CN 108531932 A CN108531932 A CN 108531932A CN 201810320972 A CN201810320972 A CN 201810320972A CN 108531932 A CN108531932 A CN 108531932A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- 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
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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 electrolysis water catalyst preparation technical field, a kind of hollow carbon sphere encapsulation Ru NPs electrolysis water catalyst and preparation method thereof is disclosed.The catalyst is hollow carbon sphere structure, is inside packaged with Ru NPs.SiO is prepared using St ber methods2Nanosphere, with silane coupling agent to SiO2Nanosphere is modified；By quality ratio, SiO2Nanosphere: RuCl3=4 ~ 10: 1, by the SiO after modification2Nanosphere, RuCl3SiO is made in hydro-thermal reaction2@RuO2 L；In SiO2@RuO2 Phenolic resin is coated outside L, and SiO is made2@RuO2 L@phenolic resin；Roasting, HF solution etches obtain hollow carbon sphere encapsulation Ru NPs catalyst.Hollow carbon sphere prepared by the method for the present invention encapsulates Ru NPs catalyst, evolving hydrogen reaction（HER）Catalytic activity is high, and stability is good, at the same it is at low cost, be easy to industrialization.
Description
Technical field
The invention belongs to electrolysis water catalyst preparation technical fields, and in particular to a kind of hollow carbon sphere encapsulation Ru NPs electrolysis
Water catalyst and preparation method thereof.
Background technology
As traditional energy lays in increasingly depleted, the mankind have been devoted to the exploitation of new energy.Due to hydrogen energy density
Height, green non-pollution can be as outstanding energy carrier.In various hydrogen production process, evolving hydrogen reaction（HER）It is most economical to have
The method of effect.So far, Pt sills are considered as most effective HER catalyst, and catalytic activity, which has become, judges other
The touchstone of alternative catalysts.But high cost and low dynamics limit their large-scale production and large-scale commercial applications application.
Many researchs attempt exploitation and are based on transition metal（Including Ni, Mo, Co bases catalyst and its derivative such as-N ,-C and-S）Catalysis
Agent.Unfortunately, the not no facilitation of Pt, the above-mentioned catalyst with internal corrosion and oxidation sensitive cannot be fundamentally
Solve the problems, such as the low performance to HER.
In recent years, since there is porous carbon sill of sheet high-ratio surface, excellent electric conductivity and good physical chemistry to stablize
The characteristics such as property, have attracted the attention of researcher in electro-catalysis and energy conversion aspect.Even so, the catalysis of carbon nanomaterial is lived
Property is still not enough to compare favourably with metal_based material.Therefore, the carbon-based material that active component or metal phase are adjusted and activated
It is the attractive strategy for improving catalytic activity.For example, traditional doping hetero atom（N, P, S and B）Method can adjust carbon
The electronics and electrochemical properties of skeleton, but it is still very limited to the enhancing efficiency of HER.Although N doped carbons and base metal knot
Conjunction is also studied, but its intrinsic activity（TOF）And/or quality specific activity is also far below Pt catalyst.Therefore, very urgently
It needs to adjust and activate carbon using more effective and moderate cost method, to develop the new catalyst suitable for HER.
Invention content
In place of overcoming the shortcomings of the prior art, the purpose of the present invention is to provide a kind of hollow carbon spheres to encapsulate Ru
NPs（NPs, nano particle Nanoparticles's writes a Chinese character in simplified form）Electrolysis water catalyst and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of electrolysis water catalyst, the catalyst are hollow ball structure, are hollow carbon sphere structure, are inside packaged with Ru NPs.
Preparation method, steps are as follows：
（a）, using St ber methods prepare SiO2Nanosphere；
（b）, in anhydrous conditions, using toluene as solvent, with silane coupling agent to SiO2Nanosphere is modified；
（c）, by the SiO after modification2Nanosphere, RuCl3It is dissolved in mixed solvent I, then in 100 ~ 200 DEG C of hydro-thermal reactions
10 ~ 24 h are detached, dry, and intermediate compound I is made, and are labeled as SiO2@RuO2NPs；Wherein, by quality ratio, SiO2Nanosphere
∶RuCl3=4~10∶1；Mixed solvent I 1: 1 ~ 5 is made of by volume absolute ethyl alcohol and water, every 50 mg RuCl3, mixed solvent I
Dosage be 35 ~ 45 mL；
（d）, by SiO obtained2@RuO2 NPs is added in mixed solvent II, sequentially add ethyl orthosilicate, phenolic compound and
Cetyl trimethylammonium bromide is added the aqueous solution of aldehyde compound, then stirs under stiring, detaches, dry, in being made
Mesosome II is labeled as SiO2@RuO2NPs@phenolic resin；Wherein, mixed solvent II is by absolute ethyl alcohol and ammonium hydroxide by volume 30
The mass concentration of ~ 60: 1 composition, the ammonium hydroxide is 25 ~ 28 %；
（e）, by SiO obtained2@RuO2NPs@phenolic resin roasts under an inert atmosphere, and intermediate III is made, is labeled as
SiO2@Ru NPs@C；
（f）, by SiO obtained2@Ru NPs@C, which are dispersed in HF solution, to be etched, and hollow carbon sphere encapsulation Ru NPs catalyst is obtained,
Labeled as HCRN.
Preferably, step（d）In, the phenolic compound is resorcinol, and the aqueous solution of the aldehyde compound is matter
Measure the formalin of concentration 35 ~ 40%.
Preferably, step（d）In, in terms of mass volume ratio, SiO2@RuO2NPs: mixed solvent II: ethyl orthosilicate:
Benzenediol: 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 h are stirred after formalin is added.
Preferably, step（e）In, calcination process is carried out under an argon, and heating rate is 2 ~ 10 DEG C/min, roasting
Temperature is 650 ~ 850 DEG C, and roasting time is 2 ~ 6 h.
Preferably, step（f）In, the mass concentration of HF solution is 5 ~ 10 %, and the time of etching is 1 ~ 6 h.
Advantageous effect：Hollow carbon sphere prepared by the method for the present invention encapsulates Ru NPs catalyst, evolving hydrogen reaction（HER）It urges
Change that activity is high, and stability is good, at the same it is at low cost, be easy to industrialization.
Description of the drawings
Fig. 1：SiO prepared by the embodiment of the present invention 12Nanosphere, SiO2@RuO2 NPs、SiO2@RuO2NPs@phenolic resin,
SiO2The XRD spectrum of@Ru NPs@C and HCRN samples；
Fig. 2：SiO prepared by the embodiment of the present invention 12@RuO2The TEM of NPs schemes；
Fig. 3：The HAADF-STEM figures and energy spectrum diagram of HCRN samples prepared by the embodiment of the present invention 1；
Fig. 4：The HRTEM figures of HCRN samples prepared by the embodiment of the present invention 1；
Fig. 5：The N of HCRN samples prepared by the embodiment of the present invention 12Adsorption-desorption curve and graph of pore diameter distribution；
Fig. 6：The liberation of hydrogen polarization curve of HCRN samples and contrast sample Pt/C, Ru prepared by the embodiment of the present invention 1 ~ 11；
Fig. 7：The Tafel slope curve of HCRN samples and contrast sample Pt/C, Ru prepared by the embodiment of the present invention 1；
Fig. 8：Liberation of hydrogen polarization before and after 10000 circle of HCRN samples and contrast sample Pt/C, Ru cycle prepared by the embodiment of the present invention 1
Curve.
Specific implementation mode
To keep the present invention clearer, clear, technical scheme 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
A kind of preparation method of hollow carbon sphere encapsulation Ru NPs electrolysis water catalyst, steps are as follows：
（a）, using St ber methods prepare SiO2Nanosphere：The concentrated ammonia liquor of 10 mL mass concentrations, 28 %, 40 mL absolute ethyl alcohols,
50mL water is placed in 500 mL three-necked flasks, 1000 rpm of magnetic agitation, then measure 9 mL ethyl orthosilicates and 91 mL without
Water-ethanol is placed in 250 mL beakers, is poured into three-necked flask, and after 1000 rpm stir 1 min, rotating speed is adjusted to 260 rpm,
Stir 22 h, last centrifuge washing（Rotating speed is 8000 rpm, 5 min）, 60 DEG C of vacuum drying 6 h, obtained SiO2Nanosphere；
（b）、SiO2The modification of nanosphere：Weigh 1.5 g SiO2Nanosphere is placed in 100 mL three-necked flasks, be added 50 mL without
4.5 mL silane coupling agents are added in water-toluene, 30 min of ultrasonic disperse（KH550）, flow back 22 h at 135 DEG C of oil bath, finally from
The heart washs（Rotating speed is 8000 rpm, 5 min）, 60 DEG C of 6 h of vacuum drying；
（c）、SiO2@RuO2The preparation of NPs：Weigh the SiO of modification2Nanosphere 300mg, 50 mg RuCl3It is mixed to be dispersed in 40 mL
In bonding solvent I（Absolute ethyl alcohol: water=1: 1, volume ratio）, it is then transferred into 50 mL ptfe autoclaves, 150 DEG C of water
16 h of heat, after being cooled to room temperature, centrifuge washing（Rotating speed is 7000 rpm, 5 min）, 60 DEG C are dried in vacuo 6 h, are made intermediate
Body I is labeled as SiO2@RuO2NPs；
（d）、SiO2@RuO2The preparation of NPs@phenolic resin：Weigh 300 mg SiO2@RuO2It is molten that NPs is added to 62mL mixing
In agent II（Absolute ethyl alcohol: concentrated ammonia liquor=30 of 28 % of mass concentration: 1, volume ratio）, sequentially add 0.3 mL ethyl orthosilicates,
0.27 g Resorcinos and 0.33 g cetyl trimethylammonium bromides are transferred to 250 mL three-necked flasks after 30 min of ultrasound
In, the formalin of 0.75 mL mass concentrations 40% is added under mechanical stirring, 22 are stirred at room temperature, 500 rpm of rotating speed
H, centrifuge washing（Rotating speed is 7000 rpm, 3 min）, 60 DEG C of 6 h of vacuum drying, obtained intermediate II, labeled as SiO2@RuO2
NPs@phenolic resin；
（e）、SiO2The preparation of@Ru NPs@C：By SiO obtained2@RuO2NPs@phenolic resin roasts under an argon, heating
Rate is 3 DEG C/min, and calcination temperature is 850 DEG C, and roasting time is 2 h, and intermediate III is made, and is labeled as SiO2@Ru
NPs@C；
（f）, by SiO obtained2@Ru NPs@C, which are dispersed in the HF solution of 10 mL mass concentrations, 5 %, to be etched, and is obtained described
Hollow carbon sphere encapsulates Ru NPs catalyst, is labeled as HCRN.
Embodiment 2
Difference from example 1 is that：Step（c）In, the SiO of modification2The dosage of nanosphere is changed to 500 mg, that is, modifies
SiO2Nanosphere and RuCl3Mass ratio be changed to 10: 1, it is other with embodiment 1.
Embodiment 3
Difference from example 1 is that：Step（c）In, hydrothermal temperature is changed to 100 DEG C, other with embodiment 1.
Embodiment 4
Difference from example 1 is that：Step（c）In, hydrothermal temperature is changed to 200 DEG C, other with embodiment 1.
Embodiment 5
Difference from example 1 is that：Step（c）In, the hydro-thermal time is changed to 12 h, other with embodiment 1.
Embodiment 6
Difference from example 1 is that：Step（c）In, the hydro-thermal time is changed to 20 h, other with embodiment 1.
Embodiment 7
Difference from example 1 is that：Step（d）In, the volume ratio of absolute ethyl alcohol and ammonium hydroxide is changed to 60: 1, other same
Embodiment 1.
Embodiment 8
Difference from example 1 is that：Step（d）In, the time of stirring is changed to 24 h, other with embodiment 1.
Embodiment 9
Difference from example 1 is that：Step（e）In, the time of roasting is changed to 6 h, other with embodiment 1.
Embodiment 10
Difference from example 1 is that：Step（e）In, the temperature of roasting is changed to 750 DEG C, other with embodiment 1.
Embodiment 11
Difference from example 1 is that：Step（e）In, the temperature of roasting is changed to 650 DEG C, other with embodiment 1.
Catalyst structure characterizes
Fig. 1 is the SiO prepared by the embodiment of the present invention 12Nanosphere, SiO2@RuO2 NPs、SiO2@RuO2NPs@phenolic resin,
SiO2The XRD diagram of@Ru NPs@C and HCRN.Fig. 1 can be proved：The presence of armorphous carbon and simple substance Ru；In addition it can be seen that most
Afterwards in gained HCRN, SiO2It is corroded completely.
Fig. 2 is SiO prepared by the embodiment of the present invention 12@RuO2The transmission electron microscope picture of NPs.As can be seen from Figure 2：Utilize water
Hot method prepares SiO2@RuO2When NPs, SiO2Nanometer ball surface can equably load one layer of RuO2 NPs。
Fig. 3 is the HAADF-STEM figures of the HCRN prepared by the embodiment of the present invention 1（a-c）And energy spectrum diagram（d-f）.From Fig. 3 a
It can be seen that SiO2The carbon-based ball of monodisperse hollow is formd after etching, diameter is about 200 ~ 220 nm, and the thickness of carbon-coating is about
5 ~ 20 nm；From Fig. 3（e）With（f）It can be seen that：Ru NPs are evenly distributed in hollow carbon sphere.
Fig. 4 is the HRTEM figures of the HCRN prepared by the embodiment of the present invention 1.As can be seen from Figure 4：The diameter of Ru NPs is about
For 1 ~ 4 nm.
Fig. 5 is the N of the HCRN prepared by the embodiment of the present invention 12Adsorption-desorption curve and graph of pore diameter distribution.Known to：HCRN
It is 961 m to have the presence of a large amount of micropores, specific surface area2 g-1, pore volume is 0.78 cm3 g−1。
Catalyst performance is tested
Electrolysis water evolving hydrogen reaction catalytic performance test method：Using disk electrode three-electrode system carry out cyclic voltammetry, three
Electrode system is divided into working electrode, reference electrode and to electrode, and wherein saturated calomel electrode is reference electrode, platinum electrode conduct
To electrode, electrolyte is 1 M KOH solutions, and disk electrode rotating speed is 1600 rpm/min.
According to following preparation method preparation work electrode：Before catalyst sample test, first it is dried in vacuo 10 h for 60 DEG C, so
After weigh 3 mg catalyst samples be added 500 mL absolute ethyl alcohols in, be added 50 μ L, 5 wt % Nafion, 30 min of ultrasound,
15 μ L suspensions are measured with liquid-transfering gun to drop on the glass-carbon electrode of 5 mm of diameter, are dried at room temperature.
Meanwhile with the Pt/C catalyst of commercialized 20 wt% and metal simple-substance Ru catalyst as a comparison, according to above-mentioned
Method prepares control working electrode.
Test condition：Test temperature：Room temperature（25 ~ 28 ℃）；Linear sweep rate：2 mv/s；10000 circle of CV cycles
Voltage range：‒0.08 ~ 0.12 V（Relative to reversible hydrogen electrode）；10000 circle sweep speed of CV cycles：50 mv/s.
Fig. 6 is HCRN prepared by all embodiments of the invention and the liberation of hydrogen polarization curve of contrast sample Pt/C, Ru；From Fig. 6
It can be seen that：The corresponding overpotential of each sample is shown in Table 1.Known to：Current density is 10 mA/cm2When, prepared by embodiment 1
There is HCRN optimal hydrogen catalytic activity is precipitated.
Fig. 7 is the Tafel slope curve of the HCRN and contrast sample Pt/C, Ru prepared by the embodiment of the present invention 1；HCRN
Tafel slope be 50 mV/dec, the Tafel slope of Pt/C is 55 mV/dec, and the Tafel slope of Ru is 57 mV/
dec。
Fig. 8 is that the cycle 10000 of the HCRN and contrast sample Pt/C, Ru prepared by embodiment 1 enclose front and back liberation of hydrogen polarization
Curve.From figure 8, it is seen that after 10000 circle of HCRN cycles, overpotential increases 8 mV and Pt/C (6 mV) is close, excellent
In comparative catalyst Ru, good stability is presented.
Claims (6)
1. a kind of electrolysis water catalyst, it is characterised in that：The catalyst is hollow carbon sphere structure, is inside packaged with Ru NPs.
2. a kind of method preparing electrolysis water catalyst as described in claim 1, which is characterized in that steps are as follows：
（a）, using St ber methods prepare SiO2Nanosphere；
（b）, in anhydrous conditions, using toluene as solvent, with silane coupling agent to SiO2Nanosphere is modified；
（c）, by the SiO after modification2Nanosphere, RuCl3It is dissolved in mixed solvent I, then in 100 ~ 200 DEG C of hydro-thermal reactions 10
~ 24 h are detached, dry, and intermediate compound I is made, and are labeled as SiO2@RuO2NPs；Wherein, by quality ratio, SiO2Nanosphere:
RuCl3=4~10∶1；Mixed solvent I 1: 1 ~ 5 is made of by volume absolute ethyl alcohol and water, every 50 mg RuCl3, mixed solvent I
Dosage be 35 ~ 45 mL；
（d）, by SiO obtained2@RuO2NPs is added in mixed solvent II, sequentially add ethyl orthosilicate, phenolic compound and
Cetyl trimethylammonium bromide is added the aqueous solution of aldehyde compound, then stirs under stiring, detaches, dry, in being made
Mesosome II is labeled as SiO2@RuO2NPs@phenolic resin；Wherein, mixed solvent II is by absolute ethyl alcohol and ammonium hydroxide by volume 30
The mass concentration of ~ 60: 1 composition, the ammonium hydroxide is 25 ~ 28 %；
（e）, by SiO obtained2@RuO2NPs@phenolic resin roasts under an inert atmosphere, and intermediate III is made, is labeled as
SiO2@Ru NPs@C；
（f）, by SiO obtained2@Ru NPs@C, which are dispersed in HF solution, to be etched, and hollow carbon sphere encapsulation Ru NPs catalyst is obtained,
Labeled as HCRN.
3. preparation method as claimed in claim 2, it is characterised in that：Step（d）In, 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：Step（d）In, in terms of mass volume ratio, SiO2@RuO2
NPs: mixed solvent II: ethyl orthosilicate: resorcinol: cetyl trimethylammonium bromide: the mg of formalin=200 ~ 500
∶50~70 mL∶0.2~0.4 mL∶0.25~ 0.3 g∶0.3~0.4 g∶0.6~0.8 mL；15 are stirred after formalin is added
~ 24 h。
5. preparation method as claimed in claim 2, it is characterised in that：Step（e）In, calcination process is carried out under an argon,
Heating rate is 2 ~ 10 DEG C/min, and calcination temperature is 650 ~ 850 DEG C, and roasting time is 2 ~ 6 h.
6. preparation method as claimed in claim 2, it is characterised in that：Step（f）In, the mass concentration of HF solution is 5 ~ 10
The time of %, etching are 1 ~ 6 h.
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| CN111515409A (en) * | 2020-04-08 | 2020-08-11 | 大连理工大学 | Preparation method of carbon-coated magnetic nickel-cobalt core-shell structure microspheres |
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