CN108531932B - Hollow carbon sphere packaged Ru nanoparticle electrolytic water catalyst and preparation method thereof - Google Patents
Hollow carbon sphere packaged Ru nanoparticle electrolytic water catalyst and preparation method thereof Download PDFInfo
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- CN108531932B CN108531932B CN201810320972.7A CN201810320972A CN108531932B CN 108531932 B CN108531932 B CN 108531932B CN 201810320972 A CN201810320972 A CN 201810320972A CN 108531932 B CN108531932 B CN 108531932B
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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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- 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 preparation of an electrolytic water catalyst, and discloses a hollow carbon sphere packaged Ru NPs electrolytic water catalyst and a preparation method thereof, wherein the catalyst is in a hollow carbon sphere structure, Ru NPs are packaged in the catalyst, and a Stöber method is adopted to prepare SiO2Nanospheres of SiO with silane coupling agent2Modifying the nanospheres; in terms of mass ratio, SiO2Nanosphere RuCl3= 4-10: 1, modifying the modified SiO2Nanospheres, RuCl3Hydrothermal reaction to obtain SiO2@RuO2L; in SiO2@RuO2Coating phenolic resin outside the L to obtain SiO2@RuO2L @ phenolic resin; and roasting and etching by HF solution to obtain the hollow carbon sphere packaged Ru NPs catalyst. The hollow carbon sphere packaged Ru NPs catalyst prepared by the method has high Hydrogen Evolution Reaction (HER) catalytic activity, good stability, low cost and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of preparation of an electrolytic water catalyst, and particularly relates to a hollow carbon sphere packaged Ru NPs electrolytic water catalyst and a preparation method thereof.
Background
With the depletion of traditional energy reserves, mankind has been working on the development of new energy. The hydrogen has high energy density, is green and pollution-free, and can be used as an excellent energy carrier. Among the various hydrogen production processes, the Hydrogen Evolution Reaction (HER) is the most cost effective process. To date, Pt-based materials have been considered the most effective HER catalysts, and their catalytic activity has been the candidate for judging other alternative catalysts. But their high cost and low kinetics limit their large-scale production and large-scale commercial applications. Many studies have attempted to develop transition metal-based (including Ni, Mo, Co-based catalysts and their derivatives such as-N, -C and-S) catalysts. Unfortunately, without the promotion of Pt, the above-described catalysts with inherent corrosion and oxidation sensitivity do not fundamentally solve the problem of low performance on HER.
In recent years, porous carbon-based materials have attracted attention from researchers in terms of electrocatalysis and energy conversion due to their characteristics such as high specific surface area, excellent electrical conductivity, and good physicochemical stability. Even so, the catalytic activity of carbon nanomaterials is still insufficient to be comparable to metal-based materials. Therefore, carbon-based materials with active component or metal phase conditioning and activation are an attractive strategy to improve catalytic activity. For example, traditional heteroatom doping (N, P, S and B) approaches can modulate the electronic and electrochemical properties of the carbon backbone, but the enhancement efficiency to HER is still very limited. Although N-doped carbon has also been investigated in combination with non-noble metals, its intrinsic activity (TOF) and/or mass specific activity is also much lower than for Pt catalysts. Therefore, there is a great need to modulate and activate carbon using more efficient and moderate cost methods to develop new catalysts suitable for HER.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a hollow carbon sphere-encapsulated RuNPs (NPs, short for nanoparticle Nanoparticles) electrolytic water catalyst and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the electrolytic water catalyst is of a hollow sphere structure and a hollow carbon sphere structure, and RuNPs are packaged in the catalyst.
The preparation method comprises the following steps:
(a) preparation of SiO by the Stöber process2Nanospheres;
(b) under anhydrous condition, toluene is used as solvent, and silane coupling agent is used for coupling SiO2Modifying the nanospheres;
(c) and modifying the modified SiO2Nanospheres, RuCl3Dissolving the mixture in a mixed solvent I, carrying out hydrothermal reaction for 10-24 h at 100-200 ℃, separating and drying to obtain an intermediate I, wherein the label is SiO2@RuO2NPs; wherein, by mass ratio, SiO2Nanosphere RuCl3= 4-10: 1; the mixed solvent I is composed of absolute ethyl alcohol and water according to the volume ratio of 1: 1-5, and each 50 mg of RuCl3The dosage of the mixed solvent I is 35-45 mL;
(d) SiO to be obtained2@RuO2NPs are added into the mixed solvent II, ethyl orthosilicate, phenolic compounds and hexadecyl trimethyl ammonium bromide are sequentially added, aqueous solution of aldehyde compounds is added under stirring, and then stirring, separation and drying are carried out to obtain an intermediate II, which is marked as SiO2@RuO2NPs @ phenolic resin; wherein the mixed solvent II consists of absolute ethyl alcohol and ammonia water according to the volume ratio of 30-60: 1, and the mass concentration of the ammonia water is 25-28%;
(e) SiO to be obtained2@RuO2The NPs @ phenolic resin is roasted in inert atmosphere to prepare an intermediate III which is marked as SiO2@Ru NPs@C；
(f) SiO to be obtained2And @ Ru NPs @ C is dispersed in HF solution and etched to obtain the hollow carbon sphere packaged Ru NPs catalyst which is marked as HCRN.
Preferably, in the step (d), 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 (d), SiO is present in a mass to volume ratio2@RuO2NPs, mixed solvent II, ethyl orthosilicate, resorcinol, hexadecyl trimethyl ammonium 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 (e), 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.
Preferably, in the step (f), the mass concentration of the HF solution is 5-10%, and the etching time is 1-6 h.
Has the advantages that: the hollow carbon sphere packaged Ru NPs catalyst prepared by the method has high Hydrogen Evolution Reaction (HER) catalytic activity, good stability, low cost and easy industrialization.
Drawings
FIG. 1: SiO prepared in example 1 of the invention2Nanospheres, SiO2@RuO2NPs、SiO2@RuO2NPs @ phenolic resin, SiO2XRD spectra of @ Ru NPs @ C and HCRN samples;
FIG. 2: SiO prepared in example 1 of the invention2@RuO2TEM image of NPs;
FIG. 3: HAADF-STEM and energy spectra of HCRN samples prepared in example 1 of the invention;
FIG. 4: HRTEM of HCRN samples prepared in example 1 of the present invention;
FIG. 5: n of HCRN samples prepared in inventive example 12Adsorption-desorption curves and pore size distribution maps;
FIG. 6: the hydrogen evolution polarization curves of the HCRN samples prepared in examples 1-11 of the invention and the comparative sample Pt/C, Ru;
FIG. 7: the tafel slope curves of the HCRN sample prepared in example 1 of the present invention and the comparative sample Pt/C, Ru;
FIG. 8: the hydrogen evolution polarization curves of the HCRN sample prepared in the invention example 1 and the Pt/C, Ru comparative sample before and after 10000 cycles.
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
A preparation method of a hollow carbon sphere packaged Ru NPs water electrolysis catalyst comprises the following steps:
(a) preparation of SiO by the Stöber process2Nanosphere: 10 mL of concentrated ammonia water with the mass concentration of 28%, 40mL of absolute ethyl alcohol and 50mL of water are placed in a 500 mL three-neck flask, magnetic stirring is carried out at 1000 rpm, then 9 mL of tetraethoxysilane and 91mL of absolute ethyl alcohol are measured and placed in a 250 mL beaker, the mixture is poured into the three-neck flask, the rotation speed is adjusted to 260rpm after stirring is carried out at 1000 rpm for 1 min, stirring is carried out for 22 h, finally centrifugal washing is carried out (the rotation speed is 8000 rpm, 5 min), vacuum drying is carried out at 60 ℃ for 6 h, and SiO is prepared2Nanospheres;
（b）、SiO2modification of nanospheres: 1.5 g of SiO are weighed2Placing the nanospheres into a 100 mL three-neck flask, adding 50mL anhydrous toluene, ultrasonically dispersing for 30 min, adding 4.5 mL silane coupling agent (KH 550), refluxing in oil at 135 ℃ for 22 h, finally centrifuging and washing (rotating speed of 8000 rpm, 5 min), and vacuum drying at 60 ℃ for 6 h;
（c）、SiO2@RuO2preparation of NPs: weighing modified SiO2Nanosphere 300mg, 50 mg RuCl3Dispersing in 40mL of mixed solvent I (absolute ethyl alcohol: water = 1: 1, volume ratio), transferring into a 50mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 16 h, cooling to room temperature, carrying out centrifugal washing (rotating speed of 7000 rpm, 5 min), and carrying out vacuum drying at 60 ℃ for 6 h to obtain an intermediate I, wherein the label is SiO2@RuO2NPs；
（d）、SiO2@RuO2Preparation of NPs @ phenolic resin: weighing 300mg SiO2@RuO2NPs were added to 62mL of the mixed solvent II (absolute ethanol: 28% by mass)Concentrated ammonia = 30: 1, volume ratio), then adding 0.3 mL of ethyl orthosilicate, 0.27 g of m-diphenol and 0.33 g of hexadecyl trimethyl ammonium bromide in sequence, carrying out ultrasonic treatment for 30 min, transferring the mixture into a 250 mL three-neck flask, adding 0.75 mL of 40% formaldehyde aqueous solution under mechanical stirring, stirring the mixture for 22 h at room temperature and 500 rpm, carrying out centrifugal washing (7000 rpm and 3 min), and carrying out vacuum drying at 60 ℃ for 6 h to obtain an intermediate II marked as SiO2@RuO2NPs @ phenolic resin;
（e）、SiO2preparation of @ Ru NPs @ C: the prepared SiO2@RuO2The NPs @ phenolic resin is roasted in argon atmosphere at the temperature rise rate of 3 ℃/min, the roasting temperature of 850 ℃ and the roasting time of 2 h to prepare an intermediate III which is marked as SiO2@RuNPs@C；
(f) SiO to be obtained2And the @ Ru NPs @ C is dispersed in 10 mL HF solution with the mass concentration of 5% and etched to obtain the hollow carbon sphere packaged Ru NPs catalyst, and the label is HCRN.
Example 2
The difference from example 1 is that: in step (c), the modified SiO2The dosage of the nanosphere is changed to 500 mg, namely modified SiO2Nanospheres and RuCl3The mass ratio of (A) to (B) was changed to 10: 1, and the same procedures as in example 1 were repeated.
Example 3
The difference from example 1 is that: in the step (c), the hydrothermal temperature was changed to 100 ℃ and the procedure was otherwise the same as in example 1.
Example 4
The difference from example 1 is that: in the step (c), the hydrothermal temperature was changed to 200 ℃ and the procedure was otherwise the same as in example 1.
Example 5
The difference from example 1 is that: in the step (c), the hydrothermal time was changed to 12 hours, and the procedure was otherwise the same as in example 1.
Example 6
The difference from example 1 is that: in the step (c), the hydrothermal time was changed to 20 hours, and the procedure was otherwise the same as in example 1.
Example 7
The difference from example 1 is that: in the step (d), the volume ratio of the absolute ethanol to the aqueous ammonia was changed to 60: 1, and the rest was the same as in example 1.
Example 8
The difference from example 1 is that: in step (d), the stirring time was changed to 24 hours, and the procedure was otherwise the same as in example 1.
Example 9
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.
Example 10
The difference from example 1 is that: in the step (e), the calcination temperature was changed to 750 ℃ and the procedure was otherwise the same as in example 1.
Example 11
The difference from example 1 is that: in the step (e), the calcination temperature was changed to 650 ℃ and the same procedure as in example 1 was repeated.
Catalyst structural characterization
FIG. 1 is SiO as prepared in example 1 of the present invention2Nanospheres, SiO2@RuO2NPs、SiO2@RuO2NPs @ phenolic resin, SiO2XRD patterns of @ Ru NPs @ C and HCRN. Fig. 1 can prove that: the existence of amorphous carbon and elementary substance Ru; in addition, it can be seen that SiO is contained in the HCRN obtained finally2Is completely corroded.
FIG. 2 is SiO prepared according to example 1 of the present invention2@RuO2Transmission electron microscopy images of NPs. As can be seen from fig. 2: preparation of SiO by hydrothermal method2@RuO2NPs, SiO2The surface of the nanosphere can be uniformly loaded with a layer of RuO2NPs。
FIG. 3 is HAADF-STEM graphs (a-c) and energy spectra (d-f) of HCRNs prepared in example 1 of the present invention. As can be seen from FIG. 3a, SiO2Forming monodisperse hollow carbon-based spheres after etching, wherein the diameter of the spheres is about 200-220 nm, and the thickness of the carbon layer is about 5-20 nm; as can be seen from fig. 3 (e) and (f): the Ru NPs are uniformly distributed in the hollow carbon spheres.
FIG. 4 is a HRTEM image of HCRN prepared in example 1 of the present invention. As can be seen from fig. 4: the diameter of the Ru NPs is about 1-4 nm.
FIG. 5 is N of HCRN prepared in example 1 of the present invention2Adsorption-desorption curve and aperture distribution diagram. Therefore, the following steps are carried out: HCRN has a large number of micropores and a specific surface area of 961 m2g-1Pore volume of 0.78 cm3g−1。
Testing of catalyst Performance
The method for evaluating the catalytic performance of the electrolytic water hydrogen evolution reaction comprises the following steps: a circular disk electrode three-electrode system is adopted for cyclic voltammetry testing, the three-electrode system is divided into a working electrode, a reference electrode and a counter electrode, wherein a saturated calomel electrode is the reference electrode, a platinum wire electrode is the counter electrode, electrolyte is 1M KOH solution, and the rotating speed of the circular disk electrode is 1600 rpm/min.
The working electrode was prepared according to the following preparation method: before testing the catalyst sample, vacuum drying at 60 ℃ for 10 h, then weighing 3 mg of the catalyst sample, adding the catalyst sample into 500 mL of absolute ethyl alcohol, adding 50 mu L of 5 wt% Nafion, carrying out ultrasonic treatment for 30 min, weighing 15 mu L of suspension liquid drop on a glassy carbon electrode with the diameter of 5 mm by using a liquid transfer gun, and drying at room temperature.
Meanwhile, a control working electrode was prepared as described above with a commercial 20 wt% Pt/C catalyst and elemental metal Ru as comparative catalysts.
And (3) testing conditions are as follows: and (3) testing temperature: room temperature (25-28 ℃); linear scan rate: 2 mv/s; CV cycle 10000 voltage range: ‒ 0.08.08-0.12V (relative to the reversible hydrogen electrode); CV cycle 10000 cycles scan rate: 50 mv/s.
FIG. 6 is a hydrogen evolution polarization curve for HCRN prepared according to all examples of the invention and for a comparative sample Pt/C, Ru; as can be seen from fig. 6: the overpotentials for each sample are shown in table 1. Therefore, the following steps are carried out: the current density is 10 mA/cm2The HCRN prepared in example 1 had the best hydrogen evolution catalytic activity.
FIG. 7 is a Tafel slope plot of HCRN prepared according to example 1 of the present invention and comparative sample Pt/C, Ru; the Taffel slope of HCRN is 50 mV/dec, that of Pt/C is 55 mV/dec, and that of Ru is 57 mV/dec.
FIG. 8 is a hydrogen evolution polarization curve before and after 10000 cycles of HCRN prepared in example 1 and Pt/C, Ru as a comparative sample. As can be seen from FIG. 8, after the HCRN cycles 10000 cycles, the overpotential is increased by 8 mV, which is similar to Pt/C (6 mV), and is superior to that of the comparative catalyst Ru, showing good stability.
Claims (5)
1. A preparation method of an electrolytic water catalyst, wherein the catalyst is in a hollow carbon sphere structure and Ru NPs are packaged in the catalyst, and the preparation method is characterized by comprising the following steps:
(a) preparation of SiO by the Stöber process2Nanospheres;
(b) under anhydrous condition, toluene is used as solvent, and silane coupling agent is used for coupling SiO2Modifying the nanospheres;
(c) and modifying the modified SiO2Nanospheres, RuCl3Dissolving the mixture in a mixed solvent I, carrying out hydrothermal reaction for 10-24 h at 100-200 ℃, separating and drying to obtain an intermediate I, wherein the label is SiO2@RuO2NPs; wherein, by mass ratio, SiO2Nanosphere RuCl3= 4-10: 1; the mixed solvent I is composed of absolute ethyl alcohol and water according to the volume ratio of 1: 1-5, and each 50 mg of RuCl3The dosage of the mixed solvent I is 35-45 mL;
(d) SiO to be obtained2@RuO2NPs are added into the mixed solvent II, ethyl orthosilicate, phenolic compounds and hexadecyl trimethyl ammonium bromide are sequentially added, aqueous solution of aldehyde compounds is added under stirring, and then stirring, separation and drying are carried out to obtain an intermediate II, which is marked as SiO2@RuO2NPs @ phenolic resin; wherein the mixed solvent II consists of absolute ethyl alcohol and ammonia water according to the volume ratio of 30-60: 1, and the mass concentration of the ammonia water is 25-28%;
(e) SiO to be obtained2@RuO2Roasting the NPs @ phenolic resin in an inert atmosphere at the roasting temperature of 650-850 ℃ for 2-6 h to obtain an intermediateIII, mark SiO2@Ru NPs@C；
(f) SiO to be obtained2And @ Ru NPs @ C is dispersed in HF solution and etched to obtain the hollow carbon sphere packaged Ru NPs catalyst which is marked as HCRN.
2. The method of claim 1, wherein: in the step (d), 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 (d), SiO is present in a mass to volume ratio2@RuO2NPs, mixed solvent II, ethyl orthosilicate, resorcinol, hexadecyl trimethyl ammonium 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 (e), roasting treatment is carried out in an argon atmosphere, and the heating rate is 2-10 ℃/min.
5. The method of claim 1, wherein: in the step (f), the mass concentration of the HF solution is 5-10%, and the etching time is 1-6 h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721075A (en) * | 2005-05-24 | 2006-01-18 | 南京大学 | Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls |
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| CN105502342A (en) * | 2016-01-07 | 2016-04-20 | 上海工程技术大学 | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source |
| CN105694356A (en) * | 2016-03-14 | 2016-06-22 | 北京科技大学 | Porous hollow phenolic resin nanospheres and carbon nanospheres and preparation method |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN107597143A (en) * | 2017-09-25 | 2018-01-19 | 东华大学 | A kind of metal nanoparticle is uniformly embedded into the controllable method for preparing of the elctro-catalyst of mesoporous carbon spheres internal structure |
| CN107867726A (en) * | 2016-09-27 | 2018-04-03 | 北京化工大学 | A kind of preparation method of nano oxidized ruthenium |
| CN108043437A (en) * | 2017-11-09 | 2018-05-18 | 国家电网公司 | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst |
-
2018
- 2018-04-11 CN CN201810320972.7A patent/CN108531932B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721075A (en) * | 2005-05-24 | 2006-01-18 | 南京大学 | Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls |
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| CN105502342A (en) * | 2016-01-07 | 2016-04-20 | 上海工程技术大学 | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN105694356A (en) * | 2016-03-14 | 2016-06-22 | 北京科技大学 | Porous hollow phenolic resin nanospheres and carbon nanospheres and preparation method |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN107867726A (en) * | 2016-09-27 | 2018-04-03 | 北京化工大学 | A kind of preparation method of nano oxidized ruthenium |
| CN107597143A (en) * | 2017-09-25 | 2018-01-19 | 东华大学 | A kind of metal nanoparticle is uniformly embedded into the controllable method for preparing of the elctro-catalyst of mesoporous carbon spheres internal structure |
| CN108043437A (en) * | 2017-11-09 | 2018-05-18 | 国家电网公司 | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Tumelo N. Phaahlamohlaka等.Effects of Co and Ru Intimacy in Fischer−Tropsch Catalysts UsingHollow Carbon Sphere Supports: Assessment of the Hydrogen Spillover Processes.《ACS Catal》.2016,(第7期), * |
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