CN112246288A - Preparation method of supported noble metal catalyst based on plasma - Google Patents
Preparation method of supported noble metal catalyst based on plasma Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012876 carrier material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000009832 plasma treatment Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
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- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- -1 tungsten nitride Chemical class 0.000 claims description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 2
- 229910039444 MoC Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 206010001497 Agitation Diseases 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
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- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 229910009819 Ti3C2 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
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- 230000009467 reduction Effects 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
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- 239000000446 fuel Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000012943 hotmelt Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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Abstract
The invention relates to a preparation method of a plasma-based supported noble metal catalyst. The preparation method comprises the following steps: 1) and treating the carrier by plasma under different atmospheres to synthesize the defect and doped carrier material. 2) The defect or doping carrier material is immersed into the solution containing noble metal salt, and the noble metal is reduced and deposited on the surface of the carrier by stirring. 3) And washing and drying to prepare the supported noble metal catalyst. The preparation method has the advantages of convenient and fast process, simplicity, high efficiency, selectable and strong controllability of various conditions, wide application and preparation range, capability of synthesizing single or various noble metal alloy supported materials, adjustable proportional components, easiness in amplified preparation and capability of effectively reducing the cost. The synthesized supported noble metal catalyst can be applied to various types of catalytic reactions or electrocatalytic reactions, such as micromolecular redox reactions and the like, achieves better performance than commercial noble metals, and has wider application prospect.
Description
Technical Field
The invention relates to a preparation method of a plasma-based supported noble metal catalyst, belonging to the technical field of catalyst synthesis.
Background
Catalysis and electrocatalysis play a huge role in modern chemical and energy industriesAnd (4) acting. It is understood that more than about 90% of the chemical industry products are derived from catalytic and electrocatalytic processes. For example, various alcohols, acetone and other chemical basic raw materials can be further synthesized from fossil energy (coal and petroleum) through catalysis, and further, various artificial products such as fibers, plastics, rubber, fertilizers, medicines and the like can be synthesized. For another example, by electrocatalysis, various small molecules can be converted, driving their application in energy conversion, such as CO2Electroreduction to various organic fuels, N2The application of electro-reduction to ammonia, electrolysis of water to produce hydrogen, and electro-oxidation of organic matter in fuel cells. The catalyst is the core of these catalytic and electrocatalytic processes, determining the rate and energy consumption of these reaction processes. Among various catalysts, the noble metal catalyst has good adsorption performance on reactants due to the unique unfilled d-track structure, has moderate strength, and is beneficial to forming intermediate compounds in various activated states, thereby being beneficial to the catalytic and electrocatalytic processes. In addition, the noble metal material also has the performances of high temperature resistance, oxidation resistance, corrosion resistance and the like, and is one of the most ideal choices among a plurality of catalysts. Common noble metal catalysts include platinum, palladium, rhodium, gold, ruthenium, and the like. The size of the particles, the surface structure and the state of dispersion, and the interaction with the support, all affect the performance of the noble metal catalyst.
At present, many methods for synthesizing catalysts have been developed at home and abroad, and the methods are commonly known as impregnation, precipitation, blending, thermal decomposition, leaching, hot-melt, electrolysis, ion exchange, and peptization. Some of these methods are complicated in process, lack effective control over surface structure and dispersibility, and have high requirements for equipment and energy consumption. It is particularly important to develop new, simple, scalable, and universal methods of preparation. The invention utilizes plasma to manufacture defects and doped surface structures on a carrier, and prepares various supported noble metal catalyst materials through a simple mixing process and a weak reducing agent. The method can realize simple preparation of various noble metal catalysts, is favorable for scale-up production, and has a certain regulation and control function on the surface atomic structure, especially atomic dispersity, of the prepared noble metal, so that the performance of the supported noble metal catalyst can be better regulated and controlled, and the method has important significance for development of the catalyst.
Disclosure of Invention
The invention aims to develop a simple and effective preparation method of a novel supported noble metal catalyst with adjustable atomic structure and dispersibility, and realize the application of the supported noble metal catalyst in various catalytic reactions and electrocatalytic reactions. The invention provides a plasma synthesis method of a supported noble metal catalyst and application thereof, and the typical synthesis characteristic is that transition metal ions are self-adsorbed to the surface of a carrier for deposition. Its typical structural features are a support with surface defects and heteroatom doping, and a noble metal with atomic/nanoscale dispersion. The typical performance characteristics are the regulation of the electronic structure of the active center on the surface of the noble metal by doping/defects and the synergistic effect in the catalytic/electrocatalytic process.
The process of plasma synthesis of supported noble metal catalysts generally requires the following steps:
1) the carrier material is firstly treated by deionized water, acetone or ethanol for 1 hour by ultrasonic and dried. This step is used to remove surface impurities;
the carrier material is a carbon carrier or a metal compound carrier;
the carbon carrier is graphene, bp2000 activated carbon, XC-72R activated carbon, carbon cloth or carbon paper;
the metal compound carrier is titanium dioxide, aluminum oxide, iron/cobalt/nickel oxide, stannic oxide, tungsten trioxide, titanium nitride, titanium carbide, molybdenum oxide, molybdenum carbide, molybdenum nitride, tungsten carbide or tungsten nitride.
2) Placing the carrier material subjected to ultrasonic treatment in plasma treatment equipment, vacuumizing, introducing specific gas, and performing plasma treatment, wherein the carrier material is turned over or stirred for 1-6 times in the plasma treatment process;
the specific gas is nitrogen, argon, ammonia, hydrogen, oxygen or air;
the plasma treatment lasts for 0.1-24 hours;
and introducing specific gas, wherein the gas flow rate is controlled to be 5-200 sccm.
3) One or more noble metal salts containing noble metals are dissolved in a selected solvent in an amount of 1-1000 mg per 100ml of the selected solvent, and a weak reducing agent in an amount of 0-0.5 vol/ml is added as required. For partial insoluble precious metal salt, adjusting the acidity of the solution to completely dissolve the precious metal salt;
the noble metal is Pt, Ir, Au, Ru, Pd or Rh;
the noble metal salt is chloride, nitrate or acetylacetone salt;
the selected solvent is deionized water, ethanol, acetone or ethylene glycol;
the weak reducing agent is formaldehyde, acetaldehyde, formic acid or ascorbic acid, thereby ensuring that the noble metal is reduced and deposited on the surface of the carrier to be fully loaded.
4) Immersing the carrier material treated in the step 2) into a noble metal salt solution for carrying out a load reaction at 0-100 ℃. Carrying out ultrasonic stirring treatment on the powder carrier material, and carrying out common stirring treatment on the blocky/flaky carrier material;
the ultrasonic stirring treatment is carried out, wherein the stirring treatment time is 0.5 hour to 7 days;
and the stirring speed is 100-1000 r/min by common stirring.
5) And (3) washing and filtering the sample obtained in the step (4) for 3-5 times by using deionized water, and drying to obtain the supported noble metal catalyst.
Compared with the existing synthesis method of the supported noble metal catalyst and the synthesized supported noble metal catalyst, the plasma preparation method of the supported noble metal catalyst and the prepared material have the following obvious synthesis and structural characteristics:
(1) in the preparation process of a general supported noble metal catalyst, a carrier needs to be pretreated firstly, and then noble metal is deposited on the carrier under certain conditions through various deposition means, so that the synthesis process is complicated. The plasma synthesis method related in the patent is simple to operate and has low requirements on condition control. In many cases, after the carrier is subjected to plasma treatment, the loading of the noble metal on the carrier can be completed through one-step self-reduction and deposition processes, the requirement on equipment conditions is low, the loading can be realized through an ultrasonic or stirring process under conventional conditions, the whole controllability is high, and the expanded production is facilitated.
(2) In general, a surfactant or a precisely controlled reduction process is needed in the synthesis process to realize the control of atoms and nanostructures in the supported noble metal catalyst. In the patent, the plasma preparation method realizes the self-reduction and deposition process of noble metal ions at the defect or doping site through atomic-scale defect/doping, and further realizes the control of the atomic-scale structure of the noble metal catalyst and the control of the dispersity on the surface of the carrier.
(3) As described above, based on the control of the atomic structure and the surface dispersibility of the surface of the noble metal, an optimizable electronic structure can be provided in the design of the catalyst, and a possible carrier synergistic effect can be provided in the catalytic process, so that a basis is provided for the preparation of the high-activity supported noble metal catalyst.
The plasma preparation method of the supported noble metal catalyst can effectively prepare various high-activity noble metal-based catalysts, has the advantages of simple synthesis, wide applicability and the like, and has high practical value and application prospect for the preparation of the supported noble metal electrocatalyst.
Drawings
FIG. 1 is a graph showing the performance of oxygen evolution by electrolytic water of a sample of Ru/C electrocatalyst powder prepared in example 2;
FIG. 2 is an SEM representation of the Ru/C catalyst prepared in example 2.
Detailed Description
The technical solution of the present invention is further explained by way of embodiments with reference to the accompanying drawings.
Example 1
Preparation of supported Au catalyst by carbon cloth plasma treatment
1. Commercially available hydrophilic carbon cloth is cut into a strip shape, and the area for loading noble metal in the middle is 1 x 1 cm. Immersing the carbon cloth in ethanol for ultrasonic treatment for 1 hour, and drying for later use;
2. the ultrasonically treated carbon cloth was placed in a plasma cleaner. After vacuum pumping, argon gas is introduced for plasma treatment for 4 hours, and then the argon gas is introduced for maintaining the speed of 100 sccm. Turning over the carbon cloth for 3 times in the treatment process;
3. preparing 18.9 mM chloroauric acid aqueous solution, and adding 10 ml chloroauric acid aqueous solution into 90ml deionized water for dissolving and diluting. Immediately immersing the carbon cloth treated by the plasma into a chloroauric acid aqueous solution, keeping 300 rpm and stirring for 2 hours to reduce and deposit gold ions in the chloroauric acid on the carbon cloth;
4. after reduction and deposition are finished, washing for 3 times by using deionized water to remove redundant chloroauric acid;
5. and keeping the temperature of the mixture in a vacuum drying oven at 80 ℃ for drying overnight to prepare the gold-loaded carbon cloth electrode. The prepared electrode can be used in the reaction of preparing CO by electrochemical reduction of CO 2.
Example 2
Preparation of supported Ru catalyst by carbon black plasma treatment
American cabot activated carbon (XC-72R) was purchased, washed with deionized water, filtered, and dried. 1g of the suspension was spread in a petri dish and placed in the center of a plasma cleaner. Vacuumizing, and introducing NH with the flow rate of 80 sccm3And plasma treatment was performed for 4 hours. A ruthenium trichloride solution was prepared in 1g/100ml of water, and 10 ml of the solution was diluted 10-fold with ionized water. And immediately adding the activated carbon powder treated by the plasma into a ruthenium trichloride solution, and carrying out ultrasonic treatment for 1 hour to ensure that ruthenium trichloride is fully and uniformly dispersed and reduced and deposited on a carrier. After the reaction was complete, the system was filtered, washed three times with deionized water, and dried in a freeze-drying oven for 48 hours to prepare a Ru/C electrocatalyst powder sample (fig. 1). Ru/C Performance ratio commercial RuO in the electrolytic Water oxygen evolution test2The performance of (2) is better.
Example 3
Preparation of Pt @ MXenes catalyst by MXenes carrier plasma treatment
（1）Ti3C2Powder sample preparation (one of MXenes): purchase of Ti from commercial sources3AlC22g of Ti is taken3AlC2Mixed with 20ml of 40% HF solution by slow addition and sonicated for 0.5 hours. The system was heated to 40 ℃ and stirred at 400rpm for 48 hours to dissolve the Ti3AlC2The Al component in (c) was filtered, washed with deionized water to a pH near neutral, and dried in a vacuum oven overnight. Uniformly mixing the dried sample with 40ml of DMSO under the action of ultrasonic for 1 hour, stirring for 2 days, filtering, further dispersing the sample into 1M KOH, performing ultrasonic for 1 hour, stirring for 1 day, filtering, washing with deionized water for several times, drying in a vacuum drying oven overnight to obtain Ti3C2Powder samples.
(2) 500mg of the prepared Ti was taken3C2The powder samples were spread in a petri dish and placed in the center of a plasma cleaner. Vacuumizing, and introducing O into the mixture at 80 sccm2And plasma treatment was performed for 8 hours. The concentration of the prepared chloroplatinic acid solution is 1g/100 ml. 5ml of the solution was taken and diluted 20-fold. Plasma treated Ti3C2The powder sample was immediately added to the chloroplatinic acid solution and sonicated for 0.5 hour to disperse the sample uniformly. Adding formic acid reducing agent to make platinum on Ti3C2Carrying out reduction deposition on the carrier. After the reaction is finished, filtering the system, washing the system for three times by deionized water, and drying the system in a freeze drying oven for 24 hours to prepare Pt/Ti3C2A sample of catalyst powder.
It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of a supported noble metal catalyst based on plasma is characterized by comprising the following steps:
1) carrying out ultrasonic treatment on the carrier material for 1 hour by using deionized water, acetone or ethanol, and drying;
2) placing the carrier material subjected to ultrasonic treatment in plasma treatment equipment, vacuumizing, and introducing specific gas for plasma treatment;
3) dissolving one or more noble metal salts containing noble metals in a selected solvent according to 1-1000 mg per 100ml of the solvent, and adding a weak reducing agent in an amount of 0-0.5 volume per milliliter of the selected solvent according to needs;
4) immersing the carrier material treated in the step 2) into a noble metal salt solution for carrying out a load reaction at 0-100 ℃;
5) and (3) washing and filtering the sample obtained in the step (4) for 3-5 times by using deionized water, and drying to obtain the supported noble metal catalyst.
2. The method of claim 1, wherein the support material is a carbon support or a metal compound support.
3. The method of claim 1, wherein the carbon support is graphene, bp2000 activated carbon, XC-72R activated carbon, carbon cloth or carbon paper.
4. The method according to claim 1, wherein the metal compound carrier is titanium dioxide, aluminum oxide, iron/cobalt/nickel oxide, tin dioxide, tungsten trioxide, titanium nitride, titanium carbide, molybdenum oxide, molybdenum carbide, molybdenum nitride, tungsten carbide, or tungsten nitride.
5. The method of preparing a plasma-based supported noble metal catalyst according to claim 1, wherein the specific gas is nitrogen, argon, ammonia, hydrogen, oxygen, or air; and introducing specific gas, wherein the gas flow rate is controlled to be 5-200 sccm.
6. The method for preparing a supported noble metal catalyst based on plasma according to claim 1, wherein the plasma treatment is carried out for 0.1-24 h.
7. The method of claim 1, wherein the noble metal is Pt, Ir, Au, Ru, Pd or Rh; the noble metal salt is chloride, nitrate or acetylacetone salt.
8. The method of claim 1, wherein the selected solvent is deionized water, ethanol, acetone, or ethylene glycol.
9. The method of claim 1, wherein the weak reducing agent is formaldehyde, acetaldehyde, formic acid or ascorbic acid.
10. The method for preparing a supported noble metal catalyst based on plasma according to claim 1, wherein the ultrasonic agitation treatment is carried out for 0.5 hour to 7 days; and the stirring speed is 100-1000 r/min by common stirring.
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