CN111570788A - Bimetal nano material, catalyst, preparation method and application thereof - Google Patents
Bimetal nano material, catalyst, preparation method and application thereof Download PDFInfo
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- CN111570788A CN111570788A CN202010438048.6A CN202010438048A CN111570788A CN 111570788 A CN111570788 A CN 111570788A CN 202010438048 A CN202010438048 A CN 202010438048A CN 111570788 A CN111570788 A CN 111570788A
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- Prior art keywords
- iridium
- catalyst
- core
- bimetallic
- precursor
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 82
- 239000011258 core-shell material Substances 0.000 claims abstract description 58
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 40
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 4
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 claims description 4
- KBXXFKPVKJZGJG-UHFFFAOYSA-K tribromoiridium;hydrate Chemical compound O.Br[Ir](Br)Br KBXXFKPVKJZGJG-UHFFFAOYSA-K 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- JHULURRVRLTSRD-UHFFFAOYSA-N 1-cyclohexylpyrrolidine-2,5-dione Chemical compound O=C1CCC(=O)N1C1CCCCC1 JHULURRVRLTSRD-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229940095068 tetradecene Drugs 0.000 claims description 3
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000004683 dihydrates Chemical class 0.000 claims description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims 1
- 235000020778 linoleic acid Nutrition 0.000 claims 1
- 229910017399 Au—Ir Inorganic materials 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000010587 phase diagram Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 26
- 239000011943 nanocatalyst Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- -1 hexachloroiridium (IV) hydrate Chemical compound 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000013112 stability test Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- UOGKUSJGQWFRBI-UHFFFAOYSA-N [C].[Ir].[C].[Pt] Chemical compound [C].[Ir].[C].[Pt] UOGKUSJGQWFRBI-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 229940071240 tetrachloroaurate Drugs 0.000 description 2
- KVDBPOWBLLYZRG-UHFFFAOYSA-J tetrachloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)(Cl)Cl KVDBPOWBLLYZRG-UHFFFAOYSA-J 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- POAPOGPNFCCSJW-UHFFFAOYSA-H Br[Ir](Br)(Br)(Br)(Br)Br.[Na] Chemical compound Br[Ir](Br)(Br)(Br)(Br)Br.[Na] POAPOGPNFCCSJW-UHFFFAOYSA-H 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- AHNSTIUMACVREU-UHFFFAOYSA-H [K].Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl Chemical compound [K].Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl AHNSTIUMACVREU-UHFFFAOYSA-H 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical compound [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- AGGAVQQLOURVRQ-UHFFFAOYSA-J potassium;gold(3+);tetrabromide;dihydrate Chemical compound O.O.[K+].[Br-].[Br-].[Br-].[Br-].[Au+3] AGGAVQQLOURVRQ-UHFFFAOYSA-J 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Images
Classifications
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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
- B22F1/17—Metallic particles coated with metal
-
- 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
-
- B01J35/33—
-
- B01J35/397—
-
- B01J35/61—
-
- 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
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- 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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
- C25B11/095—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 at least one of the compounds being organic
-
- 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
- C25B11/097—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 comprising two or more noble metals or noble metal alloys
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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 application discloses a bimetallic nano-material, a catalyst, a preparation method and an application thereof. The bimetallic nano material is of a core-shell structure, the inner core is made of metal gold, the outer shell is made of metal iridium, the particle size of the bimetallic nano material is 2-200 nm, the rule that an Au-Ir bimetallic structure is difficult to obtain in a traditional phase diagram is broken through, and the catalyst prepared from the material has the advantages of large specific surface area, simple preparation process, excellent catalytic effect and the like.
Description
Technical Field
The application relates to a core-shell structure bimetal nano material, a catalyst, and a preparation method and application thereof, and belongs to the technical field of nano materials.
Background
In recent years, with the increasing energy crisis, people strive to find various alternative energy sources meeting the requirements to reduce the dependence on fossil fuels. Hydrogen energy is a clean secondary energy, has the advantages of high energy density, high combustion heat value, wide source, storage, regeneration, electric combustibility, zero pollution, zero carbon emission and the like, is favorable for solving the problems of energy crisis, environmental pollution and the like, and has attracted wide attention of people. The electrochemical full-hydrolytic water can generate hydrogen and oxygen at the same time, and is a technology for efficiently preparing clean and sustainable energy. However, since the full water splitting half reaction-Oxygen Evolution Reaction (OER) kinetics are slow and the OER catalyst is rapidly deactivated, OER becomes an obstacle to limiting the overall water splitting efficiency. So far, the best catalysts for hydrogen evolution and oxygen evolution reactions are still nanocatalysts based on Pt and Ir (or Ru) throughout the water splitting process, but unfortunately, due to their poor electrocatalytic stability, it is difficult to achieve their wide industrial application. In addition, water decomposition is now mainly industrialized in alkaline media. With the development of proton exchange membrane water electrolysis cells (PEMWE), designing catalysts with high catalytic efficiency and good durability in acidic media has become a focus of research. The Ir-based catalyst has excellent hydrogen production and oxygen production performance, and is expected to be prepared into a dual-function catalyst for full water splitting. However, reducing the amount of these catalysts used and improving their catalytic activity and stability remain a great challenge for reasons of cost and poor stability. The catalyst with the core-shell structure not only improves the catalytic activity and stability, but also improves the utilization rate of Ir. However, it remains a great challenge to obtain a bifunctional catalyst with both excellent hydrogen and oxygen evolution activity and stability.
Disclosure of Invention
According to the first aspect of the application, the bimetal nanomaterial is provided, the bimetal nanomaterial is of a core-shell structure, the inner core is made of metal gold, the outer shell is made of metal iridium, and the particle size of the bimetal nanomaterial is 2-200 nm. The material breaks through the rule that an Au-Ir bimetal structure is difficult to obtain in a traditional phase diagram, and the catalyst prepared from the material has the advantages of large specific surface area, simple preparation process, excellent catalytic effect and the like.
Optionally, the particle size of the bimetal nano material is 8-10 nm. When the bimetallic nano-material is in the particle size range, the catalytic performance is optimal.
In a second aspect of the application, a catalyst is provided, which comprises a carrier and a bimetallic nano material loaded on the carrier, wherein the bimetallic nano material is in a core-shell structure, a core is made of metal gold, a shell is made of metal iridium, and the particle size of the bimetallic nano material is 2-200 nm.
Optionally, the particle size of the bimetal nano material is 8-10 nm.
Optionally, the support is a carbon support;
preferably, the carbon support is selected from at least one of carbon black (vulcan xc-72), graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes;
preferably, the loading amount of the bimetallic material is 5-60 wt%.
In a third aspect of the present application, a preparation method of a core-shell structure bimetal nanomaterial is provided, which at least includes the following steps:
reacting a mixed solution containing a gold precursor, an iridium precursor and a reducing agent to obtain a core-shell structure bimetal nano material;
optionally, the reducing agent is a compound with a double bond having a chain length of C10-C19.
Preferably, the reducing agent is in a liquid state, and the mixed solution consists of a gold precursor, an iridium precursor and the reducing agent.
Optionally, the reducing agent is selected from at least one of tetradecene, hexadecene, 2-hexadecenoic acid, oleylamine, oleic acid, linoleic acid, octadecene;
preferably, the gold precursor is selected from at least one of tetrachloroauric acid trihydrate, gold acetate, tetrabromohydrogold (III) hydrate, potassium tetrachloroauric (III) hydrate, and potassium tetrabromohalic (III) dihydrate;
preferably, the iridium precursor is selected from at least one of iridium chloride, iridium chloride hydrate, hexachloroiridic acid hydrate, iridium acetate, iridium bromide, iridium iodide, iridium bromide hydrate, sodium chloroiridate hydrate, iridium acetylacetonate, potassium hexachloroiridate, potassium hexabromoiridate and sodium hexabromoiridate; more preferably, the iridium precursor is selected from at least one of iridium chloride, Iridium (IV) chloride hydrate, iridium (III) chloride hydrate, hexachloroiridium (IV) hydrate, iridium acetate, iridium (III) bromide, iridium (III) iodide, iridium (III) bromide hydrate, sodium chloroiridate hydrate, iridium (III) acetylacetonate, potassium hexachloroiridium (III) hexabromide, potassium hexabromoiridium (IV) hexabromide, and sodium hexabromoiridium (IV) hexabromide.
Optionally, the concentration of the gold precursor in the mixed solution is 0.0067-0.05 mmol/ml; the concentration of the iridium precursor in the mixed solution is 0.00134-0.025 mmol/ml;
optionally, the upper limit of the concentration of the gold precursor in the mixed solution is selected from 0.01mmol/ml, 0.0125mmol/ml, 0.03mmol/ml and 0.05mmol/ml, and the lower limit is selected from 0.0067mmol/ml, 0.01mmol/ml, 0.0125mmol/ml and 0.03 mmol/ml;
optionally, the upper limit of the concentration of the iridium precursor in the mixed solution is selected from 0.0125mmol/ml, 0.01mmol/ml and 0.025mmol/ml, and the lower limit is selected from 0.00134mmol/ml, 0.0125mmol/ml and 0.01 mmol/ml.
Wherein the molar amount of the gold precursor is calculated by the molar amount of gold element, and the molar amount of the iridium precursor is calculated by the molar amount of iridium element.
Alternatively, the specific conditions of the reaction include:
the reaction temperature is 180-260 ℃;
the reaction time is 15-180 min.
Optionally, the upper limit of the reaction temperature is selected from 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, and the lower limit is selected from 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃;
optionally, the upper limit of the reaction time is selected from 25min, 45min, 75min, 105min, 180min, and the lower limit is selected from 15min, 25min, 45min, 75min, 105 min;
in a fourth aspect of the present application, there is provided a method for preparing the catalyst, comprising:
preparing a bimetallic nanomaterial with a core-shell structure according to any one of the methods;
and adding a carrier into the dispersion liquid of the bimetallic nano material to obtain the catalyst.
Optionally, the solvent in the dispersion is selected from at least one of cyclohexane and n-hexane.
Optionally, the content of the bimetallic nano-material in the dispersion liquid is 0.5-5 mg/mL.
In one embodiment, the method for preparing the catalyst comprises:
(1) adding gold precursor salt and iridium precursor salt into oleylamine according to a certain molar ratio, and performing ultrasonic dispersion to obtain a mixture. According to the invention, the molar concentrations of the gold precursor and iridium precursor salts in the mixture are 0.0067-0.05 mmol/ml and 0.00134-0.025 mmol/ml, respectively, such as 0.0134mmol/ml and 0.0067mmol/ml, respectively. In order to prevent gold from being reduced, the iridium (III) chloride hydrate is preferably added into oleylamine, ultrasonically dispersed at room temperature, then the tetrachloroaurate trihydrate is added, and ultrasonically dispersed.
(2) Preheating a metal bath to 180-260 ℃, and preferably 250 ℃. And (3) preheating the metal bath in the step (2) to 250 ℃ in advance so as to quickly raise the temperature to the reaction temperature after the flask is placed. The reaction time was recorded from the time the temperature was raised to the reaction temperature.
(3) And (3) putting the mixture obtained in the step (1) into a preheated metal bath kettle, and reacting at constant temperature. According to the invention, the reaction time is 15-180 min.
(4) According to the invention, after the temperature is kept constant, the temperature is naturally reduced to room temperature, for example, 15-25 ℃.
(5) Adding ethanol into the obtained product, precipitating, centrifuging, washing with a mixed solution of ethanol and cyclohexane for multiple times, and dispersing in n-hexane to obtain Au-Ir bimetallic nanoparticles with a core-shell structure;
(6) and (3) adding a proper amount of carbon carrier into the Au-Ir bimetal nanoparticle dispersion liquid with the core-shell structure obtained in the step (5), stirring for 1-12 h, and drying in an oven to obtain the Au-Ir bimetal nano catalyst with the core-shell structure.
According to the invention, the iridium precursor salt is iridium (III) chloride hydrate. The gold precursor salt is tetrachloroauric acid trihydrate.
According to the invention, the solvent is oleylamine with a purity of 50-90%, preferably 90%.
According to the invention, the carbon support can be selected from carbon black (vulcan xc-72), graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, and the like.
Because the reduction potential difference of Au and Ir is large, Au is easy to reduce, metal precursor salt of Ir and metal precursor salt of Au are added into a reaction vessel at the same time, oleylamine is used as a reducing agent, metal Au with higher oxidation-reduction potential is firstly deposited and nucleated in the reduction process, and metal Ir with low potential is reduced after being deposited with the temperature rise, and then deposited on the surface of Au to form a shell, thereby forming an Au-Ir nuclear shell structure. In the sequential reduction process of Au and Ir, the added oleylamine simultaneously plays the role of a surfactant, changes the nucleation and growth energy barrier of two metals, effectively inhibits the independent nucleation of Ir, and avoids the occurrence of phase separation. By varying the reaction time and the amount of reaction substrate, the shell thickness can also be precisely controlled. The catalyst has the advantages of large specific surface area, simple preparation process, excellent catalytic effect and the like.
The invention also aims to research the Au-Ir core-shell structure, which not only can improve the OER activity in an acid medium, but also can obviously improve the stability of the Au-Ir core-shell structure. Meanwhile, the prepared Au-Ir bimetallic nano-catalyst with the core-shell structure has excellent hydrogen evolution activity and oxygen evolution activity and stability, and is a bifunctional catalyst capable of being used for full water splitting. In addition, the bimetallic core-shell catalyst with different Ir shell thicknesses can be obtained by only changing the reaction time and the amount of reaction substrates. The core-shell structure enables Ir atoms at the reaction active sites to be fully exposed, and the atom utilization rate is improved, so that the catalytic activity of the catalyst is influenced; meanwhile, the electronic environment of the Au is changed due to the electronic effect induced by the Au, so that the stability of the Au is improved. Through researching the influence of the shell thickness on the activity and the stability, the Au-Ir core-shell nano catalyst with the proper Ir layer thickness is screened out for full water splitting.
In a fifth aspect of the present application, there is provided an application of at least one of the bimetallic nanomaterial, the catalyst, the bimetallic nanomaterial prepared by the method, and the catalyst prepared by the method in an electrocatalytic oxygen evolution reaction, an electrocatalytic hydrogen evolution reaction, and a total hydrolysis reaction.
Optionally, by making the catalyst into a catalyst ink application.
The beneficial effects that this application can produce include:
(1) the thickness ratio of the core to the shell can be regulated and controlled by changing the proportion of the iridium precursor to the gold precursor.
(2) The thickness of the Ir shell can be regulated and controlled by changing the reaction time.
(3) The catalyst is of a core-shell structure, Ir is distributed on a shell layer, and the catalyst has the advantages of large specific surface area, large active sites and high atom utilization rate.
(4) At the same voltage (1.49V), the catalyst prepared by the invention has 10.7 times higher catalytic activity of oxygen evolution reaction than the commercial iridium black.
(5) When the nano catalyst prepared by the invention is applied to full hydrolysis, the overpotential is far less than that of the commercial platinum carbon iridium carbon when the same current density is achieved.
(6) Compared with the oxygen evolution reaction stability of commercially available iridium black, the Au-Ir nano catalyst with the core-shell structure prepared by the invention is also greatly improved.
(7) Compared with the commercially available iridium black, the Au-Ir nano catalyst with the core-shell structure prepared by the invention has greatly improved full hydrolytic stability.
Drawings
FIG. 1 shows Au provided in example 32And the transmission electron microscope photo, the high-resolution transmission electron microscope photo and the line scanning picture of the Ir core-shell nano catalyst are obtained, and the model of a testing instrument is Talos-F200X.
FIG. 2 is a diagram of: example 2-1 Transmission Electron microscopy and high resolution Transmission Electron microscopy of Au-Ir core-shell nanocatalysts of different Ir layer thicknesses prepared with controlled reaction time.
FIG. 3 is a diagram of: catalyst prepared in inventive example 3 and commercially available iridium carbon at 0.5MH2SO4And (3) testing the electrochemical performance of the electrocatalytic oxygen evolution reaction in a solution and oxygen atmosphere.
FIG. 4 is a diagram of: the catalyst prepared in the embodiment 3 of the invention, and the platinum carbon and iridium carbon sold in the market are 0.5MH2SO4And (3) testing the electrochemical performance of the electrocatalytic hydrogen evolution reaction in a solution and nitrogen atmosphere.
FIG. 5 is a diagram: the catalyst prepared in the embodiment 3 of the invention and the commercial iridium carbon | | | platinum carbon are at 0.5MH2SO4And (4) testing the electrochemical performance of the solution and full-hydrolytic reaction.
FIG. 6 is a diagram of: the catalyst prepared in inventive example 3 was at 0.5MH2SO4And (3) testing the stability of the electrocatalytic oxygen evolution reaction in a solution and oxygen atmosphere.
FIG. 7 is a diagram of: the catalyst prepared in the embodiment 3 of the invention and the platinum carbon iridium carbon sold in the market are at 0.5MH2SO4And (4) testing the electrochemical stability of the solution and full-hydrolytic reaction.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
For each example, see table 1 for specific sources and parameters of raw materials:
table 1 source of raw materials and parameter table for each example
All drugs were used directly without further treatment.
Product Au-Ir core-shell structure nanoparticle Au in the applicationnIrmWherein n and m are used for expressing the atomic number ratio of Au to Ir in the product.
Example 1: au coating2Ir nucleusPreparation method of shell structure bimetal nanoparticles
(1) Adding 0.067mmol of iridium (III) chloride hydrate into a 25ml two-neck flask, adding 10ml of oleylamine, performing ultrasonic treatment for 10min to obtain brown transparent liquid, adding 0.134mmol of tetrachloroaurate trihydrate, and performing ultrasonic treatment for 2min to obtain a mixture A.
(2) Placing the mixture A in a metal bath preheated to 250 ℃, N2And (3) rapidly raising the temperature to 220 ℃ in the atmosphere, and reacting for 3 hours to obtain a product B.
(3) Naturally cooling to room temperature, adding ethanol into the obtained product B for precipitation, centrifuging (10000 r/min), and washing for 8 times by using a mixed solution of ethanol and cyclohexane (the volume ratio is 2: 1).
(4) Dispersing the product obtained after washing in 50ml of n-hexane to obtain Au2Ir core-shell structure bimetallic nanoparticles;
example 2:
example 2-1: Au-Ir core-shell structure nanoparticles (AuIr) with different Ir layer thicknesses and prepared by controlling reaction time0.22、AuIr0.33、AuIr0.35、AuIr0.38And AuIr0.41) Method (2)
Example 2-1 contained 5 protocols of examples 2-1a, 2-1b, 2-1c, 2-1d, 2-1e, all of which were identical to example 1 except for the reaction time, which was controlled to 15min, 25min, 45min, 75min and 105min for examples 2-1a to 2-1e, respectively.
The core-shell structure nanoparticles obtained by the reactions of examples 2-1a to 2-1e are sequentially represented as AuIr0.22、AuIr0.33、AuIr0.35、AuIr0.38And AuIr0.41。
Example 2-2: method for preparing Au-Ir core-shell structure nanoparticles by adopting different reducing agents
Example 2-2 includes 6 schemes in total, namely, examples 2-2a, 2-2b, 2-2c, 2-2d, 2-2e, and 2-2f, and examples 2-2a to 2-2f all have the same steps as example 1, except that the reducing agents in examples 2-2a to 2-2f are tetradecene, hexadecene, 2-hexadecenoic acid, oleic acid, linoleic acid, and octadecene, respectively, and the resulting products are Au, respectively2Ir-a、Au2Ir-b、Au2Ir-c、Au2Ir-d、Au2Ir-e and Au2Ir-f。
Examples 2 to 3: Au-Ir core-shell structure nanoparticles (Au) with different thickness ratios of core to shell prepared by changing proportion of iridium precursor and gold precursor5Ir、Au4Ir、Au3Ir, AuIr and AuIr2) Method (2)
Examples 2-3 contained 5 protocols of examples 2-3a, 2-3b, 2-3c, 2-3d, 2-3e, all steps of each protocol being the same as in example 1, with the only difference being the ratio of iridium precursor to gold precursor. The concentrations of the iridium precursor and the gold precursor in examples 2 to 3a, 2 to 3b, 2 to 3c, 2 to 3d, and 2 to 3e are shown in Table 1:
TABLE 1 examples 2-3 raw material ratios and products
Examples 2 to 4: method for preparing Au-Ir core-shell structure nanoparticles by adopting different gold precursor salts
Examples 2-4 include 4 schemes in total, namely examples 2-4a, 2-4b, 2-4c, 2-4d, and examples 2-4 a-2-4 d all the steps are the same as example 1, except that the gold precursor salts in examples 2-4 a-2-4 d are gold acetate, gold (III) tetrabromide hydrate, gold (III) tetrachlorohydrate, and gold (III) tetrabromide potassium dihydrate, respectively, and the resulting products are Au2Ir-A1、Au2Ir-A2、Au2Ir-A3And Au2Ir-A4。
Examples 2 to 5: method for preparing Au-Ir core-shell structure nanoparticles by adopting different iridium precursor salts
Examples 2-5 included a total of 12 schemes, namely examples 2-5a, 2-5b, 2-5c, 2-5d, 2-5e, 2-5f, 2-5g, 2-5h, 2-5i, 2-5j, 2-5k, 2-5l, examples 2-5 a-2-5 l all the procedures were the same as example 1, except that the iridium precursor salts in examples 2-5 a-2-5 l were respectively Iridium (IV) chloride hydrate, Iridium (IV) hexachloride hydrate, iridium acetate, iridium chlorideIridium bromide, iridium iodide, iridium bromide hydrate, sodium chloroiridate hydrate, iridium (III) acetylacetonate, potassium hexachloroiridium (III), potassium hexabromoiridium (IV) and sodium hexabromoiridium (IV), the obtained products are Au2Ir-B1、Au2Ir-B2、Au2Ir-B3、Au2Ir-B4、Au2Ir-B5、Au2Ir-B6、Au2Ir-B7、Au2Ir-B8、Au2Ir-B9、Au2Ir-B10、Au2Ir-B11And Au2Ir-B12。
Example 3: au coating2Preparation method of Ir core-shell structure bimetallic nano-catalyst
(1) 40mg of VulcanXC-72 carbon black were added to the Au powder prepared in example 12And (3) stirring the Ir core-shell structure bimetallic nanoparticle n-hexane dispersion liquid overnight to uniformly load the nanoparticles on the carbon carrier.
(2) Standing to separate out black precipitate, and drying in an oven at 50 ℃ to obtain Au2An Ir core-shell structure bimetallic nano-catalyst.
Fig. 1 is a transmission electron micrograph of the catalyst provided in example 3, and it can be seen from fig. 1a and 1b that the synthesized bimetallic nanoparticles have a particle size of about 8 nm, and all nanoparticles are uniformly dispersed. FIG. 1c shows the results for any number of Au layers2Detailed analysis is carried out on a high-resolution transmission electron microscope image of the Ir core-shell nano-particle, and lattice spacings of 0.222 nm and 0.233 nm respectively correspond to a (111) crystal face of an Ir-rich shell and a (111) crystal face of an Au-rich core, so that the structure is a core-shell structure. FIG. 1e is several random Au2The scanning transmission electron microscope image of the Ir nuclear shell nano-particles and the energy dispersion X-ray mapping of Au and Ir prove that Au is2And forming the Ir core-shell structure nanoparticles. FIG. 1d shows any one of Au2The linear scanning of the Ir core-shell nanoparticles shows that a wide peak is arranged in the center, two strong peaks are arranged on two sides and respectively correspond to Au and Ir elements, and further discloses the core-shell structure of the Ir core-shell nanoparticles.
Example 4: Au-Ir nuclear shell with different Ir layer thicknesses prepared by controlling reaction timeStructured nanocatalyst (AuIr)0.22、AuIr0.33、AuIr0.35、AuIr0.38And AuIr0.41) Method (2)
All the procedures were the same as in example 3, except that 17.6, 26.4, 28, 30.4 and 32.8mg of VulcanXC-72 carbon black were added to the Au-Ir core-shell-structured bimetallic nanoparticles (AuIr) prepared in example 2-1 in one-to-one correspondence, respectively0.22、AuIr0.33、AuIr0.35、AuIr0.38And AuIr0.41) N-hexane dispersion.
Fig. 2 is a transmission electron micrograph of the catalyst provided in example 4, in which fig. 2a to 2e correspond to the catalysts prepared from the nanoparticles of examples 2-1a to 2-1e, respectively, and it can be seen that all the nanoparticles are uniformly dispersed. Fig. 2f to 2j are high-resolution transmission electron microscope images of the catalysts prepared from the nanoparticles of examples 2-1a to 2-1e, respectively, and it can be seen that all nanoparticle core layers and shell layers have different lattice spacings, which correspond to the (111) crystal plane of the Ir-rich shell and the (111) crystal plane of the Au-rich core, respectively, indicating that the prepared Au-Ir nanocatalysts of different Ir layer thicknesses are all core-shell structures.
The nanoparticles obtained in other embodiments of the present application are all of a core-shell structure, and the particle size is 2-200 nm.
Example 5: au for electrochemical testing2Preparation method of Ir core-shell structure bimetallic nano-catalyst ink
(1) 4mg of Au prepared in example 32And adding the Ir core-shell structure bimetallic nano-catalyst into a 10ml glass bottle, adding 1.94ml isopropanol, and performing ultrasonic treatment for 3 hours to uniformly disperse the Ir core-shell structure bimetallic nano-catalyst to obtain a mixture A.
Example 6: step of electrocatalytic oxygen evolution reaction
Preparing an electrode: a certain amount of the catalyst ink of example 5 was dropped on the surface of a glassy carbon electrode (glassy carbon electrode, straight)Diameter of 5mm and area of 0.196cm2) And naturally drying to obtain the working electrode, wherein the counter electrode is a platinum mesh, and the reference electrode is Ag/AgCl.
The amount of the catalyst added dropwise is determined according to the content of iridium in the catalyst, so that the content of Ir finally loaded on the glassy carbon electrode is 20 mu g/cm2。
And (3) electrochemical performance testing: firstly, N is20.5MH in the atmosphere2SO4Cyclic voltammetry scanning is carried out in the solution, the scanning range is 0-1.0V, and the scanning speed is 200mV s-1And scanning for 300 circles, wherein the step plays a role in cleaning and activating the surface of the catalyst. Then at O20.5MH in the atmosphere2SO4The polarization curve is tested in the solution to represent the electrocatalytic oxygen evolution performance of the catalyst, and the scanning speed is 10mV s-1The scanning range is 1.0-1.4V.
Electrochemical stability test: at O20.5MH in the atmosphere2SO4In the solution, a constant current test is adopted, the current is set to be 2mA, the test time is 10h, and the potential change is recorded.
The above set potentials are relative to an Ag/AgCl electrode.
Fig. 3 and 6 are an electrocatalytic oxygen evolution performance test and a stability test, respectively, of the catalyst provided in example 3. From the figure, it can be seen that Au synthesized by the present invention2Compared with commercially available iridium carbon, the Ir core-shell structure bimetallic nano-catalyst has better catalytic activity and stability. At a current density of 10mA/cm2The reaction overpotential required was only 260mV, much less than that of iridium carbon, which exhibited 10.7 times the catalytic activity of commercially available iridium black, while the stability test maintained a constant current for 10 hours before Au2The required potential of the Ir core-shell structure bimetallic nano-catalyst is basically unchanged.
Example 7: step of electrocatalytic hydrogen evolution reaction
Preparing an electrode: all steps were the same as in example 6, except that the counter electrode was a carbon rod.
And (3) electrochemical performance testing: firstly, N is20.5MH in the atmosphere2SO4Circulating in solutionScanning with a scanning range of 0-0.4V and a scanning speed of 50mVs-1And 20 circles are scanned, and the step plays a role in cleaning and activating the surface of the catalyst. Then testing the polarization curve to represent the electro-catalytic hydrogen evolution performance of the catalyst, wherein the scanning speed is 10mV s-1The scanning range is-0.1 to-0.3V.
The above set potentials are relative to an Ag/AgCl electrode.
Fig. 4 is an electrocatalytic hydrogen evolution performance test of the catalyst provided in example 3. From the figure, it can be seen that Au synthesized by the present invention2Compared with commercially available iridium carbon and commercially available platinum carbon, the Ir core-shell structure bimetallic nano-catalyst has better catalytic activity. At a current density of 10mA/cm2The overpotential required for the reaction is only 30mV less than that of commercially available iridium and platinum carbons.
Example 8: step of electrocatalytic full-hydrolytic reaction
Preparing an electrode: electrochemical tests were performed in a two-electrode glass electrolytic cell, working electrode: the cathode and anode materials are both catalysts prepared by the invention. A certain amount of the catalyst ink of example 5 was dropped on the surface of the carbon paper electrode (1 cm x 1cm carbon paper electrode), and the working electrode was obtained by natural drying.
The amount of the catalyst added dropwise is determined according to the content of iridium in the catalyst, so that the content of Ir finally loaded on the glassy carbon electrode is 20 mu g/cm2。
And (3) electrochemical performance testing: firstly, N is20.5M H in atmosphere2SO4Cyclic voltammetry scanning is carried out in the solution, the scanning range is 0-0.5V, and the scanning speed is 100mV-1And scanning for 100 circles, wherein the step plays a role in cleaning and activating the surface of the catalyst. Then at 0.5MH2SO4The polarization curve is tested in the solution to represent the electrocatalytic full-hydrolytic performance of the catalyst, and the scanning speed is 10mV s-1The scanning range is 1.2-1.6V.
Electrochemical stability test: at 0.5MH2SO4In the solution, a constant current test is adopted, the current is set to be 10mA, the test time is 28h, and the potential change is recorded.
Fig. 5 and 7 are an electrocatalytic full water splitting performance test and a stability test, respectively, of the catalyst provided in example 3. From the figure, it can be seen that Au synthesized by the present invention2Compared with the commercially available iridium carbon | | | platinum carbon, the Ir core-shell structure bimetallic nano catalyst has better catalytic activity and stability. At a current density of 10mA/cm2The reaction potential required was only 1.561V, which exhibited 4.3 times the catalytic activity of the commercially available iridium carbon | | platinum carbon, and the stability test Au2The Ir core-shell structure bimetallic nano-catalyst can maintain constant current for 28 hours, and commercial iridium carbon I platinum carbon is immediately inactivated.
The catalysts provided in the other examples of this application also all had similar catalytic activity to the catalyst provided in example 3. The electrocatalytic oxygen evolution reaction performance of the catalyst provided by other embodiments is also excellent, and the current density is 10mA/cm2The required overpotentials for the reactions were all less than 270mV (1.50V relative to the standard hydrogen electrode), while the stability test maintained a constant current of 10mA/cm2And the required potential of all the Au-Ir core-shell structure bimetallic nano-catalysts can be kept unchanged for 15-100 h. The electrocatalytic hydrogen evolution reaction performance of the catalyst provided by other embodiments is also excellent, and the current density is 10mA/cm2The required reaction overpotential is between 30mV and 40 mV. The electrocatalytic full water decomposition performance is tested, and the current density is 10mA/cm2In the process, the required reaction potential is 1.549-1.565V, and the Au-Ir core-shell structure bimetallic nano-catalyst can maintain constant current for 24-96 hours in a stability test.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The bimetal nanomaterial is characterized in that the bimetal nanomaterial is of a core-shell structure, the inner core is metal gold, the outer shell is metal iridium, and the particle size of the bimetal nanomaterial is 2-200 nm.
2. The catalyst is characterized by comprising a carrier and a bimetallic nano material loaded on the carrier, wherein the bimetallic nano material is of a core-shell structure, the inner core is metal gold, the shell is metal iridium, and the particle size of the bimetallic nano material is 2-200 nm.
3. The catalyst of claim 2, wherein the support is a carbon support;
preferably, the carbon support is selected from at least one of carbon black, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes;
preferably, the loading amount of the bimetallic material is 5-60 wt%.
4. The preparation method of the core-shell structure bimetal nanomaterial as claimed in claim 1, characterized by comprising at least the following steps:
and reacting the mixed solution containing the gold precursor, the iridium precursor and the reducing agent to obtain the core-shell structure bimetal nano material.
5. The method according to claim 4, wherein the reducing agent is a compound having a double bond with a chain length of C10-C19;
preferably, the reducing agent is selected from at least one of tetradecene, hexadecene, 2-hexadecenoic acid, oleylamine, oleic acid, linoleic acid and octadecene;
preferably, the gold precursor is selected from at least one of tetrachloroauric acid trihydrate, gold acetate, tetrabromohydrogold (III) hydrate, potassium tetrachloroauric (III) hydrate, and potassium tetrabromohalic (III) dihydrate;
preferably, the iridium precursor is selected from at least one of iridium chloride, iridium chloride hydrate, hexachloroiridic acid hydrate, iridium acetate, iridium bromide, iridium iodide, iridium bromide hydrate, sodium chloroiridate hydrate, iridium acetylacetonate, potassium hexachloroiridate, potassium hexabromoiridate and sodium hexabromoiridate.
6. The method of claim 4, wherein:
the concentration of the gold precursor in the mixed solution is 0.0067-0.05 mmol/ml;
the concentration of the iridium precursor in the mixed solution is 0.00134-0.025 mmol/ml;
wherein the molar amount of the gold precursor is calculated by the molar amount of gold element, and the molar amount of the iridium precursor is calculated by the molar amount of iridium element.
7. The method according to claim 4, wherein the reaction is carried out under specific conditions including:
the reaction temperature is 180-260 ℃;
the reaction time is 15-180 min.
8. A method for preparing the catalyst of claim 2, comprising:
preparing a bimetallic nanomaterial with a core-shell structure according to the method of any one of claims 4 to 7;
and adding a carrier into the dispersion liquid of the bimetallic nano material to obtain the catalyst.
9. The method according to claim 8, wherein the solvent in the dispersion is at least one selected from cyclohexane and n-hexane.
10. Use of at least one of the bimetallic nanomaterial of claim 1, the catalyst of claim 2 or 3, the bimetallic nanomaterial prepared by the method of any one of claims 4 to 7, and the catalyst prepared by the method of claim 8 or 9 in electrocatalytic oxygen evolution reaction, electrocatalytic hydrogen evolution reaction, and total hydrolysis reaction.
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