CN110115996A - A kind of gold ruthenium nanocomposite and its synthetic method, golden ruthenium nanocomposite catalyst, application - Google Patents
A kind of gold ruthenium nanocomposite and its synthetic method, golden ruthenium nanocomposite catalyst, application Download PDFInfo
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- CN110115996A CN110115996A CN201910388274.5A CN201910388274A CN110115996A CN 110115996 A CN110115996 A CN 110115996A CN 201910388274 A CN201910388274 A CN 201910388274A CN 110115996 A CN110115996 A CN 110115996A
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- ruthenium
- gold
- nanocomposite
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 143
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 116
- CQKBIUZEUFGQMZ-UHFFFAOYSA-N [Ru].[Au] Chemical compound [Ru].[Au] CQKBIUZEUFGQMZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims description 59
- 238000010189 synthetic method Methods 0.000 title claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052737 gold Inorganic materials 0.000 claims abstract description 57
- 239000010931 gold Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 230000006798 recombination Effects 0.000 claims abstract description 11
- 238000005215 recombination Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 48
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 33
- 230000003287 optical effect Effects 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- 230000001476 alcoholic effect Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000003223 protective agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 241000257465 Echinoidea Species 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- SIEBMRITFODZNV-UHFFFAOYSA-N Cl.[K].[Ru] Chemical compound Cl.[K].[Ru] SIEBMRITFODZNV-UHFFFAOYSA-N 0.000 claims description 4
- NZIGZHDIUCTKQH-UHFFFAOYSA-N Cl[Ru+2].[NH4+] Chemical compound Cl[Ru+2].[NH4+] NZIGZHDIUCTKQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 4
- 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 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 22
- 239000002086 nanomaterial Substances 0.000 abstract description 16
- 238000001228 spectrum Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 4
- 230000008033 biological extinction Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 235000013339 cereals Nutrition 0.000 description 39
- 239000000463 material Substances 0.000 description 21
- 230000008569 process Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000003863 metallic catalyst Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 chlorauride Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QYTBWVFCSVDTEC-UHFFFAOYSA-N azane;iron Chemical compound N.[Fe] QYTBWVFCSVDTEC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of golden ruthenium nanocomposite, for the gold ruthenium nanocomposite using gold nano grain as core, surface recombination has metal Ru.Gold ruthenium nanocomposite provided by the invention, using gold nano grain as core, surface recombination has metal Ru, and further can also control catalytic performance by adjusting the pattern on surface.The present invention utilizes the phasmon effect of metal nano material, and wherein gold nano grain effectively absorbs visible light as extinction center, and generates electromagnetic near field enhancing and thermoelectronic effect to drive chemical reaction；Ruthenium nanostructure plays the role of adsorption activation nitrogen molecule as active site, solar energy under normal pressure and temperature and full spectrum light irradiation realize to chemical energy Efficient Conversion, reaction efficiency is effectively promoted, a large amount of consumption in traditional industrial process to energy are avoided.
Description
Technical field
The invention belongs to phasmon metal catalyst technology field, it is related to a kind of golden ruthenium nanocomposite and its synthesis
Method, golden ruthenium nanocomposite catalyst, application more particularly to a kind of golden ruthenium nanocomposite for fixed nitrogen reaction and
Its synthetic method, the golden ruthenium nanocomposite optical drive catalyst for fixed nitrogen reaction, application.
Background technique
Catalyst is one of most common substance in chemical reaction, it refers to can change reaction materialization in chemical reaction
Reaction rate is learned without changing chemical balance, and all no change has taken place before and after chemical reaction for the quality of itself and chemical property
Substance catalyst, the relationship of it and reaction system has the selectivity of height just as locking with the relationship of key as.According to system
Meter, there are about catalyst, such as chemical industry, petrochemical industry, biochemistry, environmental protection are used in 90% or more industrial process.Thus, in field for
The research of catalyst is always maintained at the concern of height.
Catalyst type is various, classifies also very much, is usually divided into homogeneous catalyst by the phase of reaction system and multiphase is urged
Agent, and heterogeneous catalyst include solid acid catalyst, organic alkali catalyst, metallic catalyst, metal oxide catalyst,
Complex compound catalyst, rare earth catalyst and nanocatalyst etc., metallic catalyst is with metal for main active group among these
The solid catalyst divided, is to be now subjected to a kind of widely applied catalyst, especially emerging phasmon metallic catalyst.
Phasmon refers in the solid system with certain carrier concentration (such as metal, partly leading with certain carrier concentration
Body etc.), due to the Coulomb interaction between carrier so that at one in space carrier concentration fluctuation, other will be caused
The oscillation of local carrier concentration.It is this to be excited by the member of essential characteristic of the oscillation of carrier concentration, referred to as phasmon.And
And due to etc. advantage and potentiality from first metallic catalyst in optical drive field of catalytic reactions, obtained extensive pass in the industry
Note.
Solar energy is most wide as a kind of coverage area on earth, per second to arrive using time longest clean energy resource
Energy up to the earth is equivalent to 5,000,000 tons of coals of burning.Therefore, sustainable development of the effective use of solar energy to human future
It is most important.Phasmon metal nanoparticle is according to own material, the difference of shape or size, in entire solar spectrum wavelength
In range (from ultraviolet to infrared), strong interaction can be generated with incident light, excites metal nanoparticle surface
Local plasmon resonance effect.This allows phasmon metal nanoparticle will be much larger than within the scope of itself geometric area
Luminous energy concentrate to a very small extent, and cause strong light-substance interaction by energy transfer, in the realization sun
There can be very big potentiality to the conversion aspect between chemical energy.
Reacting synthesis ammonia by fixed nitrogen is a kind of common commercial synthesis process, such as the iron catalysis being widely used
Activation energy needed for agent can be effectively reduced ammonia synthesis reaction, but need to put into a large amount of energy ability during the reaction
Catalyst surface is kept there are enough temperature to deactivate nitrogen molecule.The Haber-Bosch method industrially used is in order to by nitrogen
Gas and hydrogen are converted into ammonia, generally require to provide the high temperature greater than 300 DEG C and the pressure more than 100 atmospheric pressure, this is caused
Great energy consumption.
Therefore, a kind of novel catalyst for generating ammonia for the reaction of optical drive fixed nitrogen how is developed, is able to solve above-mentioned
Problem, especially can in a mild condition, and realization conversion process of the nitrogen to ammonia has a very important significance, and
Many forward-looking researchers widely one of focus of attention in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of golden ruthenium nanocomposite and its synthesis side
Method, golden ruthenium nanocomposite catalyst, application, especially a kind of golden ruthenium nanocomposite for fixed nitrogen reaction.This hair
The golden ruthenium nanocomposite of bright offer realizes solar energy to chemical energy Efficient Conversion, can carry out under mild conditions
Fixed nitrogen reaction, realizes conversion process of the nitrogen to ammonia；And preparation synthesis can be carried out only by simple one-step method.
The present invention provides a kind of golden ruthenium nanocomposite, the gold ruthenium nanocomposite is with gold nano grain
Core, surface recombination have metal Ru.
Preferably, the partial size of the golden ruthenium nanocomposite particles is 25~65nm；
In the gold ruthenium nanocomposite, the molar ratio of gold element and ruthenium element is 1:(0.001~0.39)；
The metal Ru of the surface recombination has class antenna structure；
The gold ruthenium nanocomposite has the pattern of sea urchin shape structure；
The gold ruthenium nanocomposite has the crystal structure of face-centered cubic closest packing.
Preferably, the golden ruthenium nanocomposite during forming and changing initial gold nano grain pattern simultaneously
It is formed；
The initial gold nano grain has five heavy twin structures；
The incomplete phase of pattern of the pattern and initial gold nano grain of gold nano grain in the gold ruthenium nanocomposite
Together；
The partial size of the gold nano grain is 20~60nm；
The partial size of the initial gold nano grain is 35~100nm.
The present invention provides a kind of synthetic methods of golden ruthenium nanocomposite, comprising the following steps:
A) alcoholic solution of Jin Yuan and ruthenium source are added in the alcohol liquid after preheating and reacted, the nano combined material of golden ruthenium is obtained
Material.
Preferably, the Jin Yuan includes four hydration gold chlorides, chlorauride, aurous chloride, sodium chloraurate, potassium chloroaurate and chlorine
One of auric acid ammonium is a variety of；
The ruthenium source includes one of ruthenic chloride, ruthenium hydrochloride potassium and ruthenium hydrochloride ammonium or a variety of；
The molar ratio in the Jin Yuan and ruthenium source is 1:(0.001~1)；
The concentration in ruthenium source is 0.001~1.300mg/mL in the Jin Yuan and the alcoholic solution in ruthenium source；
Solvent in the alcoholic solution includes one in diglycol, ethylene glycol, glycerine, propylene glycol and cyclohexanol
Kind is a variety of；
The speed of the addition is 1.0~2.0mL/min.
Preferably, the alcohol liquid includes one of diglycol, ethylene glycol, glycerine, propylene glycol and cyclohexanol
Or it is a variety of；
Crystal face protective agent can also be added in the alcohol liquid；
The crystal face protective agent includes one of potassium iodide, potassium bromide, citric acid and N vinylamide polymer
Or it is a variety of；
Temperature after the preheating is 180~260 DEG C；
The temperature of the reaction is 180~260 DEG C；
The time of the reaction is 5~30 minutes；
The volume ratio of the Jin Yuan and the alcoholic solution in ruthenium source and the alcohol liquid is (3.4~4.1): (20~100).
The present invention also provides a kind of golden ruthenium nanocomposite catalyst, including carrier and load on the carrier
Golden ruthenium nanocomposite；
It is described gold ruthenium nanocomposite be above-mentioned technical proposal any one described in golden ruthenium nanocomposite or on
State golden ruthenium nanocomposite synthesized by synthetic method described in technical solution any one.
Preferably, the carrier includes carbon carrier, silica supports, alumina carrier, ceramic monolith, molecule
One of sieve, silicon carbide, kaolin, fluoropolymer and quartz glass are a variety of；
The carrier can be gel carrier；
The load capacity of the load is 10%~60%.
Described in golden ruthenium nanocomposite, above-mentioned technical proposal any one described in above-mentioned technical proposal any one
Golden ruthenium nanocomposite described in golden ruthenium nanocomposite or above-mentioned technical proposal any one synthesized by synthetic method
Application of the catalyst in the reaction of optical drive class.
Preferably, the optical drive class reaction includes that optical drive fixed nitrogen reacts；
The optical drive fixed nitrogen reaction, specifically includes the following steps:
Catalyst dispersion is placed in nitrogen atmosphere, light-catalyzed reaction is carried out under light illumination, obtains ammonia；
The pressure of the nitrogen is 1~20bar；
The temperature of the light-catalyzed reaction is room temperature~200 DEG C；
The intensity of the light irradiation is 20~3200mWcm-2。
The present invention provides a kind of golden ruthenium nanocomposite, the gold ruthenium nanocomposite is with gold nano grain
Core, surface recombination have metal Ru.Compared with prior art, the present invention is made extensively in existing fixed nitrogen reaction synthesis ammonia
Iron catalyst, which needs to put into during the reaction a large amount of energy and is just able to maintain catalyst surface, has enough temperature to deactivate
Change nitrogen molecule；And the Haber-Bosch method industrially used, then need high temperature of the offer greater than 300 DEG C and more than 100
The pressure of atmospheric pressure causes many defects of great energy consumption.
The invention has designed and synthesized a kind of golden ruthenium nanocomposite, and the nanocomposite is with gold nano
Particle is core, and surface recombination has metal Ru, and further can also control catalytic performance by adjusting the pattern on surface.This hair
The bright phasmon effect using metal nano material, wherein gold nano grain effectively absorbs visible light as extinction center, and
Electromagnetic near field enhancing and thermoelectronic effect are generated to drive chemical reaction；Ruthenium nanostructure plays adsorption activation as active site
The effect of nitrogen molecule, and then realize the solar energy under normal pressure and temperature and full spectrum light irradiation to chemical energy Efficient Conversion, 1~
Nitrogen atmosphere, room temperature and the 20~3200mWcm of 20 atmospheric pressures-2Full spectrum light irradiation is lower to carry out fixed nitrogen reaction, effectively mentions
Reaction efficiency is risen, a large amount of consumption in traditional industrial process to energy are avoided.The experimental results showed that the method ammonia in the present invention
Yield reach as high as 220 μm of olg-1·h-1。
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of initial gold nano grain prepared by the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope (TEM) of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention
Photo；
Fig. 3 is that the high-resolution of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention transmits electricity
Mirror (HRTEM) photo；
Fig. 4 is the X-ray diffraction pattern of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention
(XRD)；
Fig. 5 is the transmission electron microscope (TEM) of golden ruthenium bimetal nano sandwich prepared by the present embodiment 3 of the present invention
Photo；
Fig. 6 is the ultraviolet-ray visible absorbing of gold nano grain prepared by the present invention and golden ruthenium bimetal nanostructure catalyst
Spectrum (UV-vis) spectrogram；
Fig. 7 is the average production for the ammonia that the corresponding fixed nitrogen of catalyst reacts preceding generation in 2 hours in the embodiment of the present invention 4~6
Rate；
Fig. 8 is the average ammonia yield of fixed nitrogen reaction of the catalyst under the differential responses time and anti-in the embodiment of the present invention 7
Relation curve between seasonable；
Fig. 9 is that first 2 hours average ammonia of fixed nitrogen reaction of the catalyst of the present invention under the irradiation of different light intensity of incident light produces
The relation curve that rate changes with light intensity.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or metallic catalyst
The conventional purity of preparation field.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
All techniques of the present invention, abbreviation belong to the conventional abbreviation of this field, neck of each abbreviation in its associated uses
Be in domain it is explicit, those skilled in the art are according to referred to as, it is to be understood that its conventional processing step.
The present invention provides a kind of golden ruthenium nanocomposites, are a kind of golden ruthenium bimetal nano sandwich, institute
Golden ruthenium nanocomposite is stated using gold nano grain as core, surface recombination has metal Ru.
The present invention is in principle not particularly limited the compound definition, and those skilled in the art can be according to actually answering
It is selected and is adjusted with situation, product requirement and concrete application, the present invention is that guarantee fund's ruthenium nanocomposite has more
Good catalytic activity, it is described it is compound preferably include one of cladding, growth, deposition and insertion or a variety of, more preferably coat
And growth.Cladding of the present invention preferably refers to incomplete cladding, i.e., does not form ruthenium metal layer, the gold ruthenium nanocomposite
Without core-shell structure.
The present invention is in principle not particularly limited the partial size of the golden ruthenium nanocomposite, and those skilled in the art can
To be selected and be adjusted according to practical situations, product requirement and concrete application, the present invention is multiple for guarantee fund's ruthenium nanometer
Condensation material has better catalytic activity, and the partial size of the gold ruthenium nanocomposite particles is preferably 25~65nm, more preferably
For 30~55nm, more preferably 35~45nm, it is specifically as follows 37nm or so.Gold nano grain of the present invention, i.e. Jin Liaona
The partial size of the gold nano grain kernel of nano composite material is preferably 20~60nm, more preferably 25~50nm, more preferably 30~
40nm is specifically as follows 30nm or so.
The present invention is in principle not particularly limited the specific ratio of ingredient in the golden ruthenium nanocomposite, this field
Technical staff can select and adjust according to practical situations, product requirement and concrete application, and the present invention is to guarantee
Golden ruthenium nanocomposite has a better catalytic activity, the molar ratio of the gold element and ruthenium element be preferably 1:(0.001~
0.39), more preferably 1:(0.01~0.37), more preferably 1:(0.1~0.35), more preferably 1:(0.2~0.33) and, optimal
It is selected as 1:0.31.
The present invention is in principle not particularly limited the pattern of the golden ruthenium nanocomposite, and those skilled in the art can
To be selected and be adjusted according to practical situations, product requirement and concrete application, the present invention is multiple for guarantee fund's ruthenium nanometer
Condensation material has a better catalytic activity, and in the gold ruthenium nanocomposite, the metal Ru of surface recombination preferably has class day
Cable architecture is preferably grown in the surface of gold nano grain core in line or tufted.It may also be said that gold ruthenium nanometer of the present invention is multiple
The pattern preferably with sea urchin shape structure or gold nano grain core surface grow villous shape or antenna to condensation material on the whole
The metal Ru of shape.
The present invention is in principle not particularly limited the crystal form of the golden ruthenium nanocomposite, and those skilled in the art can
To be selected and be adjusted according to practical situations, product requirement and concrete application, the present invention is multiple for guarantee fund's ruthenium nanometer
Condensation material has better catalytic activity, and the gold ruthenium nanocomposite preferably has the crystal knot of face-centered cubic closest packing
Structure.
The present invention is in principle not particularly limited the pattern variation of the golden ruthenium nanocomposite forming process, ability
Field technique personnel can select and adjust according to practical situations, product requirement and concrete application, and the present invention is to protect
Demonstrate,proving golden ruthenium nanocomposite has better catalytic activity, and the gold ruthenium nanocomposite preferably in formation and changes initial
It is formed simultaneously during gold nano grain pattern, i.e., only prepares gold according to the synthetic method of golden ruthenium nanocomposite of the invention
Nano particle can then obtain initial gold nano grain, and when ruthenium nanocomposite golden using this method synthesis, this will be changed
The initial gold nano grain pattern of kind has been formed simultaneously golden ruthenium nanocomposite exactly during this formation and change,
Thus, the pattern of the pattern of gold nano grain and initial gold nano grain is not preferably in gold ruthenium nanocomposite of the present invention
It is identical, it is more preferably not identical.Initial gold nano grain of the present invention preferably has five heavy twin structures.Institute of the present invention
Initial gold nano grain is stated, i.e., only prepares the partial size of gold nano grain according to the synthetic method of golden ruthenium nanocomposite of the invention
Preferably 35~100nm, more preferably 45~85nm, more preferably 55~70nm, are specifically as follows 61nm or so.
Above structure of the present invention and process can obtain explanation and illustration, this field from the embodiment of the present invention and its attached drawing
Technical staff uniquely can understand and confirm.
The present invention to the pattern of above-mentioned class antenna structure, sea urchin shape structure, the crystal structure of face-centered cubic closest packing and
The definition of five weight twin structures and concept are not particularly limited, and are with usual definition well known to those skilled in the art and concept
Can, those skilled in the art can select and adjust according to practical situations, product requirement and particular use.
The present invention also provides a kind of synthetic methods of golden ruthenium nanocomposite, comprising the following steps:
A) alcoholic solution of Jin Yuan and ruthenium source are added in the alcohol liquid after preheating and reacted, the nano combined material of golden ruthenium is obtained
Material.
Selection, proportion and the technological parameter of material in the step of above-mentioned golden ruthenium nanocomposite of the invention, Yi Jixiang
Selection, proportion and the parameter of material in the optimum principle answered, with aforementioned golden ruthenium nanocomposite agent, and it is corresponding excellent
Principle is selected can preferably to be corresponded to, this is no longer going to repeat them.
The present invention is in principle not particularly limited the specific choice of the Jin Yuan, and those skilled in the art can be according to reality
Border experimental conditions, product requirement and particular use are selected and are adjusted, and the present invention is to guarantee reaction effect and Jin Liaona
Nano composite material has better pattern and catalytic performance, and the Jin Yuan, i.e. golden predecessor preferably include four hydration chlorine gold
One of acid, chlorauride, aurous chloride, sodium chloraurate, potassium chloroaurate and ammonium chloraurate are a variety of；More preferably four hydration chlorine
Auric acid, chlorauride, aurous chloride, sodium chloraurate, potassium chloroaurate or ammonium chloraurate, most preferably four hydration gold chlorides.
The present invention is in principle not particularly limited the specific choice in the ruthenium source, and those skilled in the art can be according to reality
Border experimental conditions, product requirement and particular use are selected and are adjusted, and the present invention is to guarantee reaction effect and Jin Liaona
Nano composite material has better pattern and catalytic performance, the ruthenium source, the i.e. predecessor of ruthenium, the preferably change containing trivalent ruthenium
Object is closed, more preferably includes one of ruthenic chloride, ruthenium hydrochloride potassium and ruthenium hydrochloride ammonium or a variety of, more preferably ruthenic chloride, ruthenium hydrochloride
Potassium or ruthenium hydrochloride ammonium, most preferably ruthenic chloride.
The present invention is in principle not particularly limited the specific ratio in the Jin Yuan and ruthenium source, and those skilled in the art can be with
Selected and adjusted according to actual experiment situation, product requirement and particular use, the present invention be guarantee reaction effect and
Golden ruthenium nanocomposite has better pattern and catalytic performance, and the molar ratio in the Jin Yuan and ruthenium source is preferably 1:(0.001
~1), more preferably 1:(0.01~0.8), more preferably 1:(0.1~0.79), more preferably 1:(0.3~0.78) and, more preferably
For 1:(0.5~0.77), more preferably 1:(0.6~0.76), most preferably 1:0.75.
In the present invention, the Jin Yuan and the alcoholic solution in ruthenium source can for Jin Yuan alcoholic solution and ruthenium source alcoholic solution simultaneously
It is added, or the mixing alcoholic solution for first obtaining Jin Yuan and ruthenium source adds.The present invention is in principle to the Jin Yuan and ruthenium source
The specific concentration of alcoholic solution be not particularly limited, those skilled in the art can according to actual experiment situation, product requirement with
And particular use is selected and is adjusted, the present invention is to guarantee that reaction effect and golden ruthenium nanocomposite have better shape
The concentration in ruthenium source is preferably 0.001~1.300mg/mL in the alcoholic solution in looks and catalytic performance, the Jin Yuan and ruthenium source, more preferably
For 0.01~1.200mg/mL, more preferably 0.1~1.1000mg/mL, more preferably 0.5~1.000mg/mL, the Jin Yuan
It is specifically as follows 2.600mg/mL and 1.300mg/mL with the concentration of Jin Yuan in the alcoholic solution in ruthenium source and the concentration in ruthenium source.
The present invention is in principle not particularly limited the selection of the solvent in the alcoholic solution, and those skilled in the art can be with
Selected and adjusted according to actual experiment situation, product requirement and particular use, the present invention be guarantee reaction effect and
Golden ruthenium nanocomposite has better pattern and catalytic performance, and the solvent in the alcoholic solution preferably includes a contracting diethyl two
One of alcohol, ethylene glycol, glycerine, propylene glycol and cyclohexanol are a variety of, more preferably diglycol, ethylene glycol, third
Triol, propylene glycol or cyclohexanol, most preferably diglycol.
The present invention is in principle not particularly limited the mode and speed of the addition, and those skilled in the art can basis
Actual experiment situation, product requirement and particular use are selected and are adjusted, and the present invention is to guarantee reaction effect and golden ruthenium
Nanocomposite has better pattern and catalytic performance, and the mode of the addition is preferably that syringe pump is added, the addition
Speed be preferably 1.0~2.0mL/min, more preferably 1.4~1.9mL/min, more preferably 1.6~1.85mL/min, most
Preferably 1.8mL/min.
The present invention is in principle not particularly limited the temperature of the preheating, and those skilled in the art can be according to practical reality
It tests situation, product requirement and particular use to be selected and adjusted, the present invention is to guarantee that reaction effect and golden ruthenium nanometer are multiple
Condensation material has better pattern and catalytic performance, reduces temperature-rise period, so that reaction can be carried out directly at the reaction temperatures,
The temperature of the preheating is preferably consistent with reaction temperature, and the temperature after the preheating is preferably 180~260 DEG C, more preferably 190
~250 DEG C, more preferably 200~240 DEG C, more preferably 210~230 DEG C.
The present invention is in principle not particularly limited the specific choice in the alcohol liquid, and those skilled in the art can basis
Actual experiment situation, product requirement and particular use are selected and are adjusted, and the present invention is to guarantee reaction effect and golden ruthenium
Nanocomposite has better pattern and catalytic performance, and the alcohol liquid preferably includes diglycol, ethylene glycol, the third three
One of alcohol, propylene glycol and cyclohexanol are a variety of, more preferably diglycol, ethylene glycol, glycerine, propylene glycol or ring
Hexanol, most preferably diglycol.
The present invention is in principle not particularly limited the specific ratio of the alcohol liquid, and those skilled in the art can be according to reality
Border experimental conditions, product requirement and particular use are selected and are adjusted, and the present invention is to guarantee reaction effect and Jin Liaona
Nano composite material has better pattern and catalytic performance, and the volume ratio of the alcoholic solution and the alcohol liquid in the Jin Yuan and ruthenium source is excellent
It is selected as (3.4~4.1): (20~100), more preferably (3.4~4.1): (40~80), more preferably (3.4~4.1): (50~
70), or (3.5~4.0): (20~100), perhaps (3.6~3.9): (20~100) or (3.7~3.8): (20
~100), it is specifically as follows 4:(20~100).
The present invention is further to promote reaction effect, can regulate and control the pattern of golden ruthenium nanocomposite, so that regulation is urged
Change performance, crystal face protective agent can also preferably be added in the alcohol liquid, i.e., add Jin Yuan and the alcoholic solution in ruthenium source, crystal face protective agent
Enter and reacted in the alcohol liquid to after preheating, obtains golden ruthenium nanocomposite.Crystal face protective agent of the present invention preferably includes
One of potassium iodide, potassium bromide, citric acid and N vinylamide polymer are a variety of, more preferably include potassium iodide, bromine
Change one or more, the more preferable N vinylamide polymer of potassium and N vinylamide polymer.Described and N- second
Eneamide quasi polymer is preferably polyvinylpyrrolidone, and more preferably relative molecular mass is 10000,29000,40000,
One of 55000 and 160000 polyvinylpyrrolidone is a variety of, more preferably relative molecular weight be 40000 polyethylene
Pyrrolidones.
The present invention is in principle not particularly limited the condition of the reaction, and those skilled in the art can be according to practical reality
It tests situation, product requirement and particular use to be selected and adjusted, the present invention is to guarantee that reaction effect and golden ruthenium nanometer are multiple
Condensation material has better pattern and catalytic performance, and the temperature of the reaction is preferably 180~260 DEG C, more preferably 190~
250 DEG C, more preferably 200~240 DEG C, more preferably 210~230 DEG C, most preferably 215 DEG C.The time of the reaction is preferred
It is 5~30 minutes, more preferably 10~25 minutes, more preferably 15~20 minutes, most preferably 15 minutes.
The present invention is preferably complete and refinement synthesis process, advanced optimizes preparation process, and it is nano combined to improve golden ruthenium
The synthetic method of the catalytic activity of material, the gold ruthenium nanocomposite is specifically as follows following steps:
By molar ratio be 1:(0.001~1) four hydration gold chlorides and ruthenic chloride 3.4~4.1mL of diglycol
Solution, by syringe pump with the speed of 1~2mL/min, be added be preheating to 180~260 DEG C dissolved with the poly- second of 0~177.6mg
It in 20~100mL diglycol solution of alkene pyrrolidone, is reacted 5~30 minutes at 180~260 DEG C, obtains double gold
Belong to the optical drive catalyst of nanostructure.
The present invention is practical preferably to carry out, and expands the scope of application and practicability of golden ruthenium nanocomposite, also provides
A kind of golden ruthenium nanocomposite catalyst, the golden ruthenium nanocomposite including carrier and load on the carrier；
It is described gold ruthenium nanocomposite be above-mentioned technical proposal any one described in golden ruthenium nanocomposite or on
State golden ruthenium nanocomposite synthesized by synthetic method described in technical solution any one.
Selection of the present invention to the material in above-mentioned golden ruthenium nanocomposite catalyst, the Nomenclature Composition and Structure of Complexes, and it is corresponding
Optimum principle, selection, the Nomenclature Composition and Structure of Complexes and corresponding optimum principle with the material in aforementioned golden ruthenium nanocomposite
It can preferably be corresponded to, this is no longer going to repeat them.
The present invention is in principle not particularly limited the type of the carrier, and those skilled in the art can be according to actually answering
It is selected and is adjusted with situation, product requirement and particular use, the present invention is preferably to guarantee reaction effect and golden ruthenium
Nanocomposite has better pattern and catalytic performance, and the carrier can be conventional catalyst carrier, or solidifying
Glue carrier, specifically preferably include carbon carrier, silica supports, alumina carrier, ceramic monolith, molecular sieve, silicon carbide,
One of kaolin, fluoropolymer and quartz glass are a variety of, more preferably carbon carrier, silica supports, three oxidations two
Alumina supporter, ceramic monolith, molecular sieve, silicon carbide, kaolin, fluoropolymer or quartz glass.
The present invention is in principle not particularly limited the load capacity of the golden ruthenium nanocomposite catalyst, this field skill
Art personnel can select and adjust according to practical situations, product requirement and particular use, and the present invention is better
Guarantee that reaction effect and golden ruthenium nanocomposite have better pattern and catalytic performance, the gold ruthenium nanocomposite
The load capacity of catalyst is preferably 10%~60%, and more preferably 20%~50%, more preferably 30%~40%.
The present invention also provides golden ruthenium nanocomposites, above-mentioned technical proposal described in above-mentioned technical proposal any one
Gold described in golden ruthenium nanocomposite or above-mentioned technical proposal any one prepared by synthetic method described in any one
Application of the ruthenium nanocomposite catalyst in the reaction of optical drive class.
The definition and specific type that the present invention reacts the optical drive class are not particularly limited, with those skilled in the art
The definition and specific type of well known optical drive class reaction, those skilled in the art can be according to practical situations, production
Product require and particular use is selected and adjusted, and the present invention is preferably to guarantee catalytic effect, the optical drive class reaction
Preferably include the reaction of optical drive fixed nitrogen.
Optical drive fixed nitrogen reaction of the present invention, specifically preferably includes following steps:
Catalyst dispersion is placed in nitrogen atmosphere, light-catalyzed reaction is carried out under light illumination, obtains ammonia.
Wherein, the pressure of the nitrogen is preferably 1~20bar, more preferably 3~18bar, more preferably 5~15bar,
More preferably 8~12bar.The temperature of the light-catalyzed reaction is preferably room temperature~200 DEG C, and room temperature is preferably 0~40 DEG C, more excellent
It is selected as 5~35 DEG C, more preferably 10~30 DEG C, more preferably 15~25 DEG C.The temperature of light-catalyzed reaction is more preferably 25~150
DEG C, more preferably 50~120 DEG C, more preferably 70~100 DEG C.The light irradiation is preferably full spectrum light irradiation.The light
The intensity of irradiation is preferably 20~3200mWcm-2, more preferably 200~2500mWcm-2, more preferably 500~
2000mW·cm-2, more preferably 1000~1500mWcm-2。
Optical drive fixed nitrogen reaction, more specifically preferably following steps:
It disperses catalyst in pure water, in the nitrogen atmosphere, room temperature and 400mWcm of two atmospheric pressures-2Full spectrum
It is reacted to obtain ammonia under light irradiation.
In the present invention, the solvent that the reaction of optical drive catalysis fixed nitrogen uses is preferably pure water；The reaction atmosphere can be
The nitrogen atmosphere of two atmospheric pressure；The reaction temperature can be room temperature；The full spectrum light can be 400mWcm according to intensity-2。
Above-mentioned steps of the present invention provide a kind of golden ruthenium nanocomposite and its synthetic method, use for fixed nitrogen reaction
Golden ruthenium nanocomposite optical drive catalyst, application in fixed nitrogen reaction.The present invention creates the golden ruthenium nanocomposite provided,
Using gold nano grain as core, surface recombination has metal Ru, and further can also control catalysis by adjusting the pattern on surface
Performance.The present invention utilizes the phasmon effect of metal nano material, and wherein gold nano grain is effectively absorbed as extinction center
Visible light, and electromagnetic near field enhancing and thermoelectronic effect are generated to drive chemical reaction；Ruthenium nanostructure is lighted as active sites
To the effect of adsorption activation nitrogen molecule, and then solar energy is realized to chemical energy Efficient Conversion, in 1~20 atmospheric pressure
Nitrogen atmosphere, room temperature and 20~3200mWcm-2Full spectrum light irradiation is lower to carry out fixed nitrogen reaction, effectively promotes reaction efficiency, keeps away
A large amount of consumption in traditional industrial process to energy are exempted from.
And provided by the present invention for fixed nitrogen reaction optical drive catalyst preparation method in, using alcohol liquid as solvent
And reducing agent, and in such a way that the alcoholic solution of gold and ruthenium presoma is added in syringe pump, 5~30 points are reacted at 180~260 DEG C
The nanocatalyst of composite construction is made up of simple one-step method for clock, is suitble to large-scale industrial production, has extensive work
Industry application prospect.Simultaneously, additionally it is possible to further pattern be modified by the way that crystal face protective agent is added, preferably widened compound
The application range of structure nano catalyst.A this step in the solution prepares the optical drive catalysis of golden ruthenium bimetal nanostructure
The catalyst is used for the reaction of optical drive fixed nitrogen, excellent fixed nitrogen reactivity can be shown under Room-temperature low-pressure by agent.
The experimental results showed that the yield of the method ammonia in the present invention reaches as high as 220 μm of olg-1·h-1。
In order to further illustrate the present invention, below with reference to embodiment to a kind of golden ruthenium nanocomposite provided by the invention
And its synthetic method, golden ruthenium nanocomposite catalyst, using being described in detail, but it is to be understood that these embodiments
It is to be implemented under the premise of the technical scheme of the present invention, the detailed implementation method and specific operation process are given, only
It is to further illustrate the features and advantages of the present invention, rather than limiting to the claimed invention, protection model of the invention
It encloses and is also not necessarily limited to following embodiments.
Embodiment 1
100mL three-neck flask is added with 177.6mg polyvinylpyrrolidone in 40mL diglycol to be carried out with magneton
Stirring, and it is preheating to 215 DEG C.Then, 3.5mL passes through dissolved with the diglycol solution for being hydrated gold chloride of 10.39mg tetra-
Syringe pump is with 1.8mL min-1Speed be added in three-neck flask.The solution of reaction from the beginning colourless gradually becomes red
Color.Reaction terminates after carrying out 15min, collects product with centrifuge with 8000 rpms of centrifugation 9min, and washed one time with acetone,
Deionization is washed twice, is finally re-dispersed into 2mL deionized water again, is finally obtained gold nano grain, i.e., initial Jenner
Rice grain.
Transmission electron microscope detection is carried out to initial gold nano grain prepared by the embodiment of the present invention 1, as a result such as Fig. 1 institute
Show.
Referring to Fig. 1, Fig. 1 is transmission electron microscope (TEM) photo of initial gold nano grain prepared by the embodiment of the present invention 1.By
Fig. 1 is it is found that initial gold nano grain prepared by the present invention has the crystal structure of five weight twins.
Embodiment 2
The preparation of golden ruthenium bimetal nanostructure catalyst
100mL three-neck flask is added with 177.6mg polyvinylpyrrolidone in 40mL diglycol to be carried out with magneton
Stirring, and it is preheating to 215 DEG C.Then, 4mL is hydrated a contracting diethyl of gold chloride and 3.92mg ruthenic chloride dissolved with 10.39mg tetra-
Glycol solution is by syringe pump with 1.8mL min-1Speed be added in three-neck flask.The solution of reaction from the beginning pale red
Color gradually becomes brown.Reaction terminates after carrying out 15min, collects product with centrifuge with 8000 rpms of centrifugation 9min, and
It is washed one time with acetone, deionization is washed twice, is finally re-dispersed into 2mL deionized water again.
Transmission electron microscope and high score have been carried out to golden ruthenium bimetal nano sandwich prepared by the embodiment of the present invention 2
Distinguish that transmission electron microscope detects, as a result as shown in Figures 2 and 3.
Referring to fig. 2, Fig. 2 is the transmission of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention
Electronic Speculum (TEM) photo.
Fig. 3 is that the high-resolution of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention transmits electricity
Mirror (HRTEM) photo.
By Fig. 2 and 3 it is found that gold ruthenium bimetal nano sandwich prepared by the present invention, the metal Ru of surface recombination
With class antenna structure, it is grown in the surface of gold nano grain core in line or tufted, there is sea urchin shape structure on whole pattern
Pattern.And when synthesizing golden ruthenium nanocomposite, initial gold nano grain pattern is changed, in the process for being formed and being changed
In, it is nano combined to be formed simultaneously the golden ruthenium with the gold nano grain kernel not exactly the same with initial gold nano grain pattern
Material.
The detection of XRD diffraction is carried out to golden ruthenium bimetal nano sandwich prepared by the present embodiment 2, as a result such as
Shown in Fig. 4.
Referring to fig. 4, Fig. 4 is the X-ray of golden ruthenium bimetal nano sandwich prepared by the present embodiment 2 of the present invention
Diffraction pattern (XRD).
As shown in Figure 4, golden ruthenium bimetal nano sandwich prepared by the present invention has face-centered cubic closest packing
Crystal structure.
Embodiment 3
Without using the preparation of the golden ruthenium bimetal nanostructure catalyst of polyvinylpyrrolidone in synthesis process
100mL three-neck flask is added in 40mL diglycol to be stirred with magneton, and is preheating to 215 DEG C.Then,
4mL passes through syringe pump dissolved with the diglycol solution for being hydrated gold chloride and 3.92mg ruthenic chloride of 10.39mg tetra- with 1.8mL
min-1Speed be added in three-neck flask.The light red of the solution of reaction from the beginning gradually becomes brown.Reaction carries out
Terminate after 15min, collects product with centrifuge with 8000 rpms of centrifugation 9min, and washed one time with acetone, deionization washing
It twice, is finally re-dispersed into 2mL deionized water again.
To the golden ruthenium bimetal nanostructure for not using polyvinylpyrrolidone preparation in 3 synthesis process of the embodiment of the present invention
Catalyst has carried out transmission electron microscope detection, as a result as shown in Figure 4.
Referring to Fig. 5, Fig. 5 is the transmission of golden ruthenium bimetal nano sandwich prepared by the present embodiment 3 of the present invention
Electronic Speculum (TEM) photo.
As shown in Figure 5, golden ruthenium nanocomposite prepared by the present invention, gold nano grain core surface grow villous shape
Metal Ru.
Golden ruthenium bimetal nanostructure catalysis prepared by the gold nano grain and embodiment 2 prepared to the embodiment of the present invention 1
Uv-visible absorption spectra (UV-vis) spectrogram of agent is analyzed, as a result as shown in Figure 6.
Referring to Fig. 6, Fig. 6 be gold nano grain prepared by the present invention and golden ruthenium bimetal nanostructure catalyst it is ultraviolet-
Visible absorption spectra (UV-vis) spectrogram.
Embodiment 4~6
In the nitrogen atmosphere, room temperature and 400mWcm of two atmospheric pressures-2The fixed nitrogen of the lower reaction 2 hours of full spectrum light irradiation
Reaction
According to the catalyst of the method preparation in Examples 1 to 3, embodiment 4~6 carries out fixed nitrogen catalytic reaction to it respectively
The test of efficiency.
The catalyst that 0.2mg is prepared according to the method in Examples 1 to 3 is separately added into a homemade quartz ampoule,
And supplementing deionized water to overall solution volume is 3mL.Then quartz ampoule is vacuumized, and is filled with the nitrogen of 2 atmospheric pressure, is repeated
This process is three times to remove air remaining in quartz ampoule.When carrying out the fixed nitrogen reaction of optical drive, sealed in quartz ampoule 2 big
The nitrogen of air pressure, and with magneton strong stirring, use 400mW cm-2Full spectrum light irradiate at normal temperature 2 hours.
The present invention calculates the yield for the ammonia that the corresponding fixed nitrogen reaction of catalyst in embodiment 4~6 generates, as a result such as Fig. 7
It is shown.
Referring to Fig. 7, Fig. 7 is the ammonia that the corresponding fixed nitrogen of catalyst reacts preceding generation in 2 hours in the embodiment of the present invention 4~6
Average yield.
As seen from Figure 7, as 400mW cm-2Full spectrum light irradiate quartz ampoule, react in embodiment 12 hours and be averaged
Ammonia yield is 13.9 μm of olg-1·h-1.Embodiment 2 and embodiment 3 are divided in the average ammonia yield of reaction 2 hours under the same terms
It Wei not 220 μm of olg-1·h-1With 66.1 μm of olg-1·h-1.Illustrate the gold nano grain composite nanostructure for coating ruthenium metal
Catalyst can effectively facilitate the progress that fixed nitrogen reacts under temperate condition, and use polyvinylpyrrolidone in the synthesis process
Golden ruthenium bimetal nanostructure catalyst catalytic efficiency it is higher.
Embodiment 7
In the nitrogen atmosphere, room temperature and 400mWcm of two atmospheric pressures-2The lower reaction different time of full spectrum light irradiation is consolidated
Nitrogen reaction
Fixed nitrogen reaction is carried out according to the method that the method in embodiment 2 prepares catalyst and embodiment 5, unlike, it is real
The reaction time for applying example 7 is respectively 0,1,2,3,6,9,12,15,18,21 and for 24 hours.
The present invention calculates the average ammonia yield of fixed nitrogen reaction of the catalyst under the differential responses time in embodiment 7, such as
Shown in Fig. 8.
Referring to Fig. 8, Fig. 8 is the average ammonia of fixed nitrogen reaction of the catalyst under the differential responses time in the embodiment of the present invention 7
The relation curve of yield and reaction time.
Embodiment 8
Consolidating for full spectrum light irradiation 2 hours of different light intensity is used under the nitrogen atmosphere, normal temperature condition of two atmospheric pressures
Nitrogen reaction
Fixed nitrogen reaction is carried out according to the method that the method in embodiment 2 prepares catalyst and embodiment 5, unlike, it is real
The full spectrum light light intensity applied used in irradiating in example 8 is respectively 400,800,1600,2400 and 3200mWcm-2。
The average ammonia that the present invention calculates fixed nitrogen reaction of the catalyst under the irradiation of different light intensity of incident light in embodiment 8 produces
Rate, as shown in Figure 8.
Referring to Fig. 9, Fig. 9 is first 2 hours of fixed nitrogen reaction of the catalyst of the present invention under the irradiation of different light intensity of incident light
The relation curve that average ammonia yield changes with light intensity.
Above to a kind of golden ruthenium nanocomposite and its synthetic method, use for fixed nitrogen reaction provided by the present invention
In the golden ruthenium nanocomposite optical drive catalyst of fixed nitrogen reaction, using being described in detail, it is used herein specifically
Principle and implementation of the present invention are described for a example, the present invention that the above embodiments are only used to help understand
Method and its core concept, including best mode, and but also any person skilled in the art can practice this hair
It is bright, including any device or system of manufacture and use, and implement the method for any combination.It should be pointed out that for the art
Those of ordinary skill for, without departing from the principle of the present invention, can also to the present invention carry out it is several improvement and repair
Decorations, these improvements and modifications also fall within the scope of protection of the claims of the present invention.The range of the invention patent protection passes through power
Benefit requires to limit, and may include those skilled in the art it is conceivable that other embodiments.If these other embodiments have
Have a structural element for being not different from claim character express, or if they include with the character express of claim without
The equivalent structural elements of essence difference, then these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of gold ruthenium nanocomposite, which is characterized in that the gold ruthenium nanocomposite is using gold nano grain as core, table
Face is compounded with metal Ru.
2. gold ruthenium nanocomposite according to claim 1, which is characterized in that the gold ruthenium nanocomposite particles
Partial size be 25~65nm；
In the gold ruthenium nanocomposite, the molar ratio of gold element and ruthenium element is 1:(0.001~0.39)；
The metal Ru of the surface recombination has class antenna structure；
The gold ruthenium nanocomposite has the pattern of sea urchin shape structure；
The gold ruthenium nanocomposite has the crystal structure of face-centered cubic closest packing.
3. gold ruthenium nanocomposite according to claim 1, which is characterized in that the gold ruthenium nanocomposite is in shape
At with change initial gold nano grain pattern during be formed simultaneously；
The initial gold nano grain has five heavy twin structures；
The pattern of the pattern and initial gold nano grain of gold nano grain is not exactly the same in the gold ruthenium nanocomposite；
The partial size of the gold nano grain is 20~60nm；
The partial size of the initial gold nano grain is 35~100nm.
4. a kind of synthetic method of gold ruthenium nanocomposite, which comprises the following steps:
A) alcoholic solution of Jin Yuan and ruthenium source are added in the alcohol liquid after preheating and reacted, golden ruthenium nanocomposite is obtained.
5. synthetic method according to claim 4, which is characterized in that the Jin Yuan include four hydration gold chlorides, chlorauride,
One of aurous chloride, sodium chloraurate, potassium chloroaurate and ammonium chloraurate are a variety of；
The ruthenium source includes one of ruthenic chloride, ruthenium hydrochloride potassium and ruthenium hydrochloride ammonium or a variety of；
The molar ratio in the Jin Yuan and ruthenium source is 1:(0.001~1)；
The concentration in ruthenium source is 0.001~1.300mg/mL in the Jin Yuan and the alcoholic solution in ruthenium source；
Solvent in the alcoholic solution include one of diglycol, ethylene glycol, glycerine, propylene glycol and cyclohexanol or
It is a variety of；
The speed of the addition is 1.0~2.0mL/min.
6. synthetic method according to claim 4, which is characterized in that the alcohol liquid include diglycol, ethylene glycol,
One of glycerine, propylene glycol and cyclohexanol are a variety of；
Crystal face protective agent can also be added in the alcohol liquid；
The crystal face protective agent includes one of potassium iodide, potassium bromide, citric acid and N vinylamide polymer or more
Kind；
Temperature after the preheating is 180~260 DEG C；
The temperature of the reaction is 180~260 DEG C；
The time of the reaction is 5~30 minutes；
The volume ratio of the Jin Yuan and the alcoholic solution in ruthenium source and the alcohol liquid is (3.4~4.1): (20~100).
7. a kind of gold ruthenium nanocomposite catalyst, which is characterized in that including the golden ruthenium of carrier and load on the carrier
Nanocomposite；
The gold ruthenium nanocomposite is that golden ruthenium nanocomposite described in claims 1 to 3 any one or right are wanted
Seek golden ruthenium nanocomposite synthesized by synthetic method described in 4~6 any one.
8. gold ruthenium nanocomposite catalyst according to claim 7, which is characterized in that the carrier includes that carbon carries
Body, silica supports, alumina carrier, ceramic monolith, molecular sieve, silicon carbide, kaolin, fluoropolymer and quartzy glass
One of glass is a variety of；
The carrier can be gel carrier；
The load capacity of the load is 10%~60%.
9. conjunction described in golden ruthenium nanocomposite, claim 4~6 any one described in claims 1 to 3 any one
It is urged at golden ruthenium nanocomposite described in golden ruthenium nanocomposite synthesized by method or claim 7~8 any one
Application of the agent in the reaction of optical drive class.
10. application according to claim 9, which is characterized in that the optical drive class reaction includes that optical drive fixed nitrogen reacts；
The optical drive fixed nitrogen reaction, specifically includes the following steps:
Catalyst dispersion is placed in nitrogen atmosphere, light-catalyzed reaction is carried out under light illumination, obtains ammonia；
The pressure of the nitrogen is 1~20bar；
The temperature of the light-catalyzed reaction is room temperature~200 DEG C；
The intensity of the light irradiation is 20~3200mWcm-2。
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| CN112129819A (en) * | 2020-10-12 | 2020-12-25 | 江南大学 | Construction method and application of specific electrochemical sensor for detecting tumor marker |
| CN112129820A (en) * | 2020-10-12 | 2020-12-25 | 江南大学 | Construction method and application of specific electrochemical sensor for HER2 detection |
| CN112129819B (en) * | 2020-10-12 | 2021-07-06 | 江南大学 | Construction method and application of specific electrochemical sensor for detecting tumor marker |
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| CN117564289A (en) * | 2024-01-12 | 2024-02-20 | 中国科学技术大学 | Iridium ruthenium gold core-shell structure nano material and preparation method and application thereof |
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