CN111589444A - Noble metal quantum dot and preparation method and application thereof - Google Patents
Noble metal quantum dot and preparation method and application thereof Download PDFInfo
- Publication number
- CN111589444A CN111589444A CN202010367124.9A CN202010367124A CN111589444A CN 111589444 A CN111589444 A CN 111589444A CN 202010367124 A CN202010367124 A CN 202010367124A CN 111589444 A CN111589444 A CN 111589444A
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- CN
- China
- Prior art keywords
- quantum dots
- noble metal
- quantum dot
- vanadate
- quantum
- Prior art date
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- Granted
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 90
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001354 calcination Methods 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 239000011812 mixed powder Substances 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000010970 precious metal Substances 0.000 claims abstract description 18
- -1 alkali metal cations Chemical class 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000011858 nanopowder Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002343 gold Chemical class 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002503 iridium Chemical class 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 9
- 150000003283 rhodium Chemical class 0.000 claims description 9
- 150000003303 ruthenium Chemical class 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 150000003057 platinum Chemical class 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 150000003378 silver Chemical class 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002907 osmium Chemical class 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- YDHJLJIJUCHSBV-UHFFFAOYSA-M Cl[Os+3].N Chemical compound Cl[Os+3].N YDHJLJIJUCHSBV-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 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
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007769 metal material Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019475 NaV3O8 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PSLMOSLVUSXMDQ-UHFFFAOYSA-N iridium;pentane-2,4-dione Chemical compound [Ir].CC(=O)CC(C)=O PSLMOSLVUSXMDQ-UHFFFAOYSA-N 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ZJYSTCMILDFRDL-UHFFFAOYSA-N N.[Os+4] Chemical compound N.[Os+4] ZJYSTCMILDFRDL-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BQHZBCPRRFCFNZ-UHFFFAOYSA-N [Au].CC(=O)CC(C)=O Chemical compound [Au].CC(=O)CC(C)=O BQHZBCPRRFCFNZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Images
Classifications
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- 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
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
The invention belongs to the technical field of quantum dot materials, and particularly relates to a noble metal quantum dot and a preparation method and application thereof. The method comprises the following steps: 1) soaking the vanadate powder of alkali metal cations or transition metal cations with a layered structure into an aqueous solution of soluble noble metal salt for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the vanadate of the noble metal; 2) calcining the vanadate of the noble metal obtained in the step 1) to obtain mixed powder formed by dispersing the quantum dots of the noble metal in the vanadium oxide residue; 3) acid cleaning is carried out on the mixed powder obtained in the step 2), vanadium oxide residues are removed, and the precious metal quantum dots are obtained.
Description
Technical Field
The invention belongs to the technical field of quantum dot materials, and particularly relates to a noble metal quantum dot and a preparation method and application thereof.
Background
A quantum dot is a low dimensional semiconductor material whose dimensions in all three dimensions are no greater than twice the exciton bohr radius of its corresponding semiconductor material. Quantum dots are generally spherical or spheroidal, often between 1-20nm in diameter, and can also be considered as nanomaterials in nature. Due to good physical and chemical properties such as catalysis and optics, precious metal nano materials have recently received wide attention from many researchers in the industry and scientific research community, and have been widely applied to the fields of fuel cells, chemical catalysis and the like.
To date, scientists have explored various methods for preparing monodisperse precious metal nanoparticles, mainly including physical methods and chemical methods. The physical method can prepare nanoparticles with higher purity but uneven particle size distribution, so that the nanoparticles with small particle size can be prepared more difficultly by effectively controlling the size of the nanoparticles. The chemical method mainly comprises a thermal decomposition method, a micro-emulsion method, a chemical reduction method, a microwave reduction method, a phase transfer reduction method and the like. However, these methods are not very practical, generally require expensive noble metal precursors and phase transfer agents, use toxic organic solvents which may cause environmental pollution, and are difficult to separate, especially when the size of nanoparticles is 1nm to 2nm, require a centrifuge to centrifuge at high speed for a long time to separate, which greatly limits the large-scale preparation of small-size nanoparticles.
At present, researchers at home and abroad do much work on the preparation of small-particle-size and monodisperse precious metal nanoparticles. Wherein the Brust-Schiffrin two-phase method has great success in the aspect of synthesizing 1-6 nm monodisperse noble metal nano particles. The method mainly uses some quaternary ammonium salts as phase transfer agents, transfers noble metal inorganic salts from a water phase to an organic phase (toluene and the like), and prepares monodisperse nanoparticles of Au, Ag, Cu and the like by reduction. Chinese patent CN101992302A discloses a method for preparing high-dispersion noble metal nanoparticles by mixing ethylene glycol with oleylamine or oleic acid, adding a noble metal precursor, and heating to 100-300 ℃. Japanese patent application 200580007501.1 of Dai chemical industry Co., Ltd.utilizes thermal decomposition of a quaternary ammonium salt noble metal complex to prepare noble metal particles having a particle diameter of 20nm or less. It has been found that the prior art is more advanced in the preparation process, but mostly involves the use of organic phases.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a noble metal quantum dot and a preparation method and application thereof. The preparation method of the noble metal quantum dot provided by the invention realizes the preparation of the noble metal quantum dot in the inorganic phase.
The technical scheme provided by the invention is as follows:
a preparation method of a noble metal quantum dot comprises the following steps:
1) soaking alkali metal cation or transition metal cation vanadate nano powder into an aqueous solution of soluble precious metal salt, wherein the concentration of the precious metal salt is 0.001-1 mol/L, soaking, performing ion exchange, and sequentially performing solid-liquid separation, washing and drying to obtain precious metal vanadate;
2) calcining the vanadate of the noble metal obtained in the step 1) to obtain mixed powder formed by dispersing the quantum dots of the noble metal in vanadium oxide residues;
3) acid washing is carried out on the mixed powder obtained in the step 2), and the vanadium oxide residue is removed, so that the noble metal quantum dots are obtained.
In the above technical scheme:
in the step 2), carrying out ion exchange on vanadate nano powder of alkali metal cations or transition metal cations and an aqueous solution of soluble noble metal salt to obtain vanadate of noble metal; and calcining the obtained vanadate of the noble metal ions to obtain mixed powder formed by dispersing the quantum dots of the noble metal in the vanadium oxide residue.
And in the step 3), carrying out acid washing on the obtained mixed powder to remove the vanadium oxide residues, so as to obtain the noble metal quantum dots.
The technical scheme does not adopt organic solvent.
According to the technical scheme, the precious metal quantum dots can be obtained through simple ion exchange, solid-liquid separation and calcination.
The technical scheme can obtain a single noble metal quantum dot and can also obtain a mixed noble metal quantum dot.
Preferably, in the above technical solution, a layer-structured vanadate nanopowder of alkali metal cations or transition metal cations is used.
Specifically, in the step 1), the soluble precious metal salt is selected from one or more of a soluble salt containing gold, a soluble salt containing silver, a soluble salt containing platinum, a soluble salt containing ruthenium, a soluble salt containing rhodium, a soluble salt containing palladium, a soluble salt containing osmium or a soluble salt containing iridium.
Specifically, in step 1), the soluble precious metal salt is selected from one or more of chloroauric acid, gold acetylacetonate, silver nitrate, chloroplatinic acid, platinum acetylacetonate, ammonium chlororuthenate, ruthenium acetylacetonate, ammonium chlororhodate, rhodium acetylacetonate, ammonium chloropalladate, palladium acetylacetonate, ammonium chloroosmium, ammonium chloroiridate and iridium acetylacetonate.
For each of the above salts that are insoluble in cold water, the solvent may be heated appropriately to increase solubility while avoiding exceeding the decomposition temperature.
Specifically, in step 3), the noble metal quantum dots are selected from any one or a mixture of more of gold quantum dots, silver quantum dots, platinum quantum dots, ruthenium quantum dots, rhodium quantum dots, palladium quantum dots, osmium quantum dots and iridium quantum dots.
Specifically, in step 1), the cation in the vanadate of the alkali metal cation or the transition metal cation is selected from any one or more of lithium ion, sodium ion, potassium ion, ammonium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, or zinc ion.
For the salts of each of the above cations that are insoluble in cold water, the solvent may be heated appropriately to increase solubility while avoiding exceeding the decomposition temperature.
Specifically, the soaking time in the step 1) is 1-72 h
Specifically, the drying temperature in the step 1) is 50-80 ℃.
Based on the technical scheme, the separation of vanadate of noble metal can be realized.
Specifically, in the step 2), the calcining temperature is 200-800 ℃; the calcining time is 1-72 h; the temperature rise rate of the calcination is 0.5-10 ℃/min.
Based on the technical scheme, the precious metal quantum dots can be obtained after the precious metal salt is calcined.
Specifically, in the step 3), the acid is selected from any one or more of 0.8-1.2 mol/L oxalic acid, formic acid, acetic acid, citric acid, hydrochloric acid, nitric acid or sulfuric acid.
Based on the technical scheme, the vanadium oxide residues generated after the precious metal salt is calcined can be dissolved by each acid.
The invention also provides the noble metal quantum dot prepared by the preparation method of the noble metal quantum dot.
Specifically, the quantum dots are gold quantum dots, silver quantum dots, platinum quantum dots, ruthenium quantum dots, rhodium quantum dots, palladium quantum dots, osmium quantum dots or iridium quantum dots;
or, the quantum dot is a mixed quantum dot of at least two of gold quantum dots, silver quantum dots, platinum quantum dots, ruthenium quantum dots, rhodium quantum dots, palladium quantum dots, osmium quantum dots, or iridium quantum dots.
Based on the technical scheme, the simple substance quantum dots or the mixed quantum dots can be selected and obtained according to the requirements. The elementary substance quantum dots are uniform in size, and the particle size is less than 20 nm; and the single substances in the mixed quantum dots have uniform size, and the particle size is less than 20nm, so that the excellent performance of the material in application is ensured.
The invention also provides application of the noble metal quantum dots,
as a catalyst;
as a fluorescent material;
or as a structural reinforcement for the metallic material.
The noble metal quantum dot provided by the invention can be used as a catalyst for heterogeneous catalysis and electrochemical catalysis.
The emission wavelength range of the noble metal quantum dot as the fluorescent material provided by the invention is 400-750 nm.
The noble metal quantum dots provided by the invention can be used as a metal material structure reinforcing agent, can be used as reinforcing agents of a copper metal material, an aluminum metal material, a silver metal material and a titanium metal material, and can increase the tensile strength of the materials by dispersion strengthening, for example, the tensile strength of the copper metal material after the noble metal Pt quantum dots are reinforced can reach 460MPa, and the tensile strength of the aluminum metal material after the noble metal Ag quantum dots are reinforced can reach 400 MPa.
Overall, the present invention has the following beneficial effects:
1) the aspect of catalytic performance; the catalytic activity of the nano material is generally closely related to the crystal face, composition and structure exposed by the nano structure. As the size becomes smaller, the noble metal catalyst has the highest atom utilization efficiency, and the noble metal catalyst efficiency per unit mass also shows exponential increase. The size of the noble metal quantum dot provided by the invention can reach less than 20nm, and the noble metal quantum dot shows excellent catalytic performance.
2) Fluorescent material aspect; the noble metal nano material is applied to the aspects of heavy metal ion detection, biological imaging and the like due to the special fluorescence quantum effect. The optical properties of nanosilver depend on their size, surface structure, and micro-environmental factors. The nano silver with different sizes provided by the invention shows different optical properties, has an emission wavelength range of 400-750nm as a fluorescent material, and has important application in the aspects of biological labeling, sensing, fluorescent labeling and the like.
3) The tensile strength aspect of the material; the noble metal quantum dots are added into the metal matrix composite material to inhibit the growth of crystal grains, so that the crystal grains are refined, after the crystal grains are refined, the length of a dislocation plug group is reduced, the number of the plug dislocations is reduced, the stress concentration degree is reduced, the deformation can be distributed into more crystal grains, and uniform plastic deformation is easier to occur. The increased strength of the grain refinement (Δ σ) can be estimated according to the Hall-Petch equation: Δ σ ═ K (D)-0.5-D0 -0.5) Where K is a constant (related to the nature of the metal), D and D0Is the average grain size of the metal matrix composite and the corresponding pure metal. For example, the tensile strength of the copper metal material reinforced by the noble metal Pt quantum dots can reach 460MPa, and the tensile strength of the aluminum metal material reinforced by the noble metal Ag quantum dots can reach 400 MPa.
Drawings
FIG. 1 is a TEM image of a sample in which noble metal quantum dots prepared in example 1 of the present invention are dispersed in a vanadium oxide residue.
FIG. 2 is a TEM image of a noble metal quantum dot prepared in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Specifically, the soaking time in the step 1) is 1-72 h
Specifically, the drying temperature in the step 1) is 50-80 ℃.
Example 1
Subjecting lithium vanadate LiV3O8Soaking the nano powder into 0.001mol/L chloroauric acid solution for 1h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 50 ℃ to obtain gold vanadate;
calcining the obtained gold vanadate at 800 ℃ for 72h at a heating rate of 10 ℃/min to obtain gold quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L oxalic acid for 72h to remove V2O5Obtaining the gold quantum dots, wherein the size of the quantum dots is less than 20 nm.
Example 2
Adding lithium vanadate Li0.01V3O8Soaking the nano powder into 1mol/L acetylacetone gold solution for 72 hours to perform ion exchange, and then sequentially performing solid-liquid separation, washing and drying at 80 ℃ to obtain gold vanadate;
calcining the obtained gold vanadate at the temperature of 200 ℃, the calcining time of 1h and the calcining temperature rise rate of 0.5 ℃/min to obtain gold quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L formic acid for 1h to remove V2O5Obtaining the gold quantum dots, wherein the size of the quantum dots is less than 20 nm.
Example 3
Adding lithium vanadate Li2V3O8Soaking the nano powder into 1mol/L silver nitrate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain silver vanadate;
calcining the obtained silver vanadate at the calcining temperature of 500 ℃, the calcining time of 5h and the calcining heating rate of 5 ℃/min to obtain silver quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L acetic acid for 1h to remove V2O5Obtaining the silver quantum dots, wherein the size of the quantum dots is equal to 20 nm.
Example 4
Potassium vanadate KV3O8Soaking the nano powder into 0.5mol/L chloroplatinic acid solution for 36h to perform ion exchange, and then sequentially performing solid-liquid separation, washing and drying at 60 ℃ to obtain platinum vanadate;
calcining the obtained platinum vanadate at the temperature of 200 ℃, the calcining time of 10h and the calcining temperature rise rate of 1 ℃/min to obtain platinum quantum dots embedded in V2O5Mixing the powder;
subjecting the obtained mixed powder to 1mol/L hydrochloric acid washing for 5h to remove V2O5Obtaining the quantum dots of the platinum, wherein the size of the quantum dots is less than 20 nm.
Example 5
Sodium vanadate NaV3O8Soaking the nano powder into 0.5mol/L acetylacetone platinum solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain platinum vanadate;
calcining the obtained platinum vanadate at the temperature of 200 ℃, the calcining time of 10h and the calcining temperature rise rate of 1 ℃/min to obtain platinum quantum dots embedded in V2O5Mixing the powder;
subjecting the obtained mixed powder to 1mol/L hydrochloric acid washing for 5h to remove V2O5Obtaining the quantum dots of the platinum, wherein the size of the quantum dots is less than 10 nm.
Example 6
Adding ammonium vanadate NH4V3O8Soaking the nanometer powder in 0.01mol/L ammonium ruthenate solution for 36h for ion exchange, sequentially performing solid-liquid separation, washing and drying at 60 ℃,obtaining ruthenium vanadate;
calcining the obtained ruthenium vanadate at the temperature of 200 ℃, the calcining time of 10h and the calcining temperature rise rate of 1 ℃/min to obtain ruthenium quantum dots embedded in V2O5Mixing the powder;
the obtained mixed powder was washed with 1mol/L nitric acid for 5 hours to remove V2O5And obtaining the ruthenium quantum dots, wherein the size of the quantum dots is less than 5 nm.
Example 7
MnV manganese vanadate3O8Soaking the nano powder into 1mol/L ruthenium acetylacetonate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain ruthenium vanadate;
calcining the obtained ruthenium vanadate at 800 ℃ for 10h at a temperature rise rate of 5 ℃/min to obtain ruthenium quantum dots embedded in V2O5Mixing the powder;
the obtained mixed powder was washed with 1mol/L sulfuric acid for 5 hours to remove V2O5And obtaining the ruthenium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 8
FeV (iron vanadate)3O8Soaking the nano powder into 0.1mol/L ammonium chlororhodate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain rhodium vanadate;
calcining the obtained rhodium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain rhodium quantum dots embedded in V2O5Mixing the powder;
subjecting the obtained mixed powder to 1mol/L citric acid washing for 5 hr to remove V2O5Obtaining the rhodium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 9
Cobalt vanadate Co0.5V3O8Soaking the nanometer powder in 0.1mol/L rhodium acetylacetonate solution for 36h for ion exchange, and sequentially passing throughCarrying out solid-liquid separation, washing and drying at 60 ℃ to obtain rhodium vanadate;
calcining the obtained rhodium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain rhodium quantum dots embedded in V2O5Mixing the powder;
subjecting the obtained mixed powder to 1mol/L citric acid washing for 5 hr to remove V2O5Obtaining the rhodium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 10
Nickel vanadate Ni0.3V3O8Soaking the nano powder into 0.1mol/L ammonium chloropalladate solution for 36 hours for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain palladium vanadate;
calcining the obtained palladium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain palladium quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L oxalic acid and 1mol/L formic acid for 5h to remove V2O5And obtaining the palladium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 11
Adding copper vanadate CuV3O8Soaking the nano powder into 0.1mol/L palladium acetylacetonate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain palladium vanadate;
calcining the obtained palladium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain palladium quantum dots embedded in V2O5Mixing the powder;
subjecting the obtained mixed powder to 1mol/L oxalic acid and 1mol/L hydrochloric acid washing for 5h, removing V2O5And obtaining the palladium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 11
Zinc vanadate Zn0.5V3O8Nano meterSoaking the powder in 0.1mol/L ammonium osmium chlorophosmate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain osmium vanadate;
calcining the obtained osmium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain osmium quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L oxalic acid for 5h to remove V2O5And obtaining the quantum dots of osmium, wherein the size of the quantum dots is less than 10 nm.
Example 12
Adding ammonium vanadate NH4V3O8Soaking the nano powder into 0.1mol/L ammonium chloroiridate solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain iridium vanadate;
calcining the obtained iridium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain iridium quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L oxalic acid and 1mol/L nitric acid for 5h to remove V2O5Obtaining the iridium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 13
Adding ammonium vanadate NH4V3O8Soaking the nano powder into 0.1mol/L acetylacetone iridium solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain iridium vanadate;
calcining the obtained iridium vanadate at 800 ℃ for 10h at a heating rate of 5 ℃/min to obtain iridium quantum dots embedded in V2O5Mixing the powder;
washing the obtained mixed powder with 1mol/L oxalic acid for 5h to remove V2O5Obtaining the iridium quantum dots, wherein the size of the quantum dots is less than 10 nm.
Example 14
Sodium ammonium vanadate NaV3O8NH4V3O8Soaking the nano powder into 0.1mol/L acetylacetone iridium solution and 0.1mol/L acetylacetone platinum solution for 36h for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying at 60 ℃ to obtain iridium-platinum vanadate;
calcining the obtained iridium vanadate platinum, wherein the calcining temperature is 800 ℃, the calcining time is 10h, the calcining heating rate is 5 ℃/min, and the obtained iridium and platinum mixed quantum dots are embedded in V2O5Mixing the powder;
pickling the obtained mixed powder for 5h to remove V2O5Obtaining the iridium and platinum mixed quantum dot, wherein the size of the quantum dot is less than 10 nm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a noble metal quantum dot is characterized by comprising the following steps:
1) soaking alkali metal cation or transition metal cation vanadate nano powder into an aqueous solution of soluble precious metal salt, wherein the concentration of the precious metal salt is 0.001-1 mol/L, soaking for ion exchange, and then sequentially carrying out solid-liquid separation, washing and drying to obtain precious metal vanadate;
2) calcining the vanadate of the noble metal obtained in the step 1) to obtain mixed powder formed by dispersing the quantum dots of the noble metal in vanadium oxide residues;
3) acid washing is carried out on the mixed powder obtained in the step 2), and the vanadium oxide residue is removed, so that the noble metal quantum dots are obtained.
2. The method for producing a noble metal quantum dot according to claim 1, characterized in that: in the step 1), the soluble precious metal salt is selected from one or more of a soluble salt containing gold, a soluble salt containing silver, a soluble salt containing platinum, a soluble salt containing ruthenium, a soluble salt containing rhodium, a soluble salt containing palladium, a soluble salt containing osmium or a soluble salt containing iridium.
3. The method for producing a noble metal quantum dot according to claim 2, characterized in that: in the step 1), the soluble precious metal salt is selected from one or more of chloroauric acid, gold acetylacetonate, silver nitrate, chloroplatinic acid, platinum acetylacetonate, ammonium chlororuthenate, ruthenium acetylacetonate, ammonium chlororhodate, rhodium acetylacetonate, ammonium chloropalladate, palladium acetylacetonate, ammonium chloroosmium, ammonium chloroiridate or iridium acetylacetonate.
4. The method for producing a noble metal quantum dot according to claim 2, characterized in that: in the step 3), the noble metal quantum dots are selected from any one or a mixture of more of gold quantum dots, silver quantum dots, platinum quantum dots, ruthenium quantum dots, rhodium quantum dots, palladium quantum dots, osmium quantum dots or iridium quantum dots.
5. The method for producing a noble metal quantum dot according to claim 1, characterized in that: in the step 1), the cations in the vanadate of the alkali metal cations or the transition metal cations are selected from any one or more of lithium ions, sodium ions, potassium ions, ammonium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions or zinc ions;
in the step 3), the acid is selected from any one or more of 0.8-1.2 mol/L oxalic acid, formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid or citric acid; the pickling time is 1-72 h.
6. The method for producing a noble metal quantum dot according to any one of claims 1 to 5, characterized in that: in the step 2), the calcining temperature is 200-800 ℃; the calcining time is 1-72 h; the temperature rise rate of the calcination is 0.5-10 ℃/min.
7. A noble metal quantum dot produced by the method for producing a noble metal quantum dot according to any one of claims 1 to 6.
8. The noble metal quantum dot according to claim 7, wherein:
is gold quantum dot, silver quantum dot, platinum quantum dot, ruthenium quantum dot, rhodium quantum dot, palladium quantum dot, osmium quantum dot or iridium quantum dot;
or, the quantum dot is a mixed quantum dot of at least two of gold quantum dots, silver quantum dots, platinum quantum dots, ruthenium quantum dots, rhodium quantum dots, palladium quantum dots, osmium quantum dots, or iridium quantum dots.
9. The noble metal quantum dot according to claim 7 or 8, wherein: the size of the noble metal quantum dots is less than or equal to 20 nm.
10. Use of the noble metal quantum dot according to any one of claims 7 to 9, wherein:
as a catalyst;
as a fluorescent material;
or as a reinforcing agent in metal and ceramic structural materials.
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