CN108977194A - A kind of surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid - Google Patents
A kind of surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid Download PDFInfo
- Publication number
- CN108977194A CN108977194A CN201710401288.7A CN201710401288A CN108977194A CN 108977194 A CN108977194 A CN 108977194A CN 201710401288 A CN201710401288 A CN 201710401288A CN 108977194 A CN108977194 A CN 108977194A
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- CN
- China
- Prior art keywords
- carboxylic acid
- quantum dot
- acid
- deprotonation
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 115
- 239000003446 ligand Substances 0.000 title claims abstract description 100
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 87
- 230000005595 deprotonation Effects 0.000 title claims abstract description 59
- 238000010537 deprotonation reaction Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 17
- 150000007530 organic bases Chemical class 0.000 claims abstract description 17
- 150000001734 carboxylic acid salts Chemical class 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 16
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 11
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- 229940005605 valeric acid Drugs 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims description 3
- ZVRMGCSSSYZGSM-CCEZHUSRSA-N (E)-hexadec-2-enoic acid Chemical compound CCCCCCCCCCCCC\C=C\C(O)=O ZVRMGCSSSYZGSM-CCEZHUSRSA-N 0.000 claims description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 claims description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- VZJFGSRCJCXDSG-UHFFFAOYSA-N Hexamethonium Chemical compound C[N+](C)(C)CCCCCC[N+](C)(C)C VZJFGSRCJCXDSG-UHFFFAOYSA-N 0.000 claims description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 3
- 229950002932 hexamethonium Drugs 0.000 claims description 3
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- OXDRMTKMIYRQLY-UHFFFAOYSA-N octylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[NH3+] OXDRMTKMIYRQLY-UHFFFAOYSA-N 0.000 claims description 3
- SDPBQTFSSSPDBS-UHFFFAOYSA-N pentan-1-amine;hydrate Chemical compound [OH-].CCCCC[NH3+] SDPBQTFSSSPDBS-UHFFFAOYSA-N 0.000 claims description 3
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 claims description 3
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 claims description 3
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 3
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 2
- OBBQDLHBLQTARQ-UHFFFAOYSA-N hexan-1-amine;hydrate Chemical compound [OH-].CCCCCC[NH3+] OBBQDLHBLQTARQ-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 abstract description 8
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- -1 hexyl hydrogen Chemical compound 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DLDPMTKFISTLQY-UHFFFAOYSA-N C(CCCCCCC)P(CCCCCCCC)(CCCCCCCC)=S.C(CCCCCCC)P Chemical compound C(CCCCCCC)P(CCCCCCCC)(CCCCCCCC)=S.C(CCCCCCC)P DLDPMTKFISTLQY-UHFFFAOYSA-N 0.000 description 3
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- FKLSONDBCYHMOQ-UHFFFAOYSA-N 9E-dodecenoic acid Natural products CCC=CCCCCCCCC(O)=O FKLSONDBCYHMOQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XZJZNZATFHOMSJ-KTKRTIGZSA-N cis-3-dodecenoic acid Chemical compound CCCCCCCC\C=C/CC(O)=O XZJZNZATFHOMSJ-KTKRTIGZSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BYHDDXPKOZIZRV-UHFFFAOYSA-N 5-phenylpentanoic acid Chemical compound OC(=O)CCCCC1=CC=CC=C1 BYHDDXPKOZIZRV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 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 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
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Abstract
The present invention discloses a kind of preparation method for the quantum dot that surface ligand is deprotonation carboxylic acid, wherein comprising steps of pre-processing using organic base or inorganic base to carboxylic acid, obtains carboxylic acid salt solution；Pre-configured first wife's body quantum dot solution is mixed with the carboxylic acid salt solution, after stirring the predetermined time at room temperature, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation carboxylic acid is obtained after cleaning；Surface ligand provided by the invention is that the preparation method reaction rate of the quantum dot of deprotonation carboxylic acid is fast, the cation of deprotonation carboxylic acid and quantum dot surface after exchange is firmly combined, and the surface ligand finally obtained is that the quantum dot colloidal solution stability of deprotonation carboxylic acid is strong, dissolubility is fabulous and luminous efficiency is high.
Description
Technical field
The present invention relates to a kind of systems for the quantum dot that technology of quantum dots field more particularly to surface ligand are deprotonation carboxylic acid
Preparation Method.
Background technique
Fluorescence semiconductor is nanocrystalline, also known as quantum dot, and compared with conventional fluorescent dye molecule, quantum dot has many uniquenesses
Luminescent properties, such as: resistance to photobleaching, broadband excitation, the features such as transmitting band gap is adjustable, therefore be widely used in photoelectric device
And the fields such as biomedicine.
Preparing the most common method of quantum dot at present is that heat injection is negative at high temperature using metal-organic cation predecessor
The reaction of ion predecessor generates quantum dot, and the organic matter introduced in zwitterion predecessor includes tri octyl phosphine, tributylphosphine, oil
Acid, stearic acid etc., the introducing of these organic matters are adjustable the crystal growth rate, crystal morphology, crystal size distribution of quantum dot.
In addition, these organic matters can reduce surface defect as the surface end-capping reagent of quantum dot to improve quantum dot light emitting efficiency.But
When quantum dot surface is chain alkyl acid, quantum dot surface is insecure in conjunction with chain alkyl acid, in subsequent cleaning process
Ligand is easy to fall off, thus will affect the dissolubility of quantum dot and the stability of luminescent properties.On the other hand, the function of ligand
The factors such as group, chain length determine the electronic structure of itself, to will affect the surface electronic hole wave functions and amount of quantum dot
The electronic transmission performance of son point film layer.Therefore in quantum dot device preparation process, in order to optimize entire device structure and
Performance, it usually needs corresponding ligand exchange is carried out to quantum dot.But electronic structure is suitable and the carboxylic acids of binding ability difference
How ligand is combined by force with quantum dot remains very big challenge.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
It in view of above-mentioned deficiencies of the prior art, is deprotonation carboxylic acid the purpose of the present invention is to provide a kind of surface ligand
The preparation method of quantum dot, it is intended to solve existing quantum dot surface and carboxylic acids ligand binding is insecure, lead to quantum dispensing
The problem of liquid solution stability difference.
Technical scheme is as follows:
A kind of surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein comprising steps of
A, carboxylic acid is pre-processed using organic base or inorganic base, obtains carboxylic acid salt solution；
B, pre-configured first wife's body quantum dot solution is mixed with the carboxylic acid salt solution, stirs the predetermined time at room temperature
Afterwards, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation carboxylic acid is obtained after cleaning.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein the step A is specifically included:
Organic base or inorganic base are added in carboxylic acid solution, stir 5-120min at room temperature, generates carboxylic acid salt solution and water.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein in step, described organic
The molar ratio of alkali or inorganic base and carboxylic acid is 1:1-6.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein the organic base is tetramethyl
Ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, four hexyl hydrogen
Amine-oxides, four octyl ammonium hydroxide, methyl triethylammonium hydroxide, trimethylphenyl ammonium hydroxide, cetyl trimethyl hydrogen
One of amine-oxides or hydroxide hexamethonium.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein the inorganic base is hydroxide
One of sodium, potassium hydroxide, calcium hydroxide, barium hydroxide, aluminium hydroxide, indium hydroxide or ammonium hydroxide.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein the carboxylic acid is that C atomicity is small
In or equal to 18 carboxylic acid.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein the carboxylic acid is valeric acid, amylene
Acid, caproic acid, hexenoic acid, n-nonanoic acid, capric acid, undecyl acid, undecenoic acid, dodecyl acid, lauroleic acid, myristyl acid,
One of tetradecenoic acid, cetyl acid, gaidic acid, octadecenic acid or Eighteen alkyl acid.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein in the step B further include:
After the completion of ligand exchange reaction, 10-30min is stood, after being eventually adding ethyl acetate centrifugation 2-4 times, surface is obtained and matches
Body is the quantum dot of deprotonation carboxylic acid.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein first wife's body in the step B
For one of tri octyl phosphine, trioctyl phosphine oxide, tributylphosphine, tributylphosphine oxide.
The surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid, wherein in stepb, the carboxylic acid
The molar ratio of salt and first wife's body quantum dot is 1:1-8.
The utility model has the advantages that the present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation carboxylic acid, wherein first
Carboxylic acid is pre-processed with organic base or inorganic base, obtains the Carboxylic acid ligand of deprotonation, i.e. carboxylate；Then matter is gone by described
The Carboxylic acid ligand and first wife's body quantum dot solution of son are mixed, and carry out ligand exchange reaction, and obtaining surface is deprotonation carboxylic acid
Quantum dot；Surface ligand provided by the invention is that the preparation method reaction rate of the quantum dot of deprotonation carboxylic acid is fast, after exchange
Deprotonation carboxylic acid and the cation of quantum dot surface be firmly combined, the quantum dot colloidal solution stability finally obtained is strong, hair
Light efficiency is high.
Detailed description of the invention
Fig. 1 is the process of the preparation method preferred embodiment for the quantum dot that a kind of surface ligand of the present invention is deprotonation carboxylic acid
Figure.
Fig. 2 is the launching light spectrogram in the embodiment of the present invention 1 before and after quantum dot ligand exchange.
Fig. 3 is the map that the relative luminous intensity in the embodiment of the present invention 1 before and after quantum dot ligand exchange changes over time.
Specific embodiment
The present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation carboxylic acid, to make mesh of the invention
, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 be the quantum dot that a kind of surface ligand of the present invention is deprotonation carboxylic acid preparation method it is preferably real
The flow chart of example is applied, as shown in the figure, wherein comprising steps of
S10, carboxylic acid is pre-processed using organic base or inorganic base, obtains carboxylic acid salt solution；
S20, pre-configured first wife's body quantum dot solution is mixed with the carboxylic acid salt solution, stirs the predetermined time at room temperature
Afterwards, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation carboxylic acid is obtained after cleaning.
Specifically, in the present invention, the carboxylic acid is preferably the carboxylic acid that C atomicity is less than or equal to 18, preferably, institute
Stating carboxylic acid is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, sourer, benzoic acid, phenylacetic acid, phenylpropionic acid, phenyl
Any one in butyric acid, phenylpentanoic acid, phenyl caproic acid, phenylalanine or octadecenic acid, but not limited to this；
When by the carboxylic acid directly as quantum dot surface ligand when, the H in the Carboxylic acid ligand functional group-COOH is in free
State, at this time functional group and quantum dot with coordinate bond in conjunction with correspondingly generate-COO (H)-R, wherein R is quantum dot surface cation；
And-COO- is easy to the H of free state in conjunction with to be detached from generation carboxylic acid with quantum dot surface cation；It is this direct
The quantum dot colloidal solution stability that ligand containing proton is generated in conjunction with quantum dot is very poor, ligand in conjunction with quantum dot loosely
Gu；
Insecure in conjunction with Carboxylic acid ligand containing proton to solve quantum dot, the quantum dot colloidal solution stability difference of generation is asked
Topic, the present invention use in advance organic base or inorganic base (i.e. proton-removed agent) to the Carboxylic acid ligand (i.e. ligand containing proton) at
Reason removes the H in Carboxylic acid ligand, obtains carboxylic acid salt solution (i.e. deprotonation ligand)；
Specifically, the step S10 specifically: the organic base is added in carboxylic acid solution or inorganic base is reacted, it is described
The molar ratio of organic base or inorganic base and carboxylic acid is 1:1-6, preferably 1:2；Further, to the carboxylic acid solution and the organic base
Or after inorganic base mixing, reaction 5-120min is stirred at room temperature, after being then allowed to stand 10-30min, carboxylic acid is made after fully reacting
Salting liquid.
Further, when the carboxylic acid is oil-soluble ligand, such as when ligand is octadecenic acid, organic base or nothing at this time
After machine alkali and the octadecenic acid fully reacting, solution generates split-phase, at this time should remove water phase, is obtained by liquid separation containing 18
The oil-phase solution of olefin(e) acid salt.The presence of water phase will affect oil-soluble deprotonation ligand and first wife's body quantum dot generation ligand exchange is anti-
It answers, causes to exchange the quantum dot light emitting efficiency reduction after ligand.
Further, in the present invention, the organic base is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydrogen
Amine-oxides, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, four hexyl ammonium hydroxide, four octyl ammonium hydroxide, methyl triethyl group
It is any one in ammonium hydroxide, trimethylphenyl ammonium hydroxide, cetyltrimethylammonium hydroxide or hydroxide hexamethonium
Kind, but not limited to this；
The inorganic base is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, aluminium hydroxide, indium hydroxide or hydroxide
Any one in ammonium, but not limited to this.
Further, in the present invention, the carboxylic acid is valeric acid, penetenoic acid, caproic acid, hexenoic acid, n-nonanoic acid, capric acid, 11
Alkyl acid, undecenoic acid, dodecyl acid, lauroleic acid, myristyl acid, tetradecenoic acid, cetyl acid, gaidic acid,
Any one in octadecenic acid or Eighteen alkyl acid, but not limited to this.
Further, in the step S20, by pre-configured first wife's body quantum dot solution and the carboxylic acid salt solution
After stirring the predetermined time at room temperature, ligand exchange reaction occurs for mixing, and the quantum dispensing that surface ligand is deprotonation carboxylic acid is made
Liquid solution.
In particular it is necessary to be pre-configured with first wife's body quantum dot solution, first wife's body is tri octyl phosphine, trioctylphosphine oxidation
One kind of phosphine, tributylphosphine, tributylphosphine oxide；Surface end-capping reagent of these first wife's bodies as quantum dot, can reduce quantum
Point surface defect is to improve the luminous efficiency of quantum dot, however that there are binding abilities is weak, is formed for these first wife's bodies and quantum dot
The various problems such as quantum dot colloidal solution stability difference and dissolubility are poor；
Specifically, the present invention mixes pre-configured first wife's body quantum dot solution with the carboxylic acid salt solution, the first wife
The molar ratio of body quantum dot and carboxylate ligand is 1:1-8, preferably 1:2；During ligand exchange reaction, 5- is persistently stirred
120min；Specifically, ligand exchange reaction occurs after first wife's body quantum dot solution is mixed with the carboxylic acid salt solution,
Lasting stirring can accelerate to react and make reaction more evenly.After the completion of ligand exchange reaction, 10-30min is stood, is eventually adding
After ethyl acetate is centrifuged 2-4 times, the quantum dot that surface ligand is deprotonation carboxylic acid is obtained, due to lacking the H of free state in solution
In conjunction with the carboxylic acid of deprotonation, so that quantum dot and deprotonation Carboxylic acid ligand are not easily to fall off, stability is stronger.
Further, the quantum dot is CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, Cd1-xZnxS、Cd1- xZnxSe、CdSeyS1-y、Cd1-xZnxSeyS1-y、PbSeXS1-X、ZnXCd1-XTe、CdSe/ ZnS、CdS/ ZnS、Cd1-xZnxSe/
ZnS、Cd1-xZnxS/ ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS、CdS/Cd1-xZnxS/CdyZn1-yS/ZnS、CdSe/
Cd1-xZnxSe/CdyZn1-ySe /ZnSe、InP、InP/ZnS、ZnO、MgO、CeO2、NiO、TiO2、CaF2、NaYF4Or NaCdF4
Any one in, but not limited to this luminescent quantum dot.
Surface ligand provided by the invention is that the preparation method reaction rate of the quantum dot of deprotonation carboxylic acid is fast, after exchange
The cation of deprotonation carboxylic acid and quantum dot surface is firmly combined, and the quantum dot colloidal solution stability finally obtained is strong and sends out
Light efficiency is high.
Below by specific embodiment to the preparation method for the quantum dot that a kind of surface ligand of the present invention is deprotonation carboxylic acid
It is further explained explanation:
Embodiment 1
1, ligand is the preparation of the quantum dot of tri octyl phosphine:
1) 0.8mmolCdO, 8mmol zinc acetate and 15 ml oleic acid and 20 ml1- ten, cadmium oleate-zinc precursor liquid preparation: are taken
Eight alkene are heated to 150 DEG C of exhaust 1h under an ar atmosphere, it is molten to form transparent cadmium oleate-zinc precursor in 100mL three-necked flask
Liquid；
2), selenizing tri octyl phosphine-trioctylphosphine sulfide presoma preparation: by 0.2 mmol selenium powder (Selenium powder),
0.6 mmol sulphur powder (Sulfur powder) is dissolved in the tri octyl phosphine (Trioctylphosphine) of 2mL, obtains selenizing
Tri octyl phosphine-trioctylphosphine sulfide presoma；
3) cadmium oleate-zinc precursor liquid, is heated slowly to 300 DEG C, is once rapidly injected selenizing tri octyl phosphine-trioctylphosphine sulfide
Presoma, reaction maintain 8 min.Then temperature is reduced to 100 DEG C, ethyl acetate cleaning is added, centrifugation obtains sediment；So
Chloroform is added afterwards and acetone is centrifuged repeatedly 2 times, obtains the quantum dot that surface ligand is tri octyl phosphine and precipitates.
2, the deprotonation of ligand containing proton:
It takes 4 mmol tetramethylammonium hydroxide to be added in the hexane solution containing 4mmol octadecenic acid, is stirred at room temperature
30min is then allowed to stand 15 min, takes n-hexane phase, obtains the processed octadecenic acid solution of tetramethylammonium hydroxide.
3, ligand exchange processes:
It takes the quantum dot that 100mg surface ligand is tri octyl phosphine to be added in 10ml n-hexane, is uniformly mixed, is then added above-mentioned four
The processed octadecenic acid solution of ammonium hydroxide, is stirred at room temperature 30 min, stands 15min, be added ethyl acetate from
The heart 2 times, obtain the quantum dot that surface ligand is deprotonation octadecenic acid.
Further, Fig. 2 is the launching light spectrogram in embodiment 1 before and after quantum dot ligand exchange, as shown in Figure 2, quantum dot
Its luminous intensity increases after ligand exchange；It, can effectively and quantum dot surface after explanation is handled ligand with proton-removed agent
Cation combines, and surface defect is reduced, to improve luminous efficiency.
Further, Fig. 3 is the figure that the relative luminous intensity in embodiment 1 before and after quantum dot ligand exchange changes over time
Spectrum, from the figure 3, it may be seen that it is smaller that the luminous intensity of quantum dot changes over time reduction degree after ligand exchange；This same explanation is spent
, can be not easily to fall off effectively in conjunction with quantum dot surface cation after proton agent handles ligand, surface defect is reduced, from
And improve luminous efficiency.
Embodiment 2
1, ligand is the preparation of the quantum dot of tributylphosphine:
1) 0.8mmolCdO, 8mmol zinc acetate and 15 ml oleic acid and 20 ml1- ten, cadmium oleate-zinc precursor liquid preparation: are taken
Eight alkene are heated to 150 DEG C of exhaust 1h under an ar atmosphere, it is molten to form transparent cadmium oleate-zinc precursor in 100mL three-necked flask
Liquid；
2), selenizing tributylphosphine-vulcanization tributylphosphine presoma preparation: by 0.2 mmol selenium powder (Selenium powder),
0.6 mmol sulphur powder (Sulfur powder) is dissolved in the tributylphosphine (Trioctylphosphine) of 2mL, obtains selenizing
Tributylphosphine-vulcanization tributylphosphine presoma；
3) cadmium oleate-zinc precursor liquid, is heated slowly to 300 DEG C, is once rapidly injected selenizing tributylphosphine-vulcanization tributylphosphine
Presoma, reaction maintain 8 min.Then temperature is reduced to 100 DEG C, ethyl acetate cleaning is added, centrifugation obtains sediment；So
Chloroform is added afterwards and acetone is centrifuged repeatedly 2 times, obtains the quantum dot that surface ligand is tributylphosphine and precipitates.
2, the deprotonation of ligand containing proton:
It takes 4 mmol tetraethyl ammonium hydroxides to be added in the aqueous solution containing 4mmol valeric acid, 30min is stirred at room temperature, then
15 min are stood, the processed valeric acid solution of tetraethyl ammonium hydroxide is obtained.
3, ligand exchange processes:
It takes the quantum dot that 100mg surface ligand is tributylphosphine to be added in 10ml n-hexane, is uniformly mixed, is then added above-mentioned four
30 min are stirred at room temperature in the processed valeric acid solution of ethyl ammonium hydroxide, stand 15min, and ethyl acetate centrifugation 2 is added
It is secondary, obtain the quantum dot that surface ligand is deprotonation valeric acid.
In conclusion the present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation carboxylic acid, wherein first
Carboxylic acid is pre-processed with organic base or inorganic base, obtains the Carboxylic acid ligand of deprotonation, i.e. carboxylate；Then matter is gone by described
The Carboxylic acid ligand and first wife's body quantum dot solution of son are mixed, and carry out ligand exchange reaction, and it is to go matter that surface is obtained after cleaning
The quantum dot colloidal solution of sub- carboxylic acid；Surface ligand provided by the invention is the preparation method reaction of the quantum dot of deprotonation carboxylic acid
Rate is fast, and the cation of deprotonation carboxylic acid and quantum dot surface after exchange is firmly combined, and the quantum dot colloid finally obtained is molten
Liquid stability is strong, dissolubility is fabulous and luminous efficiency is high.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. the preparation method that a kind of surface ligand is the quantum dot of deprotonation carboxylic acid, which is characterized in that comprising steps of
A, carboxylic acid is pre-processed using organic base or inorganic base, obtains carboxylic acid salt solution；
B, pre-configured first wife's body quantum dot solution is mixed with the carboxylic acid salt solution, stirs the predetermined time at room temperature
Afterwards, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation carboxylic acid is obtained after cleaning.
2. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Step A is stated to specifically include:
Organic base or inorganic base are added in carboxylic acid solution, stir 5-120min at room temperature, generates carboxylic acid salt solution and water.
3. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that
In step A, the molar ratio of the organic base or inorganic base and carboxylic acid is 1:1-6.
4. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Stating organic base is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl
Ammonium hydroxide, four hexyl ammonium hydroxide, four octyl ammonium hydroxide, methyl triethylammonium hydroxide, trimethylphenyl ammonium hydroxide,
One of cetyltrimethylammonium hydroxide or hydroxide hexamethonium.
5. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Stating inorganic base is in sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, aluminium hydroxide, indium hydroxide or ammonium hydroxide
It is a kind of.
6. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Stating carboxylic acid is the carboxylic acid that C atomicity is less than or equal to 18.
7. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Stating carboxylic acid is valeric acid, penetenoic acid, caproic acid, hexenoic acid, n-nonanoic acid, capric acid, undecyl acid, undecenoic acid, dodecyl acid, 12
One of olefin(e) acid, myristyl acid, tetradecenoic acid, cetyl acid, gaidic acid, octadecenic acid or Eighteen alkyl acid.
8. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
It states in step B further include:
After the completion of ligand exchange reaction, 10-30min is stood, after being eventually adding ethyl acetate centrifugation 2-4 times, surface is obtained and matches
Body is the quantum dot of deprotonation carboxylic acid.
9. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that institute
Stating first wife's body in step B is one of tri octyl phosphine, trioctyl phosphine oxide, tributylphosphine, tributylphosphine oxide.
10. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation carboxylic acid, which is characterized in that
In stepb, the molar ratio of first wife's body quantum dot and carboxylate ligand is 1:1-8.
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| CN111892038A (en) * | 2020-08-12 | 2020-11-06 | 河北科技大学 | A kind of acidic carbon quantum dot and its preparation method and application |
| CN111892038B (en) * | 2020-08-12 | 2023-03-10 | 河北科技大学 | Acidic carbon quantum dot and preparation method and application thereof |
| CN116162458A (en) * | 2021-11-24 | 2023-05-26 | 四川大学 | A method for controlling the formation path of magic number clusters/quantum dots and the application of the method to prepare magic number clusters and quantum dots |
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Application publication date: 20181211 |