CN105921177A - Rare earth luminescence catalyst, and preparation method and applications thereof - Google Patents
Rare earth luminescence catalyst, and preparation method and applications thereof Download PDFInfo
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- CN105921177A CN105921177A CN201610264470.8A CN201610264470A CN105921177A CN 105921177 A CN105921177 A CN 105921177A CN 201610264470 A CN201610264470 A CN 201610264470A CN 105921177 A CN105921177 A CN 105921177A
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- rare earth
- hydrogen peroxide
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- ascorbic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 60
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004020 luminiscence type Methods 0.000 title abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 128
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 86
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 43
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 39
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- -1 rare earth terbium ions Chemical class 0.000 claims abstract description 19
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000013259 porous coordination polymer Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 55
- 238000000034 method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229940109239 creatinine Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 1
- 244000048199 Hibiscus mutabilis Species 0.000 description 1
- 235000003973 Hibiscus mutabilis Nutrition 0.000 description 1
- 244000284380 Hibiscus rosa sinensis Species 0.000 description 1
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 description 1
- NGWKGSCSHDHHAJ-UHFFFAOYSA-N Liquoric acid Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CC5OC(C(C6)(C)C(O)=O)CC5(C)C6C4=CC(=O)C3C21C NGWKGSCSHDHHAJ-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 244000105017 Vicia sativa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 1
- 229960004373 acetylcholine Drugs 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000012916 chromogenic reagent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000012621 metal-organic framework Substances 0.000 description 1
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- 235000012149 noodles Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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Abstract
The invention discloses a rare earth luminescence catalyst. The rare earth luminescence catalyst is porous coordination polymer nanoparticles capable of realizing catalysis and luminescence indication of the hydrogen peroxide reaction progress, and is prepared through a solvothermal reaction of rare earth terbium ions, copper ions and ligand molecules, wherein the ligand molecules are m-phthalic acid. The invention also discloses a preparation method of the rare earth luminescence catalyst, and applications of the rare earth luminescence catalyst in catalysis of a reaction of hydrogen peroxide and ascorbic acid, in displaying of the reaction progress and in determination of the concentration of hydrogen peroxide or ascorbic acid. The rare earth luminescence catalyst has an excellent catalysis effect on the hydrogen peroxide reaction, and also can realize luminescence indication of the reaction progress, so the rare earth luminescence catalyst is a reaction catalyst and also is a reaction indicator. The rare earth luminescence catalyst provides a simple and rapid analysis method for catalysis of the hydrogen peroxide reaction and determination of the concentration of hydrogen peroxide or ascorbic acid.
Description
Technical field
The present invention relates to a kind of rare earth luminous catalyst, further relate to the preparation method and application of above-mentioned rare earth luminous catalyst,
Belong to catalysis, luminous instruction field of material technology.
Background technology
Hydrogen peroxide, as a kind of oxidant, participates in many redox reaction, but the reaction participated in is under normal temperature condition
Many carries out slowly needing catalyst.The reaction of peroxidase energy catalyzing hydrogen peroxide is quickly carried out, but, enzyme conduct
A kind of protein, the easy degeneration when heating, some chemical environments easily lose catalysis activity, and they preparation,
Purification and storage are all wasted time and energy.The catalyst of some energy catalyzing hydrogen peroxide redox reaction is successfully developed
Coming, these catalyst include oxide, metal, sulfide, carbon and multi-metal oxygen salt.But, these synthesis at present
The preparation of catalyst more complicated, catalytic effect is the most unsatisfactory.Develop that preparation is simple, catalytic efficiency high, preferably
The catalyst of hydroperoxidation has demand and application widely.
The catalyst of many hydroperoxidations it has been reported that China Patent Publication No. CN102847531A, 2013,
Zhang Hui, Lin Huiqing, Cai is satisfactory, Wu Ping, the preparation method of a kind of attapulgite and manganese dioxide nanocomposite, discloses one
The method planting attapulgite and manganese dioxide nanocomposite catalyzing hydrogen peroxide reaction degraded dyeing waste water Methylene Blue dyestuff；
China Patent Publication No. CN103508545A, 2014, Qujiang River English, Shi Lin, peak, Shao Guanghua, Li Yuqian, stone
Ink alkene/MnO2The method of nano-complex catalyzing hydrogen peroxide degradation of methylene blue, discloses one Graphene/MnO2
The method of nano-complex catalyzing hydrogen peroxide degradation of methylene blue；China Patent Publication No. CN101130169,2008
Year, Ma Jun, Zhang Yingjie, Chen Lei, Zhang Liang, Yao Jun, the preparation of Complexing Iron catalyst and multiphase photocatalysis of hydrogen peroxide thereof
Application, disclose a kind of cation exchange resin granule or film absorption ferric complex as catalyst peroxidating
The method that hydrogen decomposes；China Patent Publication No. CN101530798,2009, Yan Xiyun, Zhuan Jie, usury increased, poplar
The east tinkling of pieces of jade, Feng Jing, the novel agent of detection content of hydrogen peroxide and new method, disclose the magnetic Nano material of a kind of enzyme simulation
The reaction of catalyzing hydrogen peroxide, the method generating color products detection hydrogen peroxide；China Patent Publication No.
CN103712983A, 2014, Wang Kun, Yang Xingwang, Qian Jing, imitate the acetylcholine of enzymatic property based on magnetic graphene
Visible detection method, discloses a kind of Fe with peroxidase property3O4/ rGO material catalyzing hydrogen peroxide substrate
3,3 ', 5,5 '-tetramethyl benzidine (TMB) generates the method for blue product detection hydrogen peroxide；China Patent Publication No.
CN104568926A, 2015, Xu Guobao, fills in agate Han Ni cottonrose hibiscus, opens dawn, Pi Teyuehan, the inspection of a kind of creatinine
Survey method, discloses a kind of cobalt ion catalyzing hydrogen peroxide oxidation creatinine, causes the method that creatinine product is luminous；China is specially
Profit publication number CN104258876A, 2015, Chen Mindong, Xu started an undertaking, Luo Yue, Zhang Tongyu, Teng Fei, and a kind of silver is micro-
Rice noodle photocatalyst and its preparation method and application, discloses a kind of method that silver micro wire catalyzing hydrogen peroxide decomposes；In
State's patent publication No. CN104777117A, 2015, Chen Wei, Lin little Qing, Deng was luxurious, Wu Gangwei, Li Guangwen, base
In the method that graphene oxide-Platinum Nanoparticles composite measures cysteine, disclose a kind of graphene oxide-Platinum Nanoparticles multiple
The method of condensation material catalyzing hydrogen peroxide oxidation TMB hydrochlorate colour developing；China Patent Publication No. CN105214646A,
2016, Peng Huaping, Liu Ailin, Chen Wei, woods Xinhua, Liu Pan, gamma hch common vetch, tungsten oxide quanta point material simulation peroxide
Compound enzyme, disclose a kind of tungsten oxide quanta point material Mimetic enzyme catalyzing hydrogen peroxide oxidation TMB, 2,2 '-
The method of azino-bis-(3-ethyl benzo thiazole phenanthroline-6-sulfonic acid) chromogenic reagent such as di-ammonium salts and o-phenylenediamine；Chinese patent is public
The number of opening CN105372236A, 2016, Li Bin, Chen Daomei, Wang Jiaqiang, the side of a kind of high-sensitivity detection cancerous cell
Method, discloses a kind of metal organic framework compound Fe-MIL-101, and catalyzing hydrogen peroxide oxidation substrates TMB occurs face
The method of complexion changed.
Summary of the invention
Goal of the invention: the technical problem to be solved is to provide a kind of rare earth luminous catalyst, this is rare earth luminous urges
Agent contains rare earth ion, is the catalyst of hydroperoxidation, is also the indicator showing hydroperoxidation progress,
There is catalysis and the function of luminous instruction hydroperoxidation the most simultaneously.
The present invention also to solve the technical problem that the preparation method being to provide above-mentioned rare earth luminous catalyst.
The present invention finally to solve the technical problem that to be to provide above-mentioned rare earth luminous catalyst bad with anti-at catalyzing hydrogen peroxide
Hematic acid reaction and the application in terms of showing the application in terms of its extent of reaction and measuring hydrogen peroxide or ascorbic acid concentrations.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of rare earth luminous catalyst, described rare earth luminous catalyst is for entering for catalysis and luminous instruction hydroperoxidation
The Porous coordination polymer nanoparticle of degree, it is passed through solvent thermal reaction by rare earth terbium ion, copper ion and ligand molecular thereof
Synthesis prepares；Wherein, described ligand molecular is M-phthalic acid (PA).
The preparation method of above-mentioned rare earth luminous catalyst, specifically includes following steps:
Step 1, is sequentially added into rare earth terbium ion aqueous solution and copper ion in the DMF of certain volume
Aqueous solution, obtains mixed solution A；While stirring the DMF solution being dissolved with M-phthalic acid is added
Enter in mixed solution A, obtain mixed solution B；Wherein, in mixed solution B, rare earth terbium ion, copper ion and
The mol ratio of M-phthalic acid is 1: 1: 2, and DMF is 7: 4 with the volume ratio of water；
Step 2, transfers to teflon-lined reaction after the mixed solution B of step 1 is stirred reaction a period of time
In still, react 3 hours at 160 DEG C, naturally cool to room temperature, the centrifugal precipitation generated of collecting, by washing of precipitate also
Dry.
Above-mentioned rare earth luminous catalyst catalyzing hydrogen peroxide and ascorbic acid react and show in terms of its extent of reaction should
With.
Above-mentioned rare earth luminous catalyst is dense with hydrogen peroxide in ascorbic acid reactant liquor or ascorbic acid at mensuration hydrogen peroxide
Application in terms of degree.
The rare earth luminous catalyst of the present invention catalyzing hydrogen peroxide react with ascorbic acid and show its extent of reaction should
With: in hydrogen peroxide and ascorbic acid reactant liquor, add the rare earth luminous catalyst suspension of the present invention, mix few minutes after
Solution starts fluorescence occur, and fluorescence intensity gradually becomes strong with reaction, until no longer changing, illustrates that reaction is completely；By
The product effect generated can be reacted with hydrogen peroxide and ascorbic acid in rare earth luminous catalyst and produce fluorescence, fluorescence intensity
Change reflects the degree that hydrogen peroxide reacts with ascorbic acid.
The rare earth luminous catalyst of the present invention can be additionally used in mensuration hydrogen peroxide and hydrogen peroxide in ascorbic acid reactant liquor or anti-
The concentration of bad hematic acid: add the rare earth luminous catalyst suspension of the present invention in liquid to be determined, after mixing 10 minutes,
Under uviol lamp, observe its fluorescence color and compare with the standard fluorescence color diagram of known hydrogen peroxide or ascorbic acid concentrations,
I.e. can obtain hydrogen peroxide or the concentration of ascorbic acid in this solution；Or with terbium ion in fluorescent spectrophotometer assay solution
Fluorescence intensity, obtain this according to terbium ion fluorescence intensity and the working curve diagram of hydrogen peroxide or ascorbic acid concentrations to be measured
Hydrogen peroxide or the content of ascorbic acid in solution.
Compared with prior art, the invention have the advantages that:
First, the rare earth luminous catalyst of the present invention is a kind of Porous coordination polymer nanoparticle, and Porous coordination polymer is received
Rice corpuscles has the mechanical performance that high specific surface area is become reconciled, and is a kind of novel catalyst material；
Secondly, the rare earth luminous catalyst of the present invention also has instruction while the hydroperoxidation catalysis having had
The function of its extent of reaction, be catalysts be also reaction indicator, and also it is anti-that luminous intensity can be utilized to measure
Answering hydrogen peroxide or the concentration of ascorbic acid in liquid, luminous intensity is directly proportional to the content of hydrogen peroxide or ascorbic acid, than
Conventional coloration method has higher mensuration sensitivity；
Again, the rare earth luminous catalyst of the present invention utilizes rare earth luminescence, and the fluorescence lifetime of rare earth ion length allows the time
The use of resolved fluorometric technology, moreover it is possible to eliminate the interference of various background fluorescence, to sample or the life with background fluorescence interference
Hydrogen peroxide or the mensuration of ascorbic acid in objects system have advantage；
Finally, the raw material that the rare earth luminous method for preparing catalyst of the present invention uses is common, and synthetic method is simple, cost of manufacture
Low.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the present invention rare earth luminous catalyst Tb-Cu-PA；
Fig. 2 is the present invention rare earth luminous catalyst Tb-Cu-PA catalyzing hydrogen peroxide and the luminous intensity of ascorbic acid reaction
Figure；
Fig. 3 is fluorescence intensity and the work of concentration of hydrogen peroxide in solution of the present invention rare earth luminous catalyst Tb-Cu-PA
Curve chart；
Fig. 4 is the fluorescence face of the ascorbic acid of variable concentrations in the present invention rare earth luminous catalyst Tb-Cu-PA instruction solution
Chromatic graph；
Fig. 5 is fluorescence intensity and the work of ascorbic acid concentrations in solution of the present invention rare earth luminous catalyst Tb-Cu-PA
Curve chart.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, technical scheme is described in detail.
Embodiment 1
The preparation method of the present invention rare earth luminous catalyst Tb-Cu-PA nanoparticle, specifically includes following steps:
Step 1, is sequentially added into the Tb (NO that 2mL concentration is 20mM in 5mL DMF3)3
Aqueous solution and the Cu (NO that 2mL concentration is 20mM3)2Aqueous solution, obtains mixed solution A after mix homogeneously；Then
Under being stirred continuously, the DMF solution that 2mL is dissolved with M-phthalic acid joins mixed solution
In A, obtain mixed solution B；It is dissolved with M-phthalic acid in the DMF solution of M-phthalic acid
Concentration be 40mM；
Step 2, is stirred at room temperature the mixed solution B of step 1 reaction 20min, transfers to teflon-lined
In reactor, react 3 hours at 160 DEG C, naturally cool to room temperature, the centrifugal greenish precipitate collecting generation；
Will precipitation the most respectively with dehydrated alcohol and milli-Q water 2 times, then precipitation is placed in dry for standby at 40～80 DEG C；Close
The rare earth luminous catalyst become is expressed as Tb-Cu-PA.
Tb-Cu-PA after drying weighs, and is resuspended in pure water the Tb-Cu-PA suspension being prepared as required mass concentration
Liquid is standby.
Fig. 1 is the transmission electron microscope picture of the rare earth luminous catalyst Tb-Cu-PA that embodiment 1 prepares, as shown in Figure 1,
Tb-Cu-PA is the nanoparticle with spherical shapes.
The rare earth luminous catalyst of the present invention is nanoparticle such that it is able to improves the specific surface area of catalyst, and then improves
Its catalytic perfomance.
Embodiment 2
The rare earth luminous catalyst Tb-Cu-PA nanoparticle that embodiment 1 prepares is anti-with ascorbic acid at catalyzing hydrogen peroxide
The application that should go up:
The H of 10 μ L is added in the HAc-NaAc buffer (10mM, pH 5.05) of 960 μ L2O2Solution (200
MM) and 10 μ L ascorbic acid (200mM), add 20 μ L Tb-Cu-PA suspensions (35 after mix homogeneously
Mg/mL), react 20min under room temperature, then excite their fluorescence intensity of lower mensuration at 310nm.
Fig. 2 is that the rare earth luminous catalyst Tb-Cu-PA that embodiment 1 prepares reacts at catalyzing hydrogen peroxide and ascorbic acid
During luminous intensity figure；Hydrogen peroxide is to react hardly with the reaction of ascorbic acid in the presence of not having catalyst
, in the presence of luminous catalyst Tb-Cu-PA, in a few minutes, there is fluorescence in solution, fluorescence intensity with reaction carry out by
Gradual change is strong, until no longer changing, illustrates that reaction is completely.
Embodiment 3
The rare earth luminous catalyst Tb-Cu-PA nanoparticle that embodiment 1 prepares concentration of hydrogen peroxide side in measuring solution
The application in face:
The Tb-Cu-PA adding 20 μ L in the HAc-NaAc buffer (10mM, pH 5.05) of 960 μ L hangs
Supernatant liquid (35mg/mL) and 10 μ L ascorbic acid (200mM), mix homogeneously, then, be separately added into different volumes
H2O2Solution (5mM) and ultra-pure water are in above-mentioned mixed liquor so that H2O2Final concentration be respectively 0,1,100,
240,360 and 500 μMs.After these mixed solutions at room temperature react 20min, 310nm excite lower mensuration it
Fluorescence spectrum, it is thus achieved that the working curve of fluorescence intensity and concentration of hydrogen peroxide, shoot under 302nm uviol lamp and contain
There is the fluorescence color figure of variable concentrations hydrogenperoxide steam generator.
The Tb-Cu-PA adding 20 μ L in the HAc-NaAc buffer (10mM, pH 5.05) of 960 μ L hangs
Supernatant liquid (35mg/mL) and 10 μ L ascorbic acid (200mM), mix homogeneously, then, add 10 μ L liquid to be measured,
After mixing 10 minutes, under uviol lamp, observe the fluorescence color of mixed liquor, with the fluorescence face of the hydrogen peroxide of concentration known
Chromatic graph compares, and i.e. can obtain the content of hydrogen peroxide in this solution to be measured；Or with spectrofluorophotometer at delay mode
Lower mensuration solution is in the terbium ion fluorescence intensity of 545nm, according to the work of terbium ion fluorescence intensity Yu concentration of hydrogen peroxide
Curve chart records the content of hydrogen peroxide in this solution to be measured.
Fig. 3 is fluorescence intensity and the working curve diagram of concentration of hydrogen peroxide in solution of Tb-Cu-PA, from the figure 3, it may be seen that
In solution, the concentration of hydrogen peroxide and terbium ion fluorescence intensity are good linear proportional relation.Experiment shows that this catalyst exists
Not by common zwitterion and the interference of coexisting substances (sugar, carbamide, aminoacid) during concentration of hydrogen peroxide in mensuration solution.
Embodiment 4
The rare earth luminous catalyst Tb-Cu-PA nanoparticle that embodiment 1 prepares ascorbic acid concentrations side in measuring solution
The application in face:
The Tb-Cu-PA adding 20 μ L in the HAc-NaAc buffer (10mM, pH 5.05) of 960 μ L hangs
Supernatant liquid (35mg/mL) and 10 μ L hydrogen peroxide (200mM), mix homogeneously.Then, it is separately added into different volumes
Ascorbic acid solution (5mM) and ultra-pure water in above-mentioned mixed liquor so that the final concentration of ascorbic acid is respectively 0,
20,250,500,700 and 1000 μMs.After these mixed solutions at room temperature react 20min, excite at 310nm
Lower their fluorescence spectrum of mensuration, it is thus achieved that fluorescence intensity and the working curve of ascorbic acid concentrations, at 302nm uviol lamp
Lower shooting contains the fluorescence color figure of variable concentrations ascorbic acid solution.
The Tb-Cu-PA adding 20 μ L in the HAc-NaAc buffer (10mM, pH 5.05) of 960 μ L hangs
Supernatant liquid (35mg/mL) and 10 μ L hydrogen peroxide (200mM), mix homogeneously, then, add 10 μ L liquid to be measured,
Under uviol lamp, observe the fluorescence color of solution, compare with the fluorescence color figure of the ascorbic acid of concentration known,
The content of ascorbic acid in this solution；Or under delay mode, measure solution 545nm's with spectrofluorophotometer
Terbium ion fluorescence intensity, records in this liquid to be measured according to the working curve diagram of terbium ion fluorescence intensity Yu ascorbic acid concentrations
The content of ascorbic acid.
Fig. 4 is the fluorescence color figure of the ascorbic acid of variable concentrations in rare earth luminous catalyst Tb-Cu-PA instruction solution,
Fig. 5 is fluorescence intensity and the working curve diagram of ascorbic acid concentrations in solution of rare earth luminous catalyst Tb-Cu-PA.
Embodiment 5
The rare earth luminous catalyst Tb-Cu-PA nanoparticle that embodiment 1 prepares concentration of hydrogen peroxide in measuring human urine
The application of aspect:
The Tb-Cu-PA adding 20 μ L in the HAc-NaAc buffer (10mM, pH 5.05) of 870 μ L hangs
Supernatant liquid (35mg/mL) and 10 μ L ascorbic acid (200mM), mix homogeneously, then, add 100 μ L people's urine samples
(having diluted 5 times), after hybrid reaction 20min, measures solution 545 with spectrofluorophotometer under delay mode
The terbium ion fluorescence intensity of nm, records in urine according to the working curve diagram of terbium ion fluorescence intensity Yu concentration of hydrogen peroxide
The content of hydrogen peroxide, the results list 1 of mensuration.
Table 1 measurement result (a: meansigma methods (n=3) ± standard deviation)
。
Obviously, above-described embodiment is only for clearly demonstrating example of the present invention, and is not the reality to the present invention
Execute the restriction of mode.For those of ordinary skill in the field, can also be made it on the basis of the above description
The change of its multi-form or variation, here without also giving exhaustive to all of embodiment, these are extended out
Change or variation are also among protection scope of the present invention.
Claims (4)
1. a rare earth luminous catalyst, it is characterised in that: described rare earth luminous catalyst is for for being catalyzed and showing
The Porous coordination polymer nanoparticle of hydrogen oxide extent of reaction, it is led to by rare earth terbium ion, copper ion and ligand molecular thereof
Cross solvent thermal reaction synthesis to prepare；Wherein, described ligand molecular is M-phthalic acid.
2. the preparation method of the rare earth luminous catalyst described in a claim 1, it is characterised in that specifically include as
Lower step:
Step 1, is sequentially added into rare earth terbium ion aqueous solution and copper ion in the DMF of certain volume
Aqueous solution, obtains mixed solution A；While stirring the DMF solution being dissolved with M-phthalic acid is added
Enter in mixed solution A, obtain mixed solution B；Wherein, in mixed solution B, rare earth terbium ion, copper ion and
The mol ratio of M-phthalic acid is 1: 1: 2, and DMF is 7: 4 with the volume ratio of water；
Step 2, transfers to teflon-lined reaction after the mixed solution B of step 1 is stirred reaction a period of time
In still, react 3 hours at 160 DEG C, naturally cool to room temperature, the centrifugal precipitation generated of collecting, by washing of precipitate also
Dry.
3. the rare earth luminous catalyst described in a claim 1 reacts with ascorbic acid at catalyzing hydrogen peroxide and shows
Application in terms of its extent of reaction.
4. the rare earth luminous catalyst described in a claim 1 is measuring hydrogen peroxide and mistake in ascorbic acid reactant liquor
Application in terms of hydrogen oxide or ascorbic acid concentrations.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105388150A (en) * | 2015-10-29 | 2016-03-09 | 大连理工大学 | Oxytetracycline test paper based on chromatic aberration comparison, using method and making method |
| CN112044471A (en) * | 2020-08-18 | 2020-12-08 | 东南大学 | Multifunctional nano enzyme, preparation method and application |
| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN112730393A (en) * | 2020-12-17 | 2021-04-30 | 广西科技大学 | Color development reagent and method for measuring ascorbic acid |
| CN112844361A (en) * | 2021-01-25 | 2021-05-28 | 江南大学 | Tb3+ -B codoped modified TiO2Photocatalytic film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238650A (en) * | 2006-03-03 | 2007-09-20 | Kyoto Univ | Rare earth metal complex and fluorescent material using the same |
| CN104610382A (en) * | 2015-01-06 | 2015-05-13 | 东北大学 | Green fluorescent complex containing terbium and preparation method and application thereof |
| CN105503965A (en) * | 2016-01-11 | 2016-04-20 | 天津师范大学 | Rare earth (III)-transition (II) mixed metal fluorescence complex and preparing method and application thereof |
-
2016
- 2016-04-26 CN CN201610264470.8A patent/CN105921177B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238650A (en) * | 2006-03-03 | 2007-09-20 | Kyoto Univ | Rare earth metal complex and fluorescent material using the same |
| CN104610382A (en) * | 2015-01-06 | 2015-05-13 | 东北大学 | Green fluorescent complex containing terbium and preparation method and application thereof |
| CN105503965A (en) * | 2016-01-11 | 2016-04-20 | 天津师范大学 | Rare earth (III)-transition (II) mixed metal fluorescence complex and preparing method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LAO YAN-NI等: "Hydrothermal synthesis，crystal structure and fluorescencent of Europium and Terbium 1，3-benzendicarboxylate complexes", 《上海师范大学学报(自然科学版)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105388150A (en) * | 2015-10-29 | 2016-03-09 | 大连理工大学 | Oxytetracycline test paper based on chromatic aberration comparison, using method and making method |
| CN112044471A (en) * | 2020-08-18 | 2020-12-08 | 东南大学 | Multifunctional nano enzyme, preparation method and application |
| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN112094416B (en) * | 2020-09-23 | 2022-04-26 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN112730393A (en) * | 2020-12-17 | 2021-04-30 | 广西科技大学 | Color development reagent and method for measuring ascorbic acid |
| CN112844361A (en) * | 2021-01-25 | 2021-05-28 | 江南大学 | Tb3+ -B codoped modified TiO2Photocatalytic film and preparation method thereof |
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