CN111229321A - Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof - Google Patents
Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof Download PDFInfo
- Publication number
- CN111229321A CN111229321A CN202010047066.1A CN202010047066A CN111229321A CN 111229321 A CN111229321 A CN 111229321A CN 202010047066 A CN202010047066 A CN 202010047066A CN 111229321 A CN111229321 A CN 111229321A
- Authority
- CN
- China
- Prior art keywords
- glutathione
- aqueous solution
- platinum alloy
- gold
- platinum
- 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.)
- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 64
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 49
- -1 Glutathione-protected platinum Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 81
- 239000010931 gold Substances 0.000 claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229960003180 glutathione Drugs 0.000 claims abstract description 55
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052737 gold Inorganic materials 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 108010024636 Glutathione Proteins 0.000 claims abstract description 23
- 239000001509 sodium citrate Substances 0.000 claims abstract description 21
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 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 claims abstract description 8
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims abstract description 8
- 150000004687 hexahydrates Chemical class 0.000 claims abstract description 7
- 239000003223 protective agent Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 44
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 13
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 10
- 229910001020 Au alloy Inorganic materials 0.000 description 9
- 239000003353 gold alloy Substances 0.000 description 9
- 239000007974 sodium acetate buffer Substances 0.000 description 9
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 9
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 102000004316 Oxidoreductases Human genes 0.000 description 2
- 108090000854 Oxidoreductases Proteins 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018885 Pt—Au Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 101150113720 aunc gene Proteins 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004325 lysozyme Substances 0.000 description 1
- 229960000274 lysozyme Drugs 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/396—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
- G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- 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
- B01J2531/18—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Abstract
Glutathione-protected platinum alloy nano-cluster with strong catalytic function and preparation method thereofThe method and the application thereof in the catalytic oxidation of 3,3',5,5' -tetramethyl benzidine in the presence of hydrogen peroxide belong to the technical field of metal nano-cluster catalysis. The gold-platinum complex is obtained by carrying out hydrothermal reaction on a chloroauric acid trihydrate aqueous solution and a chloroplatinic acid hexahydrate aqueous solution serving as a gold source and a platinum source, sodium citrate serving as a reducing agent and glutathione serving as a ligand protective agent at 100-130 ℃ for 0.5-5 hours. When the glutathione-protected platinum alloy nanoclusters are used for catalyzing the oxidation of 3,3',5,5' -tetramethylbenzidine by hydrogen peroxide, it is found that K in the reaction when hydrogen peroxide is used as a substratem42.26 mmoles, Vmax＝264×10‑8Moles per second; k in the reaction when TMB is used as a substratem0.1076 mmol, Vmax＝105.58×10‑8Moles per second, exhibit catalytic rates superior to many nanocatalysts.
Description
Technical Field
The invention belongs to the technical field of metal nano-cluster catalysis, and particularly relates to a glutathione-protected platinum alloy nano-cluster with a strong catalytic function, a preparation method and application thereof in hydrogen peroxide (H)2O2) Use in the catalytic oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB) in the presence of oxygen.
Background
Nanoclusters (NCs) consisting of metal atoms (gold, silver, platinum) containing several to several tens of different metal atoms are of great interest in the fields of detection of heavy metals and biomolecules, catalysis, bioimaging and labeling. Metal nanoparticles (including platinum, gold, platinum-gold nanoparticles) exhibit peroxidase-and oxidase-like activity and can catalyze hydrogen peroxide-mediated oxidation of peroxidase substrates, oxidation of glucose with co-substrate oxygen, and oxidation of water, among others. Metal Nanoclusters (NCs) have a larger specific surface area and exhibit high catalytic activity due to having a discrete electronic structure, as compared to metal Nanoparticles (NPs) having a diameter of more than 2 nm. In metal nanoclusters, there is typically a high percentage of metal content exposed to the nanoparticle surface, and in metal nanoclusters having a particle diameter of 2 nanometers, about 50% of the metal atoms are exposed to the surface. Thus, metal nanoclusters are highly active catalysts for some key reactions. Experiments have shown that platinum-containing nanoclusters (PtNC) exhibit exceptionally high activity in the oxidative carbon monoxide, reductive oxygen and propane oxidative dehydrogenation (Chem Rev 2)018, 118, 4981). Gold nanoclusters (AuNCs) exhibit peroxidase-like activity and may be in H2O2Catalyzes the oxidation of TMB in the presence. However, few studies have reported the use of alloy nanoclusters to mimic oxidases.
On the other hand, the metal nanoclusters show different catalytic behavior for various heterogeneous catalytic reactions. Studies have shown that many factors, including particle size, shape, chemical composition, and metal-reactant/solvent interactions, can have a significant impact on the catalytic performance of metal catalysts. For example, Au55NCs (consisting of 55 gold atoms) show effective catalytic activity, selectively oxidizing styrene by oxygen; and slightly larger gold nanoparticles (AuNPs)>2 nm) is completely inactive (ACS Nano 2017, 11, 6904). Metal nanoclusters, including platinum, gold and silver nanoclusters, typically exhibit peroxidase and oxidase-like activity, as gold nanoclusters have been reported to catalyze the oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB) by oxygen, and also in the presence of hydrogen peroxide. Methods for preparing metal nanoclusters and methods for improving catalytic activity are diverse at present, and for example, in et al, platinum nanoclusters (PtNC) similar to oxidase are prepared by using lysozyme as a template in an environment of pH 12 (Nanoscale 2014, 6, 9618); liao et al also added heavy metal ion such as Dimethine lead ion (Pb)2+) Improving the catalytic activity of glutathione-protected gold nanoclusters (AuNCs @ GSH) (chemical communications 2017, 53, 10160) and the like. However, these methods generally require a long reaction time, use of heavy metal ions, use of toxic organic solvents, and require multiple steps. In particular, there is no report on how to optimize the catalytic performance during the preparation of the material.
In the work of the invention, a new hydrothermal synthesis method for controllably preparing the platinum metal nanocluster (Pt-AuNCs @ GSH) protected by Glutathione (GSH) is established, and the nanocluster material with certain catalytic activity can be obtained by using the method. Further, the obtained platinum alloy gold nanoclusters (Pt-AuNCs @ GSH) show more excellent catalytic effect on the oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB) through fine optimization and controllable preparation regulation. Characterization of the metal nanoclusters by characterization means such as ultraviolet-visible absorption spectroscopy, high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and the like, shows that the core size and metal ratio of the alloy nanoclusters and the results are well matched to their unique function. Therefore, the current work provides a new approach for obtaining bimetallic nanoclusters with excellent catalytic activity, which will stimulate more research on exploring the use of metal nanoclusters.
Disclosure of Invention
The invention aims to provide a platinum double-alloy nanocluster (Pt-Au @ GSH NCs) based on Glutathione (GSH) protection and application thereof in catalytic oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB). The nano-cluster is a platinum alloy nano-cluster, and glutathione acts on the surface of the nano-cluster. The platinum-gold alloy nanoclusters with the maximum catalytic rate were obtained by a hydrothermal method optimized based on the preparation conditions of examples 1 to 5. The platinum alloy gold nano-cluster can be stably stored for 4 months at the temperature of 4 ℃ and the catalytic activity of the platinum alloy gold nano-cluster is kept unchanged, and the stability of the platinum alloy gold nano-cluster lays a foundation for further popularization and application of the platinum alloy gold nano-cluster. In addition, the platinum-gold alloy nanoclusters are confirmed to be a typical core-shell structure by means of ultraviolet-visible absorption spectroscopy, high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), etc., and most of gold elements are concentrated in the center of the nanoclusters in the form of zero-valent gold atoms (Au (0)), while a small amount of gold and all platinum atoms are distributed in the outer layers of the nanoclusters in the forms of Au (i), pt (i), and pt (ii). When such glutathione-protected platinum alloy nanoclusters are used to catalyze the oxidation of 3,3',5,5' -tetramethylbenzidine by hydrogen peroxide, it was found that: k in the reaction when hydrogen peroxide is used as substratem42.26 mmol/ml, Vmax＝264×10-8Moles per second; k in the reaction when TMB is used as a substratem0.1076 mmol/ml, Vmax＝105.58×10-8Moles per second.
The invention successfully prepares Pt-Au @ GSHNCs by adopting a one-step hydrothermal synthesis method, which is chloroauric acid trihydrateSolution (HAuCl)4·3H2O) and an aqueous solution of chloroplatinic acid hexahydrate (H)2PtCl6·6H2O) as a gold source and a platinum source, sodium Citrate (CA) as a reducing agent, and Glutathione (GSH) as a ligand protectant; firstly, uniformly mixing a chloroauric acid trihydrate aqueous solution and a chloroplatinic acid hexahydrate aqueous solution, adding a glutathione solution into the mixed solution, further uniformly mixing, and then adding a sodium citrate solution; and then transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction for 0.5-5 hours at the temperature of 100-130 ℃, and optimizing preparation conditions to obtain the glutathione-protected platinum alloy nano-cluster catalyst solution with the strong catalytic function.
In the method, the molar dosage of chloroauric acid trihydrate is 1-8 millimoles, and the molar dosage ratio of the chloroauric acid trihydrate aqueous solution to the chloroplatinic acid hexahydrate aqueous solution is (1-8): (8-1), the molar use ratio of the ligand glutathione to the total amount of metal ions (gold and platinum) is (1-4.5): 1, the molar use ratio of the total amount of the sodium citrate and the metal ions (gold and platinum) is (0-41.7): 1.
drawings
FIG. 1: plot (a) and bar graph (b) of catalytic efficiency of Pt-AuNCs @ GSH versus molar ratio of gold and platinum at the time of dosing.
FIG. 2: plot (a) and bar graph (b) of catalytic efficiency versus reaction time for Pt-AuNCs @ GSH.
FIG. 3: plot (a) and bar graph (b) of catalytic efficiency versus reaction temperature for Pt-AuNCs @ GSH.
FIG. 4: plot (a) and bar graph (b) of catalytic efficiency of Pt-AuNCs @ GSH versus ligand to metal ion molar ratio at feed.
FIG. 5: plot (a) and bar graph (b) of catalytic efficiency of Pt-AuNCs @ GSH versus the molar amount of reducing agent sodium Citrate (CA) used at the time of dosing.
FIG. 6: a high resolution transmission electron microscope (HR-TEM) image (a) and a particle diameter distribution histogram (b) of Pt-AuNCs @ GSH.
FIG. 7: the ultraviolet-visible absorption spectrogram of Pt-AuNCs @ GSH increases along with the reaction time in the preparation process.
FIG. 8: x-ray photoelectron spectroscopy (XPS) of gold (a) and platinum (b) elements in Pt-AuNCs @ GSH.
FIG. 9: catalytic performance curves for Pt-AuNCs @ GSH.
FIG. 10: catalytic efficiency curves (a) and bar graphs (b) for Pt-AuNCs @ GSH in the presence of nanoclusters at different concentrations.
FIG. 11: catalytic efficiency curves (a) and bar graphs (b) for Pt-AuNCs @ GSH in the presence of different hydrogen peroxide concentrations.
FIG. 12: catalytic efficiency curves (a) and bar graphs (b) for Pt-AuNCs @ GSH in the presence of different TMB concentrations.
FIG. 13: two substrates H are respectively measured by a Lineweaver-Burk double reciprocal mapping method2O2The constant of the Mie equation of (a, b) and TMB (c, d) (K)m) And maximum initial velocity (V)max)。
FIG. 1 corresponds to example 1; FIG. 2 corresponds to example 2; FIG. 3 corresponds to example 3; FIG. 4 corresponds to example 4; FIG. 5 corresponds to example 5; FIGS. 6-8 correspond to example 6; FIG. 7 corresponds to example 7; FIG. 10 corresponds to example 8; FIG. 11 corresponds to example 9; FIGS. 12 to 13 correspond to embodiment 10.
The Pt-AuNCs @ GSH prepared under the optimized condition is subjected to shape characterization by adopting a high-resolution transmission electron microscope (figure 6a), and the figure shows that the nano particles have good dispersibility and uniform particle size. The average grain size was found to be 2.39 nm by systematic analysis of approximately 200 particles (fig. 6 b). The interplanar spacing (-0.23 nm) of the particles (inset in fig. 6a) is between the 111 lattice planes of metallic platinum (0.226 nm) and metallic gold (0.236 nm). In addition, the ultraviolet-visible absorption spectrum carries out preliminary analysis on the optical properties in the process of preparing Pt-AuNCs @ GSH. As shown in fig. 7, a broad absorption peak exists near 500 nm in the absorption spectrum; and the intensity of the absorption peak is increased along with the prolonging of the reaction time. These results illustrate that: in the process of preparing the platinum-gold alloy nanoclusters, the particle diameter of the nanoclusters increases with time. The gold element and platinum element in Pt-AuNCs @ GSH have a total of four valence states, which are Au (0), Au (I), Pt (I) and Pt (II) (FIG. 8). We speculate that: the platinum alloy nanocluster is of a core-shell structure, namely Au (0) is distributed in the core, and Au (I), Pt (I) and Pt (II) are distributed outside the core of the platinum alloy nanocluster.
As shown in fig. 1 to 5, as well as by the hydrothermal synthesis method, with the change of various conditions in the preparation process, such as the ratio of gold and platinum, the reaction time, the reaction temperature, the ratio of the ligand glutathione to the metal ions, and the concentration of the reducing agent sodium Citrate (CA), the catalytic activity of the platinum alloy nanoclusters is also changed. We therefore investigated the use of hydrothermal synthesis to obtain glutathione-protected platinum-gold-alloy nanoclusters with the strongest catalytic capacity.
Furthermore, after successfully obtaining glutathione-protected platinum alloy gold nanoclusters prepared by a hydrothermal synthesis method, we investigated the influence of varying different catalytic conditions (fig. 10-12) such as concentration of nanoclusters, concentration of hydrogen peroxide and concentration of TMB in this catalytic reaction, and measured the catalytic ability of the platinum alloy gold nanoclusters by calculation of kinetic correlation constants (fig. 13).
Through the research, the glutathione-protected platinum alloy nano-cluster is prepared by a hydrothermal synthesis method, and the catalytic rate of the platinum alloy nano-cluster in the reaction of catalyzing hydrogen peroxide to oxidize TMB is superior to that of a plurality of nano-catalysts.
Detailed Description
Example 1:
the effect of different molar amounts of gold and platinum on the catalytic ability of the metal nanoclusters at the time of dosing was mainly explored in this example. Adding 800 microliters of chloroauric acid aqueous solution with the concentration of 10 mmol/ml into a polytetrafluoroethylene lining, then respectively adding 0, 100, 200, 300, 400, 500, 600, 700 and 800 microliters of chloroplatinic acid aqueous solution with the concentration of 10 mmol/ml, uniformly stirring, and then respectively adding 100 mmol/ml glutathione aqueous solution 320, 360, 400, 440, 480, 520, 560, 600 and 640 microliters; taking a polytetrafluoroethylene lining, adding 800 microliters of chloroplatinic acid aqueous solution with the concentration of 10 mmol/ml, then respectively adding 0, 100, 200, 300, 400, 500, 600, 700 and 800 microliters of chloroauric acid aqueous solution with the concentration of 10 mmol/ml, stirring uniformly, then respectively adding 320, 360, 400, 440, 480, 520, 560, 600 and 640 microliters of glutathione aqueous solution with the concentration of 10 mmol/ml (ensuring that the total molar amount of metal ions, namely the total molar amount of gold and platinum, and the ratio of glutathione is 1: 4), and then respectively adding 400 microliters and 500 mmol/ml sodium Citrate (CA) aqueous solution. And finally adding deionized water to make the volume of the solution be 10 milliliters, uniformly stirring, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, and setting the temperature of an oven to be 110 ℃ for hydrothermal reaction for 2 hours. After the reaction is finished, cooling to room temperature and taking out to obtain the Pt-AuNCs @ GSH prepared under different feeding ratios of gold and platinum.
10. mu.l of 100 mmol/ml TMB solution and 50. mu.l of the platinum alloy gold nanocluster solution obtained above were added to a quartz cuvette, followed by addition of an acetic acid-sodium acetate buffer solution having a pH of 4 to fix the volume to 1 ml, and finally addition of 3. mu.l of 10 mol/ml H2O2And (3) recording the ultraviolet absorption value at the ultraviolet absorption wavelength of 652 nm of the solution by an ultraviolet-visible spectrophotometer every 30 seconds to obtain a catalytic rate curve of the platinum alloy gold nanocluster under different gold and platinum molar ratios, as shown in figure 1, and finally determining that when the molar ratio of gold to platinum is 4: when 8, the platinum alloy nanoclusters have the strongest catalytic ability.
Example 2:
in this example, the effect of different reaction times on the catalytic ability of the nanoclusters was investigated. Adding aqueous solution of chloroauric acid and chloroplatinic acid with the concentration of 10 mmol/ml into the polytetrafluoroethylene lining, wherein the aqueous solution of chloroauric acid and chloroplatinic acid are respectively 400 microliters and 800 microliters, stirring uniformly, then adding 480 microliters of aqueous solution of glutathione with the concentration of 100 mmol/ml, and then adding aqueous solution of sodium Citrate (CA) with the concentration of 400 microliters and 500 mmol/ml. And finally, adding deionized water to ensure that the volume of the solution is 10 milliliters, uniformly stirring, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, and setting the temperature of an oven to be 120 ℃ to perform hydrothermal reaction. Then taking out the reaction kettle after 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 and 5 hours respectively, and cooling to room temperature to obtain the Pt-AuNCs @ GSH prepared under different reaction times.
10. mu.l of 100 mmol/ml TMB solution and 50. mu.l of the platinum alloy gold nanocluster solution obtained above were added to a quartz cuvette, followed by addition of an acetic acid-sodium acetate buffer solution having a pH of 4 to fix the volume to 1 ml, and finally addition of 3. mu.l of 10 mmol/ml H2O2And (3) recording the ultraviolet absorption value at the ultraviolet absorption wavelength of 652 nm by an ultraviolet-visible spectrophotometer every 30 seconds of the solution to obtain a catalytic rate curve of the platinum alloy gold nanocluster under different reaction times, as shown in fig. 2, and finally determining that the platinum alloy gold nanocluster has the strongest catalytic capability when the reaction time is 4 hours.
Example 3:
the effect of different reaction temperatures on the catalytic ability of the nanoclusters was mainly explored in this example. Adding aqueous solution of chloroauric acid and chloroplatinic acid with the concentration of 10 mmol/ml into the polytetrafluoroethylene lining, wherein the aqueous solution of chloroauric acid and chloroplatinic acid are respectively 400 microliters and 800 microliters, stirring uniformly, then adding 480 microliters of aqueous solution of glutathione with the concentration of 100 mmol/ml, and then adding aqueous solution of sodium Citrate (CA) with the concentration of 400 microliters and 500 mmol/ml. And finally adding deionized water to make the volume of the solution be 10 milliliters, uniformly stirring, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, and setting the temperature of an oven to be 100 ℃, 110 ℃, 120 ℃ and 130 ℃ respectively to perform hydrothermal reaction for 4 hours. And (4) taking out the reaction kettle after the reaction is finished, and cooling to room temperature to obtain the Pt-AuNCs @ GSH prepared at different reaction temperatures.
10. mu.l of 100 mmol/ml TMB solution and 50. mu.l of the platinum alloy gold nanocluster solution obtained above were added to a quartz cuvette, followed by addition of an acetic acid-sodium acetate buffer solution having a pH of 4 to fix the volume to 1 ml, and finally addition of 3. mu.l of 10 mmol/ml H2O2And (3) recording the ultraviolet absorption value at the ultraviolet absorption wavelength of 652 nm by an ultraviolet-visible spectrophotometer every 30 seconds to obtain a catalytic rate curve of the platinum alloy gold nanocluster at different reaction temperatures, as shown in figure 3, and finally determining that the platinum alloy gold nanocluster has the strongest catalytic capability at the reaction temperature of 120 ℃.
Example 4:
the effect of the ratio of the total molar amount of different metal ions (gold and platinum) to the molar amount of the ligand glutathione on the catalytic ability of the nanoclusters was mainly explored in this example. Adding a chloroauric acid aqueous solution with the concentration of 10 mmol/ml and a chloroplatinic acid aqueous solution with the concentration of 400 microliters and 800 microliters respectively into a polytetrafluoroethylene lining, stirring uniformly, then adding a glutathione aqueous solution with the concentration of 100 mmol/ml respectively, and enabling the ratio of the molar amount of the glutathione aqueous solution to the sum of the molar amounts of the metal ions to be 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4 and 1: 4.5, then 400. mu.l of 500 mmol/ml aqueous sodium Citrate (CA) solution was added. And finally adding deionized water to make the volume of the solution be 10 milliliters, stirring uniformly, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, setting the temperature of an oven to be 120 ℃ to perform hydrothermal reaction for 4 hours, taking out the reaction kettle, and cooling to room temperature to obtain the Pt-AuNCs @ GSH prepared under different ligand and metal ion ratios.
10. mu.l of 100 mmol/ml TMB solution and 50. mu.l of the platinum alloy gold nanocluster solution obtained above were added to a quartz cuvette, followed by addition of an acetic acid-sodium acetate buffer solution having a pH of 4 to fix the volume to 1 ml, and finally addition of 3. mu.l of 10 mmol/ml H2O2And (3) recording an ultraviolet absorption value at the ultraviolet absorption wavelength of 652 nanometers of the solution by an ultraviolet-visible spectrophotometer every 30 seconds to obtain a catalytic rate curve of the platinum alloy nano-cluster under different molar ratios of the ligand glutathione to the metal ions, as shown in fig. 4, finally determining that when the molar ratio of the ligand glutathione to the metal ions is 3: 1, the platinum alloy nanoclusters have the highest catalytic ability.
Example 5:
the effect of the ratio of the molar amount of sodium citrate, a different reducing agent, to the total molar amount of metal ions (gold and platinum), on the catalytic performance of the nanoclusters was mainly explored in this example. Adding a 10 mmol/ml aqueous solution of chloroauric acid and an aqueous solution of chloroplatinic acid into a polytetrafluoroethylene lining, wherein the concentration of the chloroauric acid and the aqueous solution of chloroplatinic acid are respectively 400 microliters and 800 microliters, stirring uniformly, then adding 360 microliters of 100 mmol/ml aqueous solution of glutathione, and then respectively adding 0, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 microliters and 500 mmol/ml aqueous solution of sodium Citrate (CA) (the molar amount of the sodium citrate to the total molar amount of metal ions (gold and platinum) is 0: 1, 4.2: 1, 8.3: 1, 12.5: 1, 16.7: 1, 20.8: 1, 25: 1, 29.2: 1, 33.3: 1, 37.5: 1 and 41.7: 1). And finally adding deionized water to make the volume of the solution be 10 milliliters, stirring uniformly, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, setting the temperature of an oven to be 120 ℃ to perform hydrothermal reaction for 4 hours, taking out the reaction kettle, and cooling to room temperature to obtain the Pt-AuNCs @ GSH prepared under different reducing agent sodium Citrate (CA) concentrations.
10. mu.l of 100 mmol/ml TMB solution and 50. mu.l of the platinum alloy gold nanocluster solution obtained above were added to a quartz cuvette, followed by addition of an acetic acid-sodium acetate buffer solution having a pH of 4 to fix the volume to 1 ml, and finally addition of 3. mu.l of 10 mmol/ml H2O2After the solution is dissolved, every 30 seconds, an ultraviolet absorption value at an ultraviolet absorption wavelength of 652 nanometers is recorded by an ultraviolet-visible spectrophotometer, so that the catalytic rate of the platinum-gold alloy nanocluster under different molar amounts of the reducing agent sodium Citrate (CA) is obtained, and finally, the platinum-gold alloy nanocluster is determined to have the highest catalytic capability when the molar amount of the reducing agent sodium Citrate (CA) is 450 millimoles (the molar amount ratio of the reducing agent sodium citrate to the sum of metal ions is 37.5: 1).
Example 6:
according to examples 1 to 5, 400. mu.l and 800. mu.l of aqueous chloroauric acid and 800. mu.l of aqueous chloroplatinic acid, respectively, were added to a polytetrafluoroethylene liner at a concentration of 10 mmol/ml, and after stirring them uniformly, 360. mu.l of aqueous glutathione at a concentration of 100 mmol/ml and 900. mu.l of aqueous sodium Citrate (CA) at a concentration of 500 mmol/ml were added. And finally adding deionized water to make the volume of the solution be 10 milliliters, stirring uniformly, transferring the polytetrafluoroethylene lining into a stainless steel reaction kettle, setting the temperature of an oven to be 120 ℃ to perform hydrothermal reaction for 4 hours, taking out the reaction kettle, and cooling to room temperature to finally obtain the Pt-AuNCs @ GSH with high catalytic capacity optimized through preparation conditions.
The results show that: the Pt-AuNCs @ GSH obtained based on example 6 has no fluorescence. The Pt-AuNCs @ GSH prepared under the optimized condition is subjected to morphology characterization by a high-resolution transmission electron microscope (HR-TEM) (shown in figure 6a), and the figure shows that the nanoparticles have good dispersibility and uniform particle size. The average grain size was found to be 2.39 nm by systematic analysis of approximately 200 particles (fig. 6 b). The interplanar spacing (-0.23 nm) of the particles (inset in fig. 6a) was between the 111 interplanar spacing of platinum (0.226 nm) and the 111 interplanar spacing of gold (0.236 nm). In addition, the ultraviolet-visible absorption spectrum carries out preliminary analysis on the optical properties in the process of preparing Pt-AuNCs @ GSH. As shown in fig. 7, a broad absorption peak exists near 500 nm in the absorption spectrum; and the intensity of the absorption peak is increased along with the prolonging of the reaction time. The results show that the particle diameter of the nanoclusters increases with time during the preparation of the platinum-alloy gold nanoclusters. The gold element and platinum element in Pt-AuNCs @ GSH have a total of four valence states, which are Au (0), Au (I), Pt (I) and Pt (II) (FIG. 8). We speculate that the platinum-alloy nanocluster is a core-shell structure, i.e., Au (0) is distributed in the core, and Au (I), Pt (I) and Pt (II) are distributed outside the core of the platinum-alloy nanocluster.
Example 7:
based on catalyst-TMB-H2O2The ternary system is further verified to determine whether the platinum alloy gold nanoclusters prepared through the optimization process have catalytic activity. The change in the uv absorbance at 652 nm was monitored with a uv-vis spectrophotometer, respectively: the first is in the presence of the platinum alloy nanoclusters and TMB only; a second platinum alloy nanocluster, TMB and H2O2All in the presence of; the third is only TMB and H2O2Under the conditions of (a); the last is in the presence of only TMB. TMB concentration 1 mmol/ml in the catalytic reaction, H2O2The concentration is 30 mmol/ml, the concentration of the platinum alloy nano-cluster is 10 micrograms/ml, and the buffer solution is acetic acid-sodium acetate buffer solution with pH of 4, and the total volume is 1 ml.
As shown in fig. 9, by monitoring the change in the uv absorbance over timeWe have found that H is only present when the platinum-gold alloy nanoclusters are present2O2The reaction of oxidizing TMB can proceed more quickly. We therefore conclude that: at H2O2In the reaction of oxidizing TMB, the glutathione-protected platinum alloy nanoclusters prepared by the method really play the role of a catalyst to participate in the reaction.
Example 8:
in optimizing the catalytic conditions, we first performed the effect of the catalyst, i.e., the concentration of the platinum-alloy gold nanoclusters, in the catalytic reaction. 1 mg/ml of platinum alloy gold nanoclusters 0, 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90 and 100 microliters are added to the quartz cuvette, respectively. To give final concentrations in solution of 0, 1, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and 100 microgram/ml, respectively; then 10 μ l of 100 mmol/ml TMB solution was added and pH 4 acetic acid-sodium acetate buffer was added to fix the volume to 1 ml; finally, 3. mu.l of 10 mol/ml H were added2O2The solution was then tested every 30 seconds for uv absorbance at 652 nm by uv-vis spectrophotometer. As shown in fig. 10, we found that as the concentration of the nanoclusters increased, the rate of catalytic reaction increased, and that the catalytic rate was optimized when the concentration reached 80 μ g/ml. From this we can conclude that the pt-au nanoclusters we made are concentration dependent catalytic materials.
Example 9:
in the optimization of catalytic conditions, we next performed an oxidant, i.e. H2O2The effect of concentration in the catalytic reaction. Adding 10 microliter of platinum-gold alloy nanoclusters of 1 mg/ml into a quartz cuvette; then 10 μ l of 100 mmol/ml TMB solution was added and pH 4 acetic acid-sodium acetate buffer was added to fix the volume to 1 ml; finally, 0, 0.1, 0.5, 1, 1.5, 2, 3, 5 and 10. mu.l, 10 mol/ml of H were added2O2Solutions to final concentrations of 0, 1, 5, 10, 15, 20, 30, 50 and 100 mmol/ml in solution, respectively;then every 30 seconds, the uv absorption value at a uv absorption wavelength of 652 nm was recorded by a uv-vis spectrophotometer. As shown in FIG. 11, we found that with H2O2The rate of the catalytic reaction increases with increasing concentration. From this we can conclude that, in common with many oxidation reactions, the oxidant H2O2There is a positive correlation between concentration and rate of chemical reaction.
Example 10:
in the optimization of catalytic conditions, we next performed the influence of the substrate, i.e. the TMB concentration, in the catalytic reaction. Adding 10 microliter of platinum alloy gold nanoclusters of 1 mg/ml into a quartz cuvette; then 1, 3, 5, 10, 15, 20 and 30 μ l, 100 mmol/ml TMB solution was added to make the concentration in the solution 0.1, 0.3, 0.5, 1.0, 1.5, 2.0 and 3.0 mmol/ml, respectively; then, an acetic acid-sodium acetate buffer solution with pH 4 was added to fix the volume to 1 ml; finally, 3. mu.l, 10 mol/ml of H2O2A solution; then every 30 seconds, the uv absorption value at a uv absorption wavelength of 652 nm was recorded by a uv-vis spectrophotometer. As shown in FIG. 12, it was found that the rate of the catalytic reaction did not change significantly with increasing TMB concentration, but did change significantly when the concentration reached 2.0 mM/mL.
Through the above studies on the catalytic conditions, the method for determining and calculating the mie constant is referred to: the absorbance at 652 nm was recorded every 30 seconds at room temperature for 10 minutes with continuous monitoring. The initial reaction velocity can be calculated by lambert beer's law:
c＝A/(εb)
where c is the substrate concentration, A is the absorbance, ε is the molar absorption coefficient of the colorimetric substrate used (39000 per mole/cm at 652 nm for TMB in the oxidized state, b is the thickness of the solution.) the enzymatic parameters were determined by fitting the absorbance data to the following Michaelis-Menten equation.
Wherein V is the initial reaction rate, VmaxFor the maximum reaction rate, [ S ]]As substrate concentration, KmIs the Michaelis-Menten constant, reflecting the affinity of the nanoenzyme for its substrate.
By means of a double reciprocal plot (FIG. 13) we can conclude that H is respectively present in this catalytic reaction2O2And affinity K with TMB as substratem42.26 and 0.1076 mmol/ml, and a maximum reaction rate Vmax264 and 105.58 (10)-8Moles per second). Our material is inferior in affinity to the relevant results reported in the literature. But for the maximum reaction rate, we prepared platinum-gold alloy nanoclusters much faster than the materials reported in the literature.
It should also be noted that the particular embodiments of the present invention are provided for illustrative purposes only and do not limit the scope of the present invention in any way, and that modifications and variations may be made by persons skilled in the art in light of the above teachings, but all such modifications and variations are intended to fall within the scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of glutathione-protected platinum alloy nano-cluster with strong catalytic function is characterized by comprising the following steps: taking a chloroauric acid trihydrate aqueous solution and a chloroplatinic acid hexahydrate aqueous solution as a gold source and a platinum source, taking sodium citrate as a reducing agent, and taking glutathione as a ligand protective agent; firstly, uniformly mixing a chloroauric acid trihydrate aqueous solution and a chloroplatinic acid hexahydrate aqueous solution, adding a glutathione solution into the mixed solution, further uniformly mixing, and then adding a sodium citrate solution; and then transferring the mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction for 0.5-5 hours at the temperature of 100-130 ℃, and optimizing preparation conditions to obtain the glutathione-protected platinum alloy gold nanocluster catalyst solution with a strong catalytic function.
2. The method for preparing glutathione-protected platinum alloy nanoclusters with strong catalytic function as claimed in claim 1, wherein: the molar dosage of the chloroauric acid trihydrate is 1-8 millimoles, and the molar dosage ratio of the chloroauric acid trihydrate aqueous solution to the chloroplatinic acid hexahydrate aqueous solution is (1-8): (8-1), wherein the molar usage ratio of the total amount of the glutathione to the total amount of the metal ions is (1-4.5): 1, the molar usage ratio of the total amount of the sodium citrate and the metal ions is (0-41.7): 1.
3. a glutathione-protected platinum alloy nano-cluster with a strong catalytic function is characterized in that: is prepared by the method of claim 1 or 2.
4. The use of the glutathione-protected platinum alloy nanoclusters having a strong catalytic function as set forth in claim 3 for the catalytic oxidation of 3,3',5,5' -tetramethylbenzidine in the presence of hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010047066.1A CN111229321A (en) | 2020-01-16 | 2020-01-16 | Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010047066.1A CN111229321A (en) | 2020-01-16 | 2020-01-16 | Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111229321A true CN111229321A (en) | 2020-06-05 |
Family
ID=70877821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010047066.1A Pending CN111229321A (en) | 2020-01-16 | 2020-01-16 | Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111229321A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044051A (en) * | 2022-05-25 | 2022-09-13 | 郑州大学 | Platinum cluster radiotherapy sensitizer for relieving tumor hypoxia |
| CN115626671A (en) * | 2022-11-02 | 2023-01-20 | 华南理工大学 | Multifunctional dual-ligand platinum nano-particle and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2026409A1 (en) * | 1989-09-29 | 1991-03-30 | Ernest G. Schutt | Method of producing a reagent containing a narrow distribution of colloidal particles of a selected size and the use thereof |
| JP2011045826A (en) * | 2009-08-26 | 2011-03-10 | Japan Science & Technology Agency | Golden cluster modified metal oxide semiconductor, photoelectrode using the same, and photoelectric transducer having the photoelectrode |
| CN102343442A (en) * | 2007-07-06 | 2012-02-08 | M技术株式会社 | Method for production of metal microparticle |
| CN106111131A (en) * | 2016-06-24 | 2016-11-16 | 许昌学院 | A kind of dendroid plation nano-particle analogue enztme and its preparation method and application |
| WO2017030974A1 (en) * | 2015-08-14 | 2017-02-23 | The Trustees Of The University Of Pennsylvania | Radiographic nanoparticle contrast agents for dual-energy x-ray imaging and computed tomography scanning and methods of using thereof |
| CN107118758A (en) * | 2017-05-03 | 2017-09-01 | 吉林大学 | A kind of gold/platinum bimetal nano cluster fluorescence probe protected based on polyethyleneimine and its application in detection aureomycin |
| CN107127354A (en) * | 2017-06-29 | 2017-09-05 | 吉林大学 | A kind of synthesis of hydro-thermal method by light sensitivity electrum nano-cluster of the small molecule AMP for protection part |
| US20190099741A1 (en) * | 2017-09-29 | 2019-04-04 | Shin-Etsu Chemical Co., Ltd. | Photocatalyst/alloy fine-particle dispersion having anitbacterial/antifungal properties, method of preparation thereof, and member having photocatalyst/alloy thin film on surface |
-
2020
- 2020-01-16 CN CN202010047066.1A patent/CN111229321A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2026409A1 (en) * | 1989-09-29 | 1991-03-30 | Ernest G. Schutt | Method of producing a reagent containing a narrow distribution of colloidal particles of a selected size and the use thereof |
| CN102343442A (en) * | 2007-07-06 | 2012-02-08 | M技术株式会社 | Method for production of metal microparticle |
| JP2011045826A (en) * | 2009-08-26 | 2011-03-10 | Japan Science & Technology Agency | Golden cluster modified metal oxide semiconductor, photoelectrode using the same, and photoelectric transducer having the photoelectrode |
| WO2017030974A1 (en) * | 2015-08-14 | 2017-02-23 | The Trustees Of The University Of Pennsylvania | Radiographic nanoparticle contrast agents for dual-energy x-ray imaging and computed tomography scanning and methods of using thereof |
| CN106111131A (en) * | 2016-06-24 | 2016-11-16 | 许昌学院 | A kind of dendroid plation nano-particle analogue enztme and its preparation method and application |
| CN107118758A (en) * | 2017-05-03 | 2017-09-01 | 吉林大学 | A kind of gold/platinum bimetal nano cluster fluorescence probe protected based on polyethyleneimine and its application in detection aureomycin |
| CN107127354A (en) * | 2017-06-29 | 2017-09-05 | 吉林大学 | A kind of synthesis of hydro-thermal method by light sensitivity electrum nano-cluster of the small molecule AMP for protection part |
| US20190099741A1 (en) * | 2017-09-29 | 2019-04-04 | Shin-Etsu Chemical Co., Ltd. | Photocatalyst/alloy fine-particle dispersion having anitbacterial/antifungal properties, method of preparation thereof, and member having photocatalyst/alloy thin film on surface |
Non-Patent Citations (2)
| Title |
|---|
| JIAYU FENG ET AL.: "Gold–platinum bimetallic nanoclusters with enhanced peroxidase-like activity and their integrated agarose hydrogel-based sensing platform for the colorimetric analysis of glucose levels in serum", 《ANALYST》 * |
| WENCHAO DING ET AL.: "Water-soluble gold nanoclusters with pH-dependent fluorescence and high colloidal stability over a wide pH range via co-reduction of glutathione and citrate", 《RSC ADV.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044051A (en) * | 2022-05-25 | 2022-09-13 | 郑州大学 | Platinum cluster radiotherapy sensitizer for relieving tumor hypoxia |
| CN115626671A (en) * | 2022-11-02 | 2023-01-20 | 华南理工大学 | Multifunctional dual-ligand platinum nano-particle and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cui et al. | Facile synthesis of iridium nanoparticles with superior peroxidase-like activity for colorimetric determination of H2O2 and xanthine | |
| Han et al. | Poly (N-isopropylacrylamide)-co-(acrylic acid) microgel/Ag nanoparticle hybrids for the colorimetric sensing of H 2 O 2 | |
| Shi et al. | A nanocomposite prepared from copper (II) and nitrogen-doped graphene quantum dots with peroxidase mimicking properties for chemiluminescent determination of uric acid | |
| Ma et al. | Peroxidase-like catalytic activity of cubic Pt nanocrystals | |
| Safavi et al. | Effect of gold nanoparticle as a novel nanocatalyst on luminol–hydrazine chemiluminescence system and its analytical application | |
| Guo et al. | Pt–Se nanostructures with oxidase-like activity and their application in a selective colorimetric assay for mercury (II) | |
| Zhang et al. | Seed‐mediated synthesis of Au nanocages and their electrocatalytic activity towards glucose oxidation | |
| CN111229321A (en) | Glutathione-protected platinum alloy nano-cluster with strong catalytic function, preparation method and application thereof | |
| Xu et al. | One-pot synthesis of Pt/CeO2/C catalyst for enhancing the SO2 electrooxidation | |
| Krajczewski et al. | Enhanced catalytic activity of solid and hollow platinum-cobalt nanoparticles towards reduction of 4-nitrophenol | |
| Nie et al. | Trimetallic PdCuAu nanoparticles for temperature sensing and fluorescence detection of H 2 O 2 and glucose | |
| Lee et al. | Antioxidative metallic copper nanoparticles prepared by modified polyol method and their catalytic activities | |
| Lv et al. | A convenient detection system consisting of efficient Au@ PtRu nanozymes and alcohol oxidase for highly sensitive alcohol biosensing | |
| Han et al. | Microbial synthesis of graphene‐supported highly‐dispersed Pd‐Ag bimetallic nanoparticles and its catalytic activity | |
| Chen et al. | Facile controlled synthesis of AuPd and AuPt bimetallic nanocrystals for enhanced electrocatalytic sensing | |
| Moon et al. | Platinum overgrowth on gold multipod nanoparticles: Investigation of synergistic catalytic effects in a bimetallic nanosystem | |
| EP2735044B1 (en) | Electrocatalytic composite(s), associated composition(s), and associated process(es) | |
| Du et al. | Coordination‐Driven One‐Step Rapid Self‐Assembly Synthesis of Dual‐Functional Ag@ Pt Nanozyme | |
| Tummala et al. | Synthesis of Cu-doped carbon dot/chitosan film composite as a catalyst for the colorimetric detection of hydrogen peroxide and glucose | |
| Chao et al. | Seed-mediated growth of Ag nanocubes and their size-dependent activities toward oxygen reduction reaction | |
| García-Morales et al. | Electrochemical glucose oxidation using glassy carbon electrodes modified with Au-Ag nanoparticles: influence of Ag content | |
| Im et al. | Spontaneous formation of core-shell silver-copper oxide by carbon dot-mediated reduction for enhanced oxygen electrocatalysis | |
| Lee et al. | Cornered silver and silverplatinum nanodisks: Preparation and promising activity for alkaline oxygen reduction catalysis | |
| Feng et al. | Facile synthesis of ultrathin MnO2 nanobelts anchoring on porous carbon with high oxidase mimetic activity for L-cysteine colorimetric detection | |
| Shan et al. | Size-controlled synthesis of monodispersed gold nanoparticles stabilized by polyelectrolyte-functionalized ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |