CN111298828A - Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof - Google Patents
Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof Download PDFInfo
- Publication number
- CN111298828A CN111298828A CN202010125763.4A CN202010125763A CN111298828A CN 111298828 A CN111298828 A CN 111298828A CN 202010125763 A CN202010125763 A CN 202010125763A CN 111298828 A CN111298828 A CN 111298828A
- Authority
- CN
- China
- Prior art keywords
- emt
- solution
- zeolite
- glucose
- under stirring
- 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
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010457 zeolite Substances 0.000 claims abstract description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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 claims abstract description 26
- 239000008103 glucose Substances 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 235000015203 fruit juice Nutrition 0.000 claims abstract description 3
- 210000002966 serum Anatomy 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 102000003992 Peroxidases Human genes 0.000 claims description 5
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 230000003278 mimic effect Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000012544 monitoring process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 26
- 239000002114 nanocomposite Substances 0.000 abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- ZBQCCTCQUCOXBO-UHFFFAOYSA-N 4-(4-aminophenyl)-2,2,6,6-tetramethylcyclohex-3-en-1-amine Chemical compound CC1(C)C(N)C(C)(C)CC(C=2C=CC(N)=CC=2)=C1 ZBQCCTCQUCOXBO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003759 clinical diagnosis Methods 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 102000016938 Catalase Human genes 0.000 description 4
- 108010053835 Catalase Proteins 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000019420 glucose oxidase Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 238000012742 biochemical analysis Methods 0.000 description 1
- 238000010256 biochemical assay Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012698 colloidal precursor Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of functionalized zeolite materials, and particularly relates to Pt/EMT with highly dispersed Pt nanoparticles on EMT, a preparation method and application thereof. The Pt NPs (5-8 nm) are uniformly loaded on the subminiature EMT zeolite (15-20 nm) carrier, and the Pt/EMT nano composite material with highly dispersed Pt is prepared. The Pt/EMT nano material can be well dispersed in water to form uniform suspension, and then can be used as a better peroxide catalyst to oxidize 3,3,5, 5-tetramethylbenzidine in the presence of hydrogen peroxide; and is used for detecting the content of glucose in the solution; the glucose sensor has high selectivity on glucose, can be used for accurately measuring the glucose concentration in samples including human serum and fruit juice, and has wide application in the fields of clinical diagnosis, pharmacy, food and the like.
Description
Technical Field
The invention belongs to the technical field of functionalized zeolite materials, and particularly relates to Pt/EMT, a preparation method thereof and application of the Pt/EMT as a peroxidase mimic.
Background
In 2007, about Fe3O4In the first report of intrinsic enzymatic activity of Nanoparticles (NPs), the study of artificial enzyme mimetics based on inorganic nanomaterials has attracted a great deal of interest in biochemical and biological assay applications due to their distinct advantages over natural enzymes, and in the past decade a large number of inorganic nanomaterials with different structures and compositions, such as metal oxides, noble metals, metal sulfides, etc., have been rationally designed to mimic nanoenzymes in peroxidase-like catalytic reactions. As one of the most common precious metals, widely used as catalysts in chemical processes, platinum (Pt) is widely recognized as one of the most active peroxidase mimics. However, the disadvantages of high cost and easy inactivation caused by Pt aggregation greatly limit its applications, and thus far, much research has not been conducted on it in practical biological applications including biosensing. One strategy to overcome these obstacles is to control the size and structure of Pt nanomaterials to achieve excellent enzymatic activity, such as synthesis of ultra-small Pt nanoclusters, porous Pt nanotubes, cubic Pt nanocrystals, irregularly shaped Pt NPs, and the like. Another strategy is based on the synthesis of Pt/support composite nanomaterials with well-designed stable structures and versatility, usually by uniformly dispersing PtNPs on some suitable supports, including Pt/CeO2 nanocomposites, Au @ Pt core-shell nanorods, dumbbell-shaped PtPd-Fe3O4NP, ferritin-Pt NP, dendrimer-coated Pt NP, mesoporous silica-coated Pt NP, and the like. Although these Pt-loaded hybrid nanocomposites show satisfactory performance in enzyme-simulated reactions, it is still difficult to obtain high quality low cost supports and achieve a highly uniform dispersion of Pt NPs on/in the support.
With mesoporous materials (e.g. mesoporous SiO)2) In contrast, zeolite is a crystalline aluminosilicate with regular micropores (pore size)<2 nm) and developed channels, shows a stable framework structure, good Broensted/Lewis acidity and shape selectivityIn general, most zeolites (e.g., Y (FAU), ZSM-5 (MFI), β (BEA), SSZ-13 (CHA), etc.) can be conveniently synthesized by conventional hydrothermal methods, and are widely used as low-cost industrial catalysts or large-scale catalyst supports<15 nm) remains a significant challenge. Recently, by precisely controlling the nucleation kinetics at low temperatures (30 ℃), Mintova and his colleagues synthesized subminiature zeolitic materials including EMT (10-20 nm) and Y (10-70 nm) from colloidal precursors without template, all with a 3-dimensional 12-membered ring channel system, which could be highly dispersed in water to form homogeneous suspensions. In addition to excellent catalyst performance as zeolite Y and the like in isomerization, alkylation and aromatization reactions, EMT zeolites can also serve as ideal hosts for silver nanoparticles by the introduction of silver ions and subsequent reduction reactions, primarily due to their low Si/Al ratio, and therefore these nanosized Ag-EMT zeolites can be stabilized in aqueous suspension for long-term antimicrobial applications. Nanoscale Pt/EMT zeolites are used as high performance enzyme mimics due to their inherent surface acidity, low silica to alumina ratio, ultra small particle size of EMT, uniform dispersion of Pt NPs and uniform suspension in water.
Disclosure of Invention
The invention aims to provide a Pt/EMT with high-performance Pt nanoparticles highly dispersed on an ultra-small EMT, a preparation method thereof and application of the Pt/EMT as a catalase simulant catalyst.
The invention utilizes the inherent characteristics of surface acidity, low silicon-aluminum ratio, ultra-small particle size and the like of the EMT zeolite to uniformly disperse Pt nano particles on the surface of the EMT zeolite by an impregnation reduction method to prepare the high-performance Pt/EMT catalyst; the catalyst can be used as catalase simulant.
The preparation method of the Pt/EMT with the Pt nanoparticles highly dispersed on the ultra-small EMT provided by the invention comprises the following specific steps.
Synthesizing ultra-small EMT zeolite:
(1) dissolving an aluminum source in distilled water under stirring, and marking as a solution A; dissolving sodium hydroxide in distilled water under stirring, and marking as solution B; both solutions were fully cooled in a 277K ice bath;
(2) then, slowly pouring the solution A into the solution B under stirring to form a mixed solution, namely a solution C, and slowly adding a silicon source under stirring to form turbid suspension; the molar ratio of the amounts of the components of the turbid suspension is: na (Na)2O﹕Al2O3﹕SiO2﹕H2O = (18.45-21): 1.0-2.3): 4-5.9): 200-; under stirring, carrying out hydrothermal crystallization reaction on the suspension in a water bath at the temperature of 20-70 ℃ for 30-40 hours;
(3) centrifuging at 8500-10000r/min for 8-15 min, separating solid product, washing with distilled water for several times until pH =7.5-8.5 to obtain ultra-small EMT zeolite;
(4) finally, the solid powder of EMT zeolite was dried at room temperature for at least 24 h.
And (II) preparing the Pt/EMT composite by adopting an in-situ reduction method combining wet impregnation and a reducing agent:
(1) firstly, 50-150mg of EMT zeolite solid powder is dispersed in water and is subjected to ultrasonic treatment for 15-25 minutes to form uniform suspension;
(2) then, dropwise adding 1-5mM of platinum source under stirring to obtain a mixed solution; dripping 0.2-0.4M reducing agent into the mixed solution at 273K, and stirring at room temperature for 12-36 h;
(3) centrifuging at 5500-6500r/min for 4-10 min, collecting solid powder, and washing with water and ethanol for multiple times; (4) and finally, drying in a vacuum oven at room temperature to obtain the EMT zeolite supported Pt compound which is marked as Pt/EMT.
The Pt/EMT prepared by the method has an ultra-small size, the general particle size is 15-20 nm, and the particle size of Pt is 5-8 nm.
In the Pt/EMT catalyst, since Pt can be contained in various amounts, it can be expressed as xPt/EMT catalyst, and x is the mass ratio (%) of Pt to EMT zeolite.
In the step (one), the aluminum source is sodium metaaluminate, and the silicon source is silica Sol (SiO)2Content of 30%), water glass or white carbon black, etc.
In the step (II), the platinum source is chloroplatinic acid; the reducing agent is NaHB4。
In the invention, Pt nano-particles with different concentrations are loaded on the surface of the EMT zeolite, so that the high dispersion of the Pt nano-particles is realized. As a high performance catalase mimetic catalyst.
As a catalase mimic catalyst, the catalyst can be used for detecting hydrogen peroxide or glucose; the specific method comprises the following steps:
the Pt/EMT is used as a peroxidase simulant, and the microminiature EMT zeolite with the size of 15-20 nm is synthesized in a template-free colloid system by a low-temperature crystallization method, and is used as a carrier for supporting the high surface dispersion of Pt NPs (5-8 nm).
The Pt/EMT nano material can be well dispersed in water to form uniform suspension; steady state kinetic analysis showed that Pt/EMT nanocomposites, in hydrogen peroxide (H)2O2) As a preferred peroxide catalyst for the oxidation of 3,3,5, 5-Tetramethylbenzidine (TMB) to H2O2And TMB has a higher affinity than HRP, allowing H to be measured in a linear range of 3 μ M-30 μ M2O2Concentration, detection limit is as low as 1.1 μ M; on the other hand, the glucose generates hydrogen peroxide under the action of the glucose-degrading enzyme, and the hydrogen peroxide and the glucose are combined to accurately detect the content of the glucose in the solution. The catalyst has high selectivity to glucose relative to other sugars. Colorimetrically, can be used to detect glucose concentrations down to 13.2 μ M, with a wide linear range (0.08 mM-0.28 mM). More importantly, the Pt/EMT nano composite material has high selectivity on glucose, can be used as a peroxidase catalyst, is used for accurately detecting the glucose concentration in a real serum sample and fruit juice, and can be used for clinical diagnosis, food detection and biochemical analysis.
Drawings
FIG. 1 shows XRD patterns of EMT (a) and Pt/EMT (b) zeolites.
FIG. 2 is a glucose detection limit test for Pt/EMT catalysts.
FIG. 3 is a glucose selectivity analysis of Pt/EMT catalyst.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings:
raw materials: sodium metaaluminate, silica sol (30%), sodium hydroxide, chloroplatinic acid, deionized water, sodium borohydride and EMT zeolite are added in a range which meets the molar ratio: 18.45 Na2O﹕1.0 Al2O3﹕5.15 SiO2﹕240 H2O; in addition, Pt/EMT catalysts with different Pt contents (0.65, 1.3, 1.95, 2.6, 3.25, 3.9 wt% expressed as xPt/EMT catalyst, x = mass ratio of Pt to EMT zeolite (%)) were prepared by the impregnation reduction method.
Example 1: synthesis of EMT zeolite
In a typical synthesis of EMT zeolite, solution a is first prepared by dissolving 2g of sodium aluminate in 10mL of distilled water with stirring. Solution B was prepared by dissolving 17g of sodium hydroxide in 30mL of distilled water with stirring. Both solutions were cooled well in a 277K ice bath. Solution a was then slowly poured into solution B with vigorous stirring to form mixed solution C, and 10.46 mL of colloidal silica was slowly added with stirring. The final cloudy suspension had the following chemical composition: 18.45 Na 2O: 1.0 Al2O 3: 5.15 SiO 2: 240H 2O. The suspension was stirred continuously for 5 minutes and then kept in a water bath at 303K for 36 hours with constant stirring for hydrothermal crystallization. The solid product was isolated by centrifugation at 8000r/min for 10 minutes, then washed several times with distilled water until pH = 8. Finally, the solid powder of EMT zeolite was dried at room temperature for at least 24 h.
Example 2: synthesis of Pt/EMT zeolite
Pt/EMT catalysts with different Pt contents (0.65, 1.3, 1.95, 2.6, 3.2, 3.9 wt%) were prepared, denoted as xPt/EMT catalyst, x = Pt with PtMass ratio (%) of EMT zeolite. In a typical 2.6Pt/EMT catalyst synthesis, sonication for 20 minutes, 100 mg of EMT zeolite was well dispersed in 15 mL of water to form a homogeneous suspension. Then, 7mL of H was added dropwise while stirring for a further 1H2PtCl6Solution (2 mM). 2 mL of freshly prepared NaBH at 273K4The solution (0.2M) was added dropwise to the mixture, which was then stirred at room temperature for 12 h. After centrifugation at 6000r/min for 5 minutes, the solid powder was collected and then washed 3 times with water and ethanol, respectively. Finally, 2.6Pt/EMT catalyst was obtained by drying overnight at room temperature.
The XRD pattern of the zeolite after complete crystallization, as shown in the graph of fig. 1, fig. 1 (a) shows the XRD patterns of the parent EMT zeolite and Pt/EMT nanocomposite, in which the diffraction peaks appear as those of typical EMT zeolite. The spread of the Bragg peak was very significant in both samples, indicating that the resultant EMT had a very small degree of crystallinity, with an average particle size of 13.8 nm as calculated by the Scherrer equation. In the Pt/EMT nanocomposites, no diffraction peaks of metallic Pt appeared (FIG. 1A-b), indicating that the Pt NPs are highly dispersed on the matrix of the EMT zeolite.
For glucose detection, glucose should first be converted to H by the oxidation reaction of glucose oxidase (GOx)2O2And gluconic acid, and then detecting the generated H by a colorimetric method based on TMB oxidation under the catalytic action of a Pt/EMT nano composite material2O2This may be closely related to the concentration of glucose in the solution. The absorbance of the solution gradually increased with the glucose concentration from 0 to 2mM (FIG. 2), and the glucose concentration response curve showed a significant linear dependence in the concentration range of 0.08 to 0.28 mM (FIG. 2B). The LOD of glucose on the Pt/EMT nanocomposite was calculated to be about 13.2. mu.M.
Fig. 3 shows the selectivity of Pt/EMT nanocomposite catalyst for glucose versus other sugars, a key factor in evaluating whether the material can be used in complex systems. Since GOx enzyme has high specificity to glucose, the Pt/EMT nanocomposite material has very weak reaction to comparative sugars such as fructose, lactose and sucrose, and shows high selectivity of the peroxidase-like catalyst of Pt/EMT to glucose even at a high concentration 10 times that of glucose.
Claims (6)
1. A preparation method of Pt/EMT with highly dispersed Pt nanoparticles on ultra-small EMT is characterized by comprising the following specific steps:
synthesis of ultra-small EMT zeolite:
(1) dissolving an aluminum source in distilled water under stirring, and marking as a solution A; dissolving sodium hydroxide in distilled water under stirring, and marking as solution B; both solutions were fully cooled in a 277K ice bath;
(2) then, slowly pouring the solution A into the solution B under stirring to form a mixed solution, namely a solution C, and slowly adding a silicon source under stirring to form turbid suspension; the molar ratio of the components of the turbid suspension is as follows: na (Na)2O﹕Al2O3﹕SiO2﹕H2O = (18.45-21): 1.0-2.3): 4-5.9): 200-; under stirring, carrying out hydrothermal crystallization reaction on the suspension in a water bath at the temperature of 20-70 ℃ for 30-40 hours;
(3) centrifuging at 8500-10000r/min for 8-15 min, separating solid product, washing with distilled water for several times until pH =7.5-8.5 to obtain ultra-small EMT zeolite;
(4) finally, the solid powder of EMT zeolite is dried at room temperature for at least 24 h;
and (II) preparing Pt/EMT by adopting an in-situ reduction method combining wet impregnation and a reducing agent:
(1) firstly, 50-150mg of EMT zeolite solid powder is dispersed in water and is subjected to ultrasonic treatment for 15-25 minutes to form uniform suspension;
(2) then, dropwise adding 1-5mM of platinum source under stirring to obtain a mixed solution; dripping 0.2-0.4M reducing agent into the mixed solution at 273K, and stirring at room temperature for 12-36 h;
(3) centrifuging at 5500-6500r/min for 4-10 min, collecting solid powder, and washing with water and ethanol for multiple times; (4) finally, drying in a vacuum oven at room temperature to obtain an EMT zeolite supported Pt compound which is marked as Pt/EMT;
wherein the particle size of Pt/EMT is 15-20 nm, and the particle size of Pt is 5-8 nm.
2. The preparation method according to claim 1, wherein in the step (one), the aluminum source is sodium metaaluminate, and the silicon source is silica sol, water glass or white carbon black.
3. The production method according to claim 1, wherein in the step (two), the platinum source used is chloroplatinic acid; the reducing agent is NaHB4。
4. Pt/EMT in which Pt nanoparticles obtained by the production method according to any one of claims 1 to 3 are highly dispersed on ultra-small EMT.
5. The use of the Pt nanoparticles of claim 4 as highly dispersed Pt/EMT on ultra small EMT as a peroxidase mimic, comprising: for H2O2Monitoring the concentration, wherein the detection limit is as low as 1.1 mu M; colorimetrically for detecting the glucose concentration, with a detection limit as low as 13.2 μ M, a linear range of 0.08 mM-0.28 mM.
6. Use according to claim 5, for the detection of glucose concentration in real serum samples and fruit juices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010125763.4A CN111298828A (en) | 2020-02-27 | 2020-02-27 | Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010125763.4A CN111298828A (en) | 2020-02-27 | 2020-02-27 | Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111298828A true CN111298828A (en) | 2020-06-19 |
Family
ID=71154780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010125763.4A Pending CN111298828A (en) | 2020-02-27 | 2020-02-27 | Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298828A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2374903A1 (en) * | 2008-12-09 | 2011-10-12 | National University Corporation Hokkaido University | Method for producing a sugar-containing liquid in which the primary ingredient is glucose |
| CN102350372A (en) * | 2011-07-12 | 2012-02-15 | 南昌大学 | Preparation method of polyaniline/graphene controllable load platinum nanoparticles |
| CN103011189A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol |
| CN104549234A (en) * | 2014-12-11 | 2015-04-29 | 江南大学 | CDs-Pt nanomaterial with catalase catalytic properties |
| CN107159301A (en) * | 2017-04-28 | 2017-09-15 | 复旦大学 | A kind of base supported mimetic enzyme catalyst of zeolite and its preparation method and application |
-
2020
- 2020-02-27 CN CN202010125763.4A patent/CN111298828A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2374903A1 (en) * | 2008-12-09 | 2011-10-12 | National University Corporation Hokkaido University | Method for producing a sugar-containing liquid in which the primary ingredient is glucose |
| CN102350372A (en) * | 2011-07-12 | 2012-02-15 | 南昌大学 | Preparation method of polyaniline/graphene controllable load platinum nanoparticles |
| CN103011189A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol |
| CN104549234A (en) * | 2014-12-11 | 2015-04-29 | 江南大学 | CDs-Pt nanomaterial with catalase catalytic properties |
| CN107159301A (en) * | 2017-04-28 | 2017-09-15 | 复旦大学 | A kind of base supported mimetic enzyme catalyst of zeolite and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| ENG-POH NG ET AL.: "Capturing Ultrasmall EMT Zeolite from Template-Free Systems", 《SCIENCE》 * |
| 尹元根等: "《多相催化剂的研究方法》", 31 October 1988 * |
| 戴遐明等: "《超微陶瓷粉体实用化处理技术》", 30 September 2009 * |
| 黄仲涛等: "《工业催化》", 31 May 1994 * |
| 黄文峰等: "CuO/EMT沸石复合材料的制备及其在无酶葡萄糖传感器中的应用", 《上海大学学报（自然科学版）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6492014B1 (en) | Mesoporous composite gels an aerogels | |
| Cheng et al. | Rational design of a stable peroxidase mimic for colorimetric detection of H2O2 and glucose: A synergistic CeO2/Zeolite Y nanocomposite | |
| Dai et al. | Bioanalysis based on nanoporous materials | |
| Qi et al. | Facile synthesis of core–shell Au@ CeO 2 nanocomposites with remarkably enhanced catalytic activity for CO oxidation | |
| CN103272634B (en) | Preparation method of nano metal loaded molecular sieve based catalyst | |
| CN107020147B (en) | MFI structure lamellar molecular sieve catalyst for packaging metal oxide or metal nanoparticles, and preparation method and application thereof | |
| Ozansoy Kasap et al. | Biosensors based on nano-gold/zeolite-modified ion selective field-effect transistors for creatinine detection | |
| Kandula et al. | A facile synthetic approach for SiO 2@ Co 3 O 4 core–shell nanorattles with enhanced peroxidase-like activity | |
| Chen et al. | Palygorskite@ Co3O4 nanocomposites as efficient peroxidase mimics for colorimetric detection of H2O2 and ascorbic acid | |
| CN102847533B (en) | Microwave method for synthesizing attapulgite and palladium nanocomposite catalyst | |
| Bronstein et al. | Mesoporous alumina and aluminosilica with Pd and Pt nanoparticles: structure and catalytic properties | |
| WO2009044146A1 (en) | Metal nanoparticles | |
| Xu et al. | Norepinephrine-induced AuPd aerogels with peroxidase-and glucose oxidase-like activity for colorimetric determination of glucose | |
| Luo et al. | Bimetallic Fe-Co nanoalloy confined in porous carbon skeleton with enhanced peroxidase mimetic activity for multiple biomarkers monitoring | |
| de Morais et al. | Gold nanoparticles on a thiol-functionalized silica network for ascorbic acid electrochemical detection in presence of dopamine and uric acid | |
| Wang et al. | A 3-dimensional C/CeO 2 hollow nanostructure framework as a peroxidase mimetic, and its application to the colorimetric determination of hydrogen peroxide | |
| Ren et al. | Hydrogen peroxide biosensor based on direct electrochemistry of hemoglobin immobilized on gold nanoparticles in a hierarchically porous zeolite | |
| Hajiagha et al. | Synthesis of cobalt-modified MSN as a model enzyme: Evaluation of the peroxidatic performance | |
| Sheikh-Mohseni et al. | Green bio-synthesis of Ni/montmorillonite nanocomposite using extract of Allium jesdianum as the nano-catalyst for electrocatalytic oxidation of methanol | |
| Rostami et al. | Using of silver nanoparticles incorporated in nanoporous ZSM-5 hierarchical zeolite prepared from bagasse as a new sensor for electrocatalytic determination of H2O2 in biological samples | |
| Aghayan et al. | Enzymatic activity of Fe-grafted mesoporous silica nanoparticles: an insight into H 2 O 2 and glucose detection | |
| CN117696050A (en) | Platinum-modified mesoporous gold nano-enzyme and preparation method and application thereof | |
| CN112717934B (en) | Attapulgite-loaded transition metal oxide composite material and preparation method and application thereof | |
| CN111298828A (en) | Pt/EMT with highly dispersed Pt nanoparticles on EMT and preparation method and application thereof | |
| Song et al. | Facile Route to Nanoporous NiO Structures from the α‐Ni (OH) 2/EG Precursor and Application in Water Treatment |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200619 |
|
| WD01 | Invention patent application deemed withdrawn after publication |