CN115739110A - Preparation method and application of platinum-based catalyst - Google Patents
Preparation method and application of platinum-based catalyst Download PDFInfo
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- CN115739110A CN115739110A CN202211374236.2A CN202211374236A CN115739110A CN 115739110 A CN115739110 A CN 115739110A CN 202211374236 A CN202211374236 A CN 202211374236A CN 115739110 A CN115739110 A CN 115739110A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 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 43
- 239000008103 glucose Substances 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 28
- 108010015776 Glucose oxidase Proteins 0.000 claims description 15
- 239000004366 Glucose oxidase Substances 0.000 claims description 15
- 229940116332 glucose oxidase Drugs 0.000 claims description 15
- 235000019420 glucose oxidase Nutrition 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 102000016938 Catalase Human genes 0.000 claims description 7
- 108010053835 Catalase Proteins 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- 238000006479 redox reaction Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 229920005615 natural polymer Polymers 0.000 claims 2
- 102000004190 Enzymes Human genes 0.000 abstract description 14
- 108090000790 Enzymes Proteins 0.000 abstract description 14
- 238000001514 detection method Methods 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 19
- 229940088598 enzyme Drugs 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention provides a preparation method and application of a platinum-based catalyst, and belongs to the technical field of biosensors. A method for preparing a platinum-based catalyst, comprising the steps of; (1) pretreating an electrode; (2) Coating a particle mixed solution of chitosan, iron oxide and copper nanochains on the surface of the electrode, and drying to prepare a platinum catalyst loading layer for loading the chitosan-iron oxide-copper nanochains; (3) The electrode coated with the platinum catalyst support layer was placed in a H2PtCl6 solution, and constant pressure deposition was performed to obtain an electrode supporting a platinum-based catalyst. The invention also provides an application of the platinum-based catalyst. The preparation method constructs a system of loading enzyme by nano platinum, chitosan, nano copper and nano tetraoxide, improves the loading stability and the loading rate of the enzyme, and simultaneously ensures the activity of the enzyme. When the catalyst is applied to a glucose biosensor, the problems of low detection sensitivity and poor response capability can be effectively solved.
Description
Technical Field
The invention belongs to the technical field of biosensors, and particularly relates to a preparation method and application of a platinum-based catalyst.
Background
The conventional glucose biosensor works on the principle that a thin layer of glucose oxidase is covered on the surface of an oxygen electrode, and the concentration of glucose can be indirectly measured by measuring the consumption of dissolved oxygen in a solution through the oxygen electrode.
Glucose sensors are divided into three types; (1) A fuel cell type glucose sensor is characterized in that two platinum mesh electrodes are clamped in three silica gel membranes, water and oxygen can penetrate through the silica gel membranes, but glucose cannot penetrate through the silica gel membranes, the glucose is oxidized under the action of platinum catalyst at an anode, the oxygen is reduced to O2-at a cathode, so a potential difference is generated between the two electrodes, and the concentration of the glucose can be measured at the anode. (2) Optical glucose sensor is a fiber sensor
The concentration of glucose can be measured by spectroscopic analysis of the degree of indicator discoloration caused by the change in oxidation of glucose. (3) The glucose sensor with enzyme electrode is to fix glucose oxidase between two semi-permeable membranes and oxidize glucose to produce hydrogen peroxide, and the produced amount and the consumed amount of oxygen are in direct proportion to the glucose concentration.
The working principle of the glucose sensor in the prior art; glucose oxidase and/or catalase is coated on the surface layer of the working electrode, hydrogen peroxide is generated after the glucose in the blood contacts with the glucose oxidase, and the concentration of the glucose in the blood is judged by observing the variation of the hydrogen peroxide or the oxygen in the system. According to the working electrode of the glucose sensor, a gold layer is deposited on the surface of a metal substrate of a conducting layer to serve as a metal transition layer, a layer of loose platinum black particles is electrodeposited on the surface of the gold electrode, and a mediator and enzyme are directly adsorbed on the surface of the platinum black electrode, so that the electrode requirement of electrochemical oxidation of hydrogen peroxide under the physiological environment of pH =7.4 is met, and the porous characteristic of the platinum black particles is utilized. However, the platinum black particles can provide few enzyme-carrying sites, the particles are easy to agglomerate, and the stability of glucose oxidase load is poor, so that the catalytic activity of the glucose oxidase is limited, and the lower limit value of glucose detection is higher, so that the detection sensitivity of the glucose biosensor is reduced, and the response capability is poor.
Disclosure of Invention
In view of the above, the invention provides a preparation method and an application of a platinum-based catalyst, so as to solve the technical problems of low detection sensitivity and poor response capability of a glucose biosensor in the prior art.
The invention provides a preparation method of a platinum-based catalyst, which comprises the following steps of;
(1) Pretreating an electrode; the electrode can be a glassy carbon electrode or a gold electrode, and the pretreatment of the electrode comprises the steps of polishing an aluminum oxide suspension into a mirror surface, and then sequentially putting ethanol and water for ultrasonic cleaning;
(2) Coating a particle mixed solution of a natural high polymer material, an iron oxide and a copper nano chain on the surface of the electrode, drying, and then preparing a platinum catalyst loading layer for loading the chitosan-iron oxide-copper nano chain, wherein the molar ratio of the natural high polymer material to the iron oxide to the copper nano chain is 10:3-4:2-3; the natural high molecular polymer material comprises one or more of chitosan, cellulose and sodium alginate.
The iron oxide is nano Fe3O4, and the preparation method of the nano Fe3O4 comprises the following steps; 1) Mixing a mixture of 1:2-2.5 of FeSO4.7H2O and FeCl3.6H2O; 2) Dropwise adding ammonia water into the solution system; 3) Stirring for 0.5h at 70 ℃ to obtain a precipitate, and cleaning and drying the precipitate to obtain the nano Fe3O4 particles.
The preparation method of the copper nano chain comprises the following steps: 1) Adding a copper salt solution and a stabilizer into an alkaline solution to obtain a mixed solution; 2) Introducing nitrogen into the mixed solution; 3) And then adding sodium borohydride solution, and carrying out redox reaction (the temperature of the redox reaction is 55-59 ℃) to obtain the copper nano chain, wherein the addition amount of the sodium borohydride is 6.5-8.8 mmol.dm-3.
(3) And placing the electrode coated with the platinum catalyst supporting layer in a H2PtCl6 solution, performing constant pressure deposition at-0.2V for 60-95s, wherein the volume concentration of the H2PtCl6 solution is 0.6-2.6%, and drying to obtain the electrode loaded with the platinum-based catalyst.
Use of a platinum-based catalyst as hereinbefore described comprising the steps of: dripping a mixed liquid drop of glucose oxidase and catalase onto the electrode loaded with the platinum-based catalyst in the step (3); after drying, a layer of Nafion solution is coated to prepare the glucose biosensor.
The deposition voltage and the concentration of chloroplatinic acid are controlled, so that the platinum catalyst obtained by constant potential deposition is nano platinum, and the platinum catalyst has high specific surface area, high catalytic capacity and stability.
According to the invention, a load layer consisting of chitosan-iron oxide-copper nanochains is coated on the surface of an electrode, and then nano platinum is prepared by potential deposition, so that the specific surface energy of the whole system can be increased, more abundant sites are provided for enzyme attachment, the sensitivity of the enzyme to substrate reaction can be improved, and the lower limit of glucose concentration detection is reduced.
The technical purpose of adding copper in the invention is that besides glucose oxidase can catalyze platinum oxide and glucose oxidative decomposition, the addition of copper can enhance the catalytic capability of platinum on glucose, the oxidation of glucose can be simplified into two steps, and the first step is that glucose is rapidly decomposed into gluconate or other intermediate products (O-R), which can be adsorbed on active Pt sites in large quantity and is slowly oxidized. Therefore, the improvement in the electrochemical catalytic activity of PtCu is related to the following two factors; one is that the species of the electric activity Pt is increased due to the doping of Cu; the second is that the Cu atom is not only a promoting center for the generation of Cu-OR species, it is also an electron donor for Pt. The incorporation of Cu atoms reduces the binding energy of the 4f orbital of Pt, which leads to the reduction of the bond energy between Pt and RO, and finally forms Cu-OR, and the process is favorable for the regeneration of Pt active sites. In conclusion, the catalytic action of the electrode on glucose is enhanced due to the synergistic action between Pt and Cu atoms, and the like. This greatly increases the sensitivity of the sensor to glucose, and it is understood that the enzyme and platinum copper together catalyze the oxidative breakdown of glucose.
When the pH value is more than 4.2, the glucose oxidase is negatively charged, and the chitosan is positively charged, so that a stable ion pair can be formed, and the good effect on enzyme immobilization is achieved. In addition, the chitosan has good biocompatibility, and the response capability of the biosensor is improved. Fe3O4 is a ferrite with a trans-spinel structure with super-pure magnetism, oxygen atoms are in cubic closest packing and have good conductivity, an iron element has two different valence states of Fe2+ and Fe3+ in the crystal, the Fe2+ and the Fe3+ are arranged in disorder in an oxygen octahedron, electrons can be transmitted through the conversion of the Fe2+ and the Fe3+, the path of transmitting the electrons in the electrochemical reaction process is shortened, the responsiveness of the biosensor is improved, and Fe3O4 nanoparticles also have good biocompatibility and are very suitable for being used as an electrode modification material of the biosensor.
In addition, the Fe3O4 magnetic nanoparticles can improve the stability and the loading rate of glucose oxidase loading, so that the prepared glucose sensor has good biocompatibility, the enzyme activity is favorably retained, the separation is easy in the enzyme loading process, and the loss of the enzyme activity is reduced.
The invention has the following beneficial effects;
(1) In the preparation method, the nano platinum is prepared through potential deposition, and the nano-sized particles can increase the specific surface energy of the whole system and reduce the lower limit of glucose concentration detection, and the preparation method is simple;
(2) Copper is introduced into the preparation method, so that the catalytic capability of platinum on glucose is improved, and the concentration sensitivity of the biosensor is improved;
(3) According to the preparation method, chitosan and Fe3O4 nanoparticles are introduced, so that the loading stability and the loading rate of the enzyme are improved, and the activity of the enzyme is ensured;
(4) Meanwhile, the invention also provides the application of the platinum-based catalyst, and the prepared glucose biosensor has low detection limit and high sensitivity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
This example is a method of preparing a platinum-based catalyst comprising the steps of;
(1) Pretreating an electrode; the electrode can be a glassy carbon electrode or a gold electrode, and the pretreatment of the electrode comprises the steps of polishing an aluminum oxide suspension into a mirror surface, and then sequentially putting ethanol and water for ultrasonic cleaning;
(2) Mixing the components in a molar ratio of 1: mixing and dissolving FeSO4.7H2O and FeCl3.6H2O of 2; dropwise adding ammonia water into the solution system; stirring for 0.5h at 70 ℃ to obtain a precipitate, and cleaning and drying the precipitate to obtain nano Fe3O4 particles;
(3) Adding copper nitrate and a stabilizer into an alkaline solution to obtain a mixed solution; introducing nitrogen into the mixed solution; then adding a sodium borohydride solution, and carrying out oxidation-reduction reaction at 55 ℃ to obtain a copper nano chain, wherein the addition amount of the sodium borohydride is 6.5 mmol/dm-3;
(4) Coating a particle mixed solution of chitosan, nano Fe3O4 particles and copper nano chains on the surface of the electrode, drying, and preparing a platinum catalyst loading layer for loading chitosan-iron oxide-copper nano chains, wherein the molar ratio of chitosan to iron oxide to copper nano chains is 10:3:2;
(5) And placing the electrode coated with the platinum catalyst supporting layer in a H2PtCl6 solution, performing constant pressure deposition at-0.2V for 60s, wherein the volume concentration of the H2PtCl6 solution is 0.6%, and drying to obtain the electrode loaded with the platinum-based catalyst.
Use of a platinum-based catalyst as hereinbefore described comprising the steps of: dripping a mixed liquid drop of glucose oxidase and catalase onto an electrode loaded with a platinum-based catalyst; after drying, a layer of Nafion solution is coated to prepare the glucose biosensor. The specific method for preparing the glucose biosensor is described herein by referring to the technical methods commonly used by those skilled in the art.
Example 2
This example is a method for preparing a platinum-based catalyst comprising the steps of;
(1) Pretreating an electrode;
(2) Mixing the components in a molar ratio of 1:2.5 of FeSO4.7H2O and FeCl3.6H2O; dropwise adding ammonia water into the solution system; stirring for 0.5h at 70 ℃ to obtain a precipitate, and cleaning and drying the precipitate to obtain nano Fe3O4 particles;
(3) Adding a copper salt solution and a stabilizer into an alkaline solution to obtain a mixed solution; introducing nitrogen into the mixed solution; then adding a sodium borohydride solution, and carrying out an oxidation-reduction reaction at 59 ℃ to obtain a copper nano-chain, wherein the addition amount of the sodium borohydride is 8.8mmol dm-3;
(4) Coating a particle mixed solution of cellulose, nano Fe3O4 particles and copper nanochains on the surface of the electrode, drying, and then preparing a platinum catalyst supporting layer for supporting cellulose-iron oxide-copper nanochains, wherein the molar ratio of the cellulose to the iron oxide to the copper nanochains is 10:4:3;
(5) And placing the electrode coated with the platinum catalyst supporting layer in a H2PtCl6 solution, performing constant pressure deposition at-0.2V for 95s, wherein the volume concentration of the H2PtCl6 solution is 2.6%, and drying to obtain the electrode loaded with the platinum-based catalyst.
Use of a platinum-based catalyst as hereinbefore described comprising the steps of: dripping a mixed liquid of glucose oxidase and catalase onto an electrode loaded with a platinum-based catalyst; after drying, a layer of Nafion solution is coated to prepare the glucose biosensor.
Example 3
This example is a method for preparing a platinum-based catalyst comprising the steps of;
(1) Pretreating an electrode;
(2) Mixing a mixture of 1:2.2, mixing and dissolving FeSO4.7H2O and FeCl3.6H2O; dropwise adding ammonia water into the solution system; stirring for 0.5h at 70 ℃ to obtain a precipitate, and cleaning and drying the precipitate to obtain nano Fe3O4 particles;
(3) Adding a copper salt solution and a stabilizer into an alkaline solution to obtain a mixed solution; introducing nitrogen into the mixed solution; then adding a sodium borohydride solution, and carrying out an oxidation-reduction reaction at 57 ℃ to obtain a copper nano-chain, wherein the addition amount of the sodium borohydride is 7.6mmol dm-3;
(4) Coating a particle mixed solution of sodium alginate, nano Fe3O4 particles and a copper nano chain on the surface of the electrode, drying, and preparing a platinum catalyst loading layer for loading sodium alginate-iron oxide-copper nano chain, wherein the molar ratio of sodium alginate to iron oxide to copper nano chain is 10:3.5:2.5;
(5) And placing the electrode coated with the platinum catalyst supporting layer in a H2PtCl6 solution, performing constant-pressure deposition for 75s at-0.2V, wherein the volume concentration of the H2PtCl6 solution is 1.3%, and drying to obtain the electrode loaded with the platinum-based catalyst.
Use of a platinum-based catalyst as hereinbefore described comprising the steps of: dripping a mixed liquid of glucose oxidase and catalase onto an electrode loaded with a platinum-based catalyst; after drying, a layer of Nafion solution is coated to prepare the glucose biosensor.
Comparative example
(1) Pretreating an electrode; the electrode can be a glassy carbon electrode or a gold electrode, and the pretreatment of the electrode is that after an aluminum oxide suspension is polished into a mirror surface, ethanol and water are sequentially put into the mirror surface for ultrasonic cleaning;
(2) And (3) placing the electrode in a H2PtCl6 solution, carrying out constant pressure deposition for 75s at-0.2V, wherein the volume concentration of the H2PtCl6 solution is 1.3%, and drying to obtain the electrode loaded with the platinum-based catalyst.
(3) Dripping a mixed liquid drop of glucose oxidase and catalase onto an electrode loaded with a platinum-based catalyst; after drying, a layer of Nafion solution is coated to prepare the glucose biosensor.
The glucose biosensors in examples 1 to 3 and comparative examples were used to measure sensitivity, response time, and lower limit of detection, and the specific measurement method can refer to the measurement method in the prior art, and the following data can be obtained:
from the data, the glucose biosensor prepared by the method has the advantages of good detection sensitivity, high response speed and low detection limit. The detection precision and rapidity of the glucose are improved.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention. Various modifications and improvements of the technical solutions of the present invention that are made by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention that are claimed shall be fully described in the claims.
Claims (9)
1. A method for preparing a platinum-based catalyst, characterized by comprising the steps of;
(1) Pretreating an electrode;
(2) Coating a particle mixed solution of a natural high polymer material, an iron oxide and a copper nano chain on the surface of the electrode, and drying to prepare a platinum catalyst loading layer for loading the chitosan-iron oxide-copper nano chain;
(3) And placing the electrode coated with the platinum catalyst loading layer in a H2PtCl6 solution, performing constant potential deposition, and drying to obtain the electrode loaded with the platinum-based catalyst.
2. The method for preparing a platinum-based catalyst according to claim 1, wherein the molar ratio of the natural polymer material, the iron oxide and the copper nanochain in the step (2) is 10:3-4:2-3.
3. The method as claimed in claim 2, wherein the natural polymer material comprises one or more of chitosan, cellulose and sodium alginate.
4. The method of claim 1, wherein the H2PtCl6 solution has a volume concentration of 0.6 to 2.6%.
5. The method of claim 1, wherein the iron oxide is nano Fe3O4.
6. The method for preparing a platinum-based catalyst according to claim 1, wherein the method for preparing the copper nanochain comprises the steps of:
(1) Adding a copper salt solution and a stabilizer into an alkaline solution to obtain a mixed solution;
(2) Introducing nitrogen into the mixed solution;
(3) And adding a sodium borohydride solution, and performing oxidation-reduction reaction to obtain the copper nanochain.
7. The method of preparing a platinum-based catalyst according to claim 6, wherein the amount of sodium borohydride added is 6.5 to 8.8mmol dm-3.
8. The method for preparing a platinum-based catalyst according to claim 1, wherein the condition of potentiostatic deposition in step (3) is constant pressure deposition at-0.2V for 60 to 95 seconds.
9. Use of a platinum-based catalyst according to any one of claims 1 to 8, comprising the steps of: dripping a mixed liquid drop of glucose oxidase and catalase on the electrode loaded with the platinum-based catalyst in the step (3); after drying, a layer of Nafion solution is coated to prepare the glucose biosensor.
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