CN112663089A - Fe3O4@ hemoglobin core-shell structure material, preparation method and application - Google Patents
Fe3O4@ hemoglobin core-shell structure material, preparation method and application Download PDFInfo
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Abstract
The invention discloses Fe3O4@ hemoglobin core-shell structure material and preparation method thereof, wherein the core of the material is nano Fe3O4The shell of the micro-bead is hemoglobin and Fe3O4The @ hemoglobin core-shell structure material can be used as an electrocatalytic material for producing oxygen by water decomposition and inhibiting the generation of hydrogen peroxide in a system, and the preparation method is simple and easy to implement and does not need special equipment and harsh conditions.
Description
Technical Field
The invention relates to the technical field of crossing of inorganic nano magnetic materials, biological materials and energy materials, in particular to Fe3O4A @ hemoglobin core-shell structure material, a preparation method and application.
Background
The excessive use of fossil fuels has led to energy crisis and environmental problems on a global scale. Hydrogen is an ideal clean energy with high energy density, and hydrogen is prepared from water and utilized by decomposing water through electrocatalysis, so that the hydrogen is an effective measure for solving energy crisis and environmental problems. Domestic and foreign researches show that the reason for improving the efficiency of electrocatalytic decomposition of water is influenced, on one hand, the dynamic barrier of the oxygen evolution reaction of the anode is high, so that the overall efficiency of water decomposition is reduced, and the hydrogen evolution half-reaction of the cathode is seriously inhibited, thereby becoming one of the bottlenecks of the water decomposition reaction; on the other hand, by-products such as peroxide and superoxide generated in the reaction system are adsorbed on the surface of the electrocatalytic material, so that the electrocatalytic material is corroded and poisoned, and the activity and the service life of the electrocatalytic material are reduced.
Therefore, it is urgently needed to search for an efficient and economical strategy for reducing the kinetic barrier of oxygen evolution reaction of the anode and inhibiting the formation of byproduct hydrogen peroxide. Hemoglobin is a specific protein for the transport of oxygen within erythrocytes, consisting of globin and heme, the globin component of which is a tetramer consisting of two different pairs of globin chains (a and β). The hemoglobin molecule is a molecular machine capable of effectively combining with oxygen molecules, and a hemoglobin layer is assembled on the surface of the superparamagnetic nano microsphere, so that oxygen precipitated on the surface of the microsphere can be effectively transferred, the electrochemical oxygen evolution efficiency of the superparamagnetic nano microsphere is improved, the oxygen evolution potential barrier is reduced, and the anode current is improved; meanwhile, hemoglobin contains two pairs of different globin chains (alpha chain and beta chain) which have chiral structures, the chiral structures can cause cross polarization of electromagnetic fields, when electrons flow through substances with the chiral structures, spin polarization can be generated under the induction of a spiral electromagnetic field, the efficiency of photoelectrocatalysis water decomposition oxygen analysis reaction can be improved through a one-pot method, the potential barrier of the reaction is reduced, and the generation of a byproduct hydrogen peroxide is inhibited.
Currently, researchers at home and abroad develop related research work of hemoglobin modified magnetic nanoparticles. For example, Zhang Shijun et al use molecular imprinting technique to prepare magnetic protein molecular imprinting material for selective recognition of hemoglobin with hemoglobin as template [1]. They are synthesized into ferroferric oxide nano-particles by a hydrothermal method, and a layer of ferroferric oxide nano-particles is coated on the surface of the ferroferric oxide nano-particlesSilicon dioxide, wherein amino groups are introduced on the surface of the particles through further modification of m-aminophenylurea isopropyl triethoxysilane to obtain an aminated magnetic material; and utilizing the interaction between copper ions and amino on the surface of the aminated magnetic material and histidine on the surface of bovine hemoglobin to make template protein be combined on the surface of the magnetic material by means of complexation, and using m-phenylenediamine as functional monomer and ammonium persulfate as initiator to prepare the hemoglobin magnetic molecularly imprinted polymer regulated by metal ions. In another example, a polyethyleneimine-functionalized core-shell type magnetic cobalt nanoparticle/hemoglobin sensor [2] was prepared in Pelamis et al](ii) a Yuan et al construct magnetic imprinted nanoparticle immobilized hemoglobin modified magnetic electrodes, which are used as hydrogen peroxide sensors; preparing the magnetic molecular imprinting nano particle Fe of the hemoglobin3O4@SiO2 NPs（MMIPs NPs）[3](ii) a The sunice flower and the hemoglobin magnetic molecular imprinting electrochemical sensor are constructed and used for electrocatalytic detection of Nitrite (NO)2 -）[4]. Preparing hemoglobin/Fe by adopting a coprecipitation method such as Nieman and the like3O4The composite being in the form of particles [5]。
However, in general, the currently reported binding process of hemoglobin and magnetic nanoparticles involves a multi-step chemical bridging coupling process, which is complicated and difficult to industrially popularize and apply; the application field mainly relates to the fields of selective recognition of molecules, sensors and dye adsorption, in fact, the three fields of selective recognition of molecules, sensors and dye adsorption are completely different research fields from photoelectrocatalytic water decomposition oxygen analysis reaction, the internal mechanism and mechanism of the three fields are completely different, and hemoglobin/Fe reported in the research fields is difficult to determine3O4Whether the products of the compound, the hemoglobin magnetic molecularly imprinted polymer and the like have the activity of the photoelectrocatalysis water decomposition oxygen analysis reaction; in addition, because the system of the hemoglobin magnetic molecularly imprinted polymer is complex, the interaction relationship among various substance compositions is difficult to be clarified.
[1] Zhangzhenjin molecular imprinting magnetic material preparation and its [ D ] recognition of bovine hemoglobin & Tianjin university of science & technology 2015.
[2] PEPTIDE FUNCTIONALIZED CORE-SHELL MAGNETIC COBALT NANOPARTICLES/HEMOGLOBIN SENSOR PREPARATION AND HYDROGEN PEROXIDE DETERMINATION [ J ] ACQUICK ASSOCIATION 2020, 6: 471 476.
[3] Yuan, Wangchanxin, Caoyuyihua, magnetic imprinted nanoparticle immobilized hemoglobin modified magnetic electrode construction of Hydrogen peroxide sensor [ J ] electrochemistry, 2019, 25: 757-.
[4] Sunrong flower, development of hemoglobin magnetic molecular imprinting electrochemical sensor [ D ]. Jiangnan university, 2017.
[5] Matthew Essandoh, Rafael A. Garcia, Makahra R.Gayle, Christine M.Nieman. Performance and mechanism of polypeptidylated hemoglobin (Hb)/iron oxide magnetic composites for enhanced dye removal. Chemosphere, 2020, 247: 125897。
Disclosure of Invention
The invention aims to provide Fe3O4The material can be used as an electro-catalytic material for producing oxygen by water decomposition and inhibiting the generation of hydrogen peroxide in a system, and the preparation method is simple and easy to implement and does not need special equipment or harsh conditions.
The technical scheme of the invention is as follows:
fe3O4The material has a structure of @ hemoglobin core-shell, and the core is nano Fe3O4The shell layer of the micro-bead is hemoglobin.
Preferably, the nano Fe3O4The micro-beads are made of 20-30nm Fe3O4The diameter of the micro-bead is 150-250nm formed by self-assembling nano-crystal, and the nano-Fe3O4The micro-bead is decorated with hydrophilic groups.
Preferably, the hydrophilic groups are hydroxyl and carboxyl; the nano Fe3O4The micro-beads are superparamagnetic.
The invention also provides Fe3O4The preparation method of the @ hemoglobin core-shell structure material comprises the following steps of sequentially connecting:
s1, Synthesis of superparamagnetic ironMagnetic nano Fe3O4Microbeads and superparamagnetic nano-Fe3O4Grafting hydrophilic functional groups on the surfaces of the microbeads;
s2, mixing the superparamagnetic nano Fe3O4Immersing the microbeads in the solution of hemoglobin, and self-assembling at room temp in the nano Fe particles with superparamagnetism3O4Assembling a hemoglobin shell layer on the surface of the microbead to obtain Fe3O4@ hemoglobin core-shell structural material.
Further, in the step S1, a hydrothermal synthesis one-pot method is adopted to prepare the superparamagnetic nano Fe3O4The micro-beads specifically comprise: deionized water as solvent and FeCl3As Fe source, NaOH is used for regulating alkalinity, citric acid and polyacrylic acid are used as surfactants, and hydrothermal temperature is 180 DEGoAnd C, reacting for 20-24h in the container.
Further, the concentration of the hemoglobin solution in the step S2 is 10mg/mL, and the assembly time is 24-72 h.
The invention also provides Fe3O4The application of the @ hemoglobin core-shell structure material as an electrocatalytic material for water decomposition to produce oxygen and simultaneously inhibiting the generation of hydrogen peroxide in a system.
The invention has the beneficial effects that:
1. preparation of Fe by self-assembly method3O4The process steps of the @ hemoglobin core-shell structure material are simple and easy to implement, special equipment and a preparation process under harsh conditions are not needed, the cost is low, the prepared material can form an obvious core-shell structure, and industrial popularization and application are facilitated.
2. The invention provides Fe3O4The @ hemoglobin core-shell structure material can be used as an electrocatalytic material for water decomposition to produce oxygen and simultaneously inhibit the generation of hydrogen peroxide in a system, and an oxygen molecule separated out on the surface of the microsphere is effectively transferred by utilizing a hemoglobin layer, so that the electrochemical oxygen evolution efficiency of the superparamagnetic nano microsphere is improved, the oxygen evolution potential barrier is reduced, and the anode current is improved; meanwhile, the chiral structures of alpha and beta globin chains in hemoglobin are utilized, the efficiency of the photoelectrocatalysis water decomposition oxygen analysis reaction is improved and reduced by a one-pot methodA barrier to the reaction, and suppresses the production of hydrogen peroxide as a by-product.
3. The invention relates to' a Fe3O4The material with the structure of the hemoglobin core-shell is synthesized into nanospheres formed by self-assembly of magnetic nano microcrystals in one step by a hydrothermal method, the nanospheres have large specific surface area and are beneficial to self-assembly of hemoglobin molecules on the surfaces of the nanospheres, hemoglobin is assembled on the surfaces of the nanospheres formed by self-assembly of the magnetic nano microcrystals by the self-assembly method to form a shell structure, and the shells are uniform.
4. Because the specific surface area of the nanosphere is large, the improvement of hemoglobin and Fe is facilitated3O4Efficiency of synergy between nanospheres.
5. The nanosphere structure can provide a large number of active sites for electrocatalytic reaction, and effectively improve the reaction activity;
6. compared with the existing magnetic molecular imprinting material and the like, Fe3O4The composition system of the @ hemoglobin core-shell structure material is simple and clear, and is favorable for clarifying the interaction relation among various composition substances and clarifying the catalytic mechanism.
Drawings
FIG. 1 is Fe prepared in example 13O4A TEM image of the hemoglobin core-shell structure material, (a) a low-resolution TEM image, and (b) a high-resolution TEM image.
FIG. 2 is Fe prepared in example 13O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4VSM contrast plots for beads as electrocatalytic anodes, respectively.
FIG. 3 is Fe prepared in example 13O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4Water decomposition oxygen rate profiles when the beads were used as electrocatalytic anodes, respectively.
FIG. 4 is Fe prepared in example 13O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4H in the reaction system when the microbeads are respectively used as electrocatalytic anodes2O2A generation situation detection map of (1).
FIG. 5 is an embodimentExample 2 preparation of Fe3O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4Water decomposition oxygen rate profiles when the beads were used as electrocatalytic anodes, respectively.
FIG. 6 is Fe prepared in example 23O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4H in the reaction system when the microbeads are respectively used as electrocatalytic anodes2O2A generation situation detection map of (1).
FIG. 7 is Fe prepared in example 33O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4Water decomposition oxygen rate profiles when the beads were used as electrocatalytic anodes, respectively.
FIG. 8 is Fe prepared in example 33O4@ hemoglobin core-shell structure material and superparamagnetic nano Fe3O4H in the reaction system when the microbeads are respectively used as electrocatalytic anodes2O2A generation situation detection map of (1).
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions are provided only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention.
Example 1 Fe3O4Preparation method of @ hemoglobin core-shell structure material
S1 with FeCl3.6H2O is taken as a raw material, 50 mL of deionized water is taken as a solvent, and a reactant FeCl3.6H2The O concentration is 0.8 mol.L-1Sodium citrate and sodium polyacrylate as surfactant, the concentration of sodium citrate is 0.05 mol.L-1Polyacrylic acid concentration of 0.5X 10-3mol·L-1Hydrothermal temperature 180oC, hydrothermal time is 20h, after the hydrothermal reaction is finished, a magnet is placed at the bottom of the container, and Fe3O4Collecting the microbeads at the bottom of the container, pouring out the reaction solution from the upper part of the container, and obtaining Fe with a diameter of about 180nm in the container3O4A microbead.
S2, preparation of step S1Fe3O4Immersing the microbeads in 10mg/mL hemoglobin water solution (pH = 7) at room temperature in superparamagnetic nano Fe3O4Self-assembling the surfaces of the microbeads for 72 hours to obtain superparamagnetic nano Fe with hemoglobin as a shell layer3O4Core-shell structure material with micro-beads as core.
FIG. 1 is Fe prepared in example 13O4A TEM image of the @ hemoglobin core-shell structure material; as shown in fig. 1, the core-shell structure is spherical; the black sphere of the inner core is superparamagnetic nano micro-bead, and the nano micro-bead is made of 20-30nm Fe3O4The nano-crystals are self-assembled; the semitransparent shell layer is a hemoglobin layer.
FIG. 2 shows superparamagnetic nano-Fe prepared in example 13O4VSM profile of beads, and Fe3O4The VSM of the hemoglobin core-shell structure material. As shown in fig. 2, superparamagnetic nano-Fe3O4The residual magnetism and coercive force of the micro-beads are low, and the micro-beads are superparamagnetic; fe3O4@ hemoglobin core-shell structure material with saturation magnetization lower than that of superparamagnetic nano Fe3O4The microsphere is wrapped by the hemoglobin shell layer, so that the residual magnetism and the coercive force are low, and the microsphere is superparamagnetic, so that the core-shell structure material is easy to magnetically separate.
Performance test of water decomposition and oxygen evolution
Fe obtained in this example3O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the performance of decomposing water and generating oxygen is tested; as contrast, superparamagnetic nano Fe3O4The microbeads are used as electrocatalytic anodes, and the performance of decomposing water and generating oxygen is tested. The test method is as follows:
introducing argon into a KOH solution with the pH value of 13 of 0.1mol/L until the KOH solution is saturated, and testing a water decomposition oxygen analysis linear voltammetry curve with the core-shell structure material as an electrocatalytic anode, wherein the scanning rate of the linear voltammetry curve is 100 mV/s; for comparison, superparamagnetic nano Fe3O4The water decomposition analysis oxygen linear sweep voltammetry of the bead as an electrocatalytic anode, the test results are shown in fig. 3.
From FIG. 3, Fe can be seen3O4The initial oxygen evolution potential of the material with the @ hemoglobin core-shell structure is 1.67V, and the superparamagnetic nano Fe3O4The overpotential of oxygen evolution of the micro-beads is 1.80V, and the initial oxygen evolution potential is reduced by 130 mV; the oxygen evolution reaction current increased from 11.9mA to 22.6mA at 2.6V (vs RHE), an increase of about 89%.
Formation of hydrogen peroxide by-product
Fe obtained in this example3O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the generation condition of a hydrogen peroxide byproduct in a system is detected in the water decomposition reaction process; as contrast, superparamagnetic nano Fe3O4The microbeads are used as electrocatalytic anodes for detecting the generation condition of hydrogen peroxide byproducts in a system in the water decomposition reaction process, and the test method comprises the following steps:
na at 0.1mol/L pH 72SO4Introducing argon into the aqueous solution until the solution is saturated, carrying out constant potential test for 1 hour under the voltage of 1.8V, taking the reaction solution in the system after the test, titrating hydrogen peroxide generated in the reaction system by using 0.1 mass percent of 4,4 '-diamino-3, 3' -dimethylbiphenyl, and detecting the absorption spectrum of the titrated solution in the wavelength range of 300-600nm by using an ultraviolet-visible spectrophotometer, wherein the test result is shown in figure 4.
As can be seen from FIG. 4, the superparamagnetic nano-Fe3O4When the micro-bead is an electrocatalytic anode, a reaction liquid after the titration test shows a remarkable absorption peak in the wavelength range of 300-600nm, which indicates that superparamagnetic nano Fe is used3O4When the micro-beads are electrocatalytic anodes, hydrogen peroxide is generated in a reaction system; relatively, with Fe3O4When the @ hemoglobin core-shell structure material is used as an electrocatalytic anode, the reaction liquid after the titration test is finished has almost no absorption peak in the wavelength range of 300-600nm, which indicates that the core-shell structure material can effectively inhibit the formation of hydrogen peroxide byproducts in the system when used as the electrocatalytic anode.
Example 2 Fe3O4Preparation method of @ hemoglobin core-shell structure material
S1 with FeCl3.6H2O is taken as a raw material, 50 mL of deionized water is taken as a solvent, and a reactant FeCl3.6H2The concentration of O is 0.8 mol.L < -1 >, and the concentration of sodium citrate is 0.05 mol.L-1Polyacrylic acid concentration of 0.5X 10-3mol·L-1Hydrothermal temperature 180oC, hydrothermal time is 24 hours, after the hydrothermal reaction is finished, a magnet is placed at the bottom of the container, Fe3O4 microbeads are gathered at the bottom of the container, the reaction liquid at the upper part of the container is poured out, and the prepared Fe is obtained in the container3O4A microbead.
S2, mixing the Fe prepared in the step S13O4Immersing the microbeads in 10mg/mL hemoglobin water solution (pH = 7) at room temperature in superparamagnetic nano Fe3O4Self-assembling the surfaces of the microbeads for 24 hours to obtain nano Fe with hemoglobin as a shell and superparamagnetism3O4Core-shell structure material with micro-beads as core.
Performance test of water decomposition and oxygen evolution
Fe obtained in example 23O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the performance of decomposing water and generating oxygen is tested; as contrast, superparamagnetic nano Fe3O4The microbeads are used as electrocatalytic anodes, and the performance of decomposing water and generating oxygen is tested. The test method is as follows:
introducing argon into a KOH solution with the pH value of 13 of 0.1mol/L until the KOH solution is saturated, and testing a water decomposition oxygen analysis linear voltammetry curve with the core-shell structure material as an electrocatalytic anode, wherein the scanning rate of the linear voltammetry curve is 100 mV/s; for comparison, superparamagnetic nano Fe3O4The water-resolved oxygen linear sweep voltammetry of the beads as an electrocatalytic anode showed the test results shown in fig. 5.
From FIG. 5, it can be seen that Fe3O4The initial oxygen evolution potential of the material with the @ hemoglobin core-shell structure is 1.74V, and the superparamagnetic nano Fe3O4The overpotential of oxygen evolution of the micro-beads is 1.80V, and the initial oxygen evolution potential is reduced by 60 mV; the oxygen evolution reaction current increased from 11.9mA to 24.1mA at 2.6V (vs RHE), an increase of about 102%.
Formation of hydrogen peroxide by-product
Fe obtained in example 23O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the generation condition of a hydrogen peroxide byproduct in a system is detected in the water decomposition reaction process; as contrast, superparamagnetic nano Fe3O4The microbeads are used as electrocatalytic anodes for detecting the generation condition of hydrogen peroxide byproducts in a system in the water decomposition reaction process, and the test method comprises the following steps:
na at 0.1mol/L pH 72SO4Introducing argon into the aqueous solution until the solution is saturated, carrying out constant potential test for 1 hour under the voltage of 1.8V, taking the reaction solution in the system after the test, titrating hydrogen peroxide generated in the reaction system by using 0.1% by mass of 4,4 '-diamino-3, 3' -dimethylbiphenyl, and detecting the absorption spectrum of the titrated solution in the wavelength range of 300-600nm by using an ultraviolet-visible spectrophotometer, wherein the test result is shown in figure 6. As can be seen from FIG. 6, the superparamagnetic nano-Fe3O4When the microbeads are electrocatalytic anodes, significant absorption peaks appear in the reaction liquid after titration test within the wavelength range of 300-600nm, which indicates that hydrogen peroxide is generated in the reaction system when the superparamagnetic nano microbeads are electrocatalytic anodes; relatively, with Fe3O4When the @ hemoglobin core-shell structure material is used as an electrocatalytic anode, the absorption peak of the reaction liquid after the titration test in the wavelength range of 300-600nm is obviously reduced, which indicates that the core-shell structure material can effectively inhibit the formation of hydrogen peroxide byproducts in the system when used as the electrocatalytic anode.
Example 3 Fe3O4Preparation method of @ hemoglobin core-shell structure material
S1 with FeCl3.6H2O is taken as a raw material, 50 mL of deionized water is taken as a solvent, and a reactant FeCl3.6H2The concentration of O is 0.8 mol.L < -1 >, and the concentration of sodium citrate is 0.05 mol.L-1Polyacrylic acid concentration of 0.5X 10-3mol·L-1Hydrothermal temperature 180oC, hydrothermal time is 24 hours, after the hydrothermal reaction is finished, a magnet is placed at the bottom of the container, and Fe3O4Collecting the microbeads at the bottom of the container, pouring out the reaction liquid at the upper part of the container, and obtaining Fe in the container3O4A microbead.
S2, mixing the Fe prepared in the step S13O4Immersing the microbeads in 10mg/mL hemoglobin water solution (pH = 7) at room temperature in superparamagnetic nano Fe3O4Self-assembling the surfaces of the microbeads for 48 hours to obtain nano Fe with hemoglobin as a shell and superparamagnetism3O4Core-shell structure material with micro-beads as core.
Performance test of water decomposition and oxygen evolution
Fe obtained in example 33O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the performance of decomposing water and generating oxygen is tested; as contrast, superparamagnetic nano Fe3O4The microbeads are used as electrocatalytic anodes, and the performance of decomposing water and generating oxygen is tested. The test method is as follows:
introducing argon into a KOH solution with the pH value of 13 of 0.1mol/L until the KOH solution is saturated, and testing a water decomposition oxygen analysis linear voltammetry curve with the core-shell structure material as an electrocatalytic anode, wherein the scanning rate of the linear voltammetry curve is 100 mV/s; for comparison, superparamagnetic nano Fe3O4The water-resolved oxygen linear sweep voltammetry of the beads as an electrocatalytic anode showed the test results shown in fig. 7.
Fe can be seen from FIG. 73O4The initial oxygen evolution potential of the material with the @ hemoglobin core-shell structure is 1.70V, and the superparamagnetic nano Fe3O4The oxygen evolution overpotential of the micro-beads is 1.80V, and the initial oxygen evolution potential is reduced by 100 mV; the oxygen evolution reaction current increased from 11.9mA to 23.8mA at 2.6V (vs RHE), an increase of about 100%.
Formation of hydrogen peroxide by-product
Fe obtained in this example3O4The @ hemoglobin core-shell structure material is used as an electrocatalytic anode, and the generation condition of a hydrogen peroxide byproduct in a system is detected in the water decomposition reaction process; as contrast, superparamagnetic nano Fe3O4Microbead as electrocatalytic anodeIn the water decomposition reaction process, the generation condition of the hydrogen peroxide byproduct in the system is detected, and the test method comprises the following steps:
na at 0.1mol/L pH 72SO4Introducing argon into the aqueous solution until the solution is saturated, carrying out constant potential test for 1 hour under the voltage of 1.8V, taking the reaction solution in the system after the test, titrating the hydrogen peroxide generated in the reaction system by using 0.1 mass percent of 4,4 '-diamino-3, 3' -dimethylbiphenyl, and detecting the absorption spectrum of the titrated solution in the wavelength range of 300-600nm by using an ultraviolet-visible spectrophotometer, wherein the test result of the absorption spectrum is shown in figure 8.
As can be seen from FIG. 8, superparamagnetic nano-Fe3O4When the micro-bead is an electrocatalytic anode, a reaction liquid after the titration test shows a remarkable absorption peak in the wavelength range of 300-600nm, which indicates that superparamagnetic nano Fe is used3O4When the micro-beads are electrocatalytic anodes, hydrogen peroxide is generated in a reaction system; relatively, with Fe3O4When the @ hemoglobin core-shell structure material is used as an electrocatalytic anode, the absorption peak of the electrolyte after the titration test in the wavelength range of 300-600nm is obviously reduced, which indicates that the core-shell structure material can effectively inhibit the formation of hydrogen peroxide byproducts in the system when used as the electrocatalytic anode.
The above description is only a preferred embodiment of the present invention, and all equivalent changes or modifications of the structure, characteristics and principles described in the present invention are included in the scope of the present invention.
Claims (8)
1. Fe3O4The material with the structure of @ hemoglobin core-shell is characterized in that the inner core is nano Fe3O4The shell layer of the micro-bead is hemoglobin.
2. Core-shell structured material according to claim 1, wherein the nano-Fe is3O4The micro-beads are made of 20-30nm Fe3O4The diameter of the micro-bead is 150-250nm formed by self-assembling nano-crystal, and the nano-Fe3O4The micro-bead is decorated with hydrophilic groups.
3. The core-shell structured material according to claim 2, wherein the hydrophilic groups are hydroxyl groups and carboxyl groups.
4. Core-shell structured material according to claim 1, wherein the nano-Fe is3O4The micro-beads are superparamagnetic.
5. Fe3O4The preparation method of the @ hemoglobin core-shell structure material is characterized by comprising the following steps of sequentially connecting:
s1, synthesizing superparamagnetic nano Fe3O4Microbeads and superparamagnetic nano-Fe3O4Grafting hydrophilic functional groups on the surfaces of the microbeads;
s2, mixing the superparamagnetic nano Fe3O4Immersing the microbeads in the solution of hemoglobin, and self-assembling to obtain superparamagnetic nano Fe3O4Assembling a hemoglobin shell layer on the surface of the microbead to obtain Fe3O4@ hemoglobin core-shell structural material.
6. The method as claimed in claim 5, wherein the step S1 is carried out by hydrothermal synthesis one-pot method to obtain superparamagnetic nano Fe3O4The micro-beads specifically comprise: deionized water as solvent and FeCl3As Fe source, NaOH is used for regulating alkalinity, citric acid and polyacrylic acid are used as surfactants, and hydrothermal temperature is 180 DEGoC-200oAnd C, reacting for 20-24h in the container.
7. The preparation method according to claim 5, wherein the concentration of the hemoglobin solution in the step S2 is 10mg/mL, and the assembly time is 24-72 h.
8. Fe as claimed in any one of claims 1 to 43O4The application of the @ hemoglobin core-shell structure material as an electrocatalytic material for water decomposition to produce oxygen and simultaneously inhibiting the generation of hydrogen peroxide in a system.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502858A (en) * | 2011-10-24 | 2012-06-20 | 中国科学院理化技术研究所 | Preparation method of polyacrylic-acid modified water-soluble ferrite nano-cluster |
| CN104436199A (en) * | 2014-08-16 | 2015-03-25 | 金陵科技学院 | Preparation method of porous ferroferric oxide composite nanometre microspheres efficiently loaded with pharmorubicin |
| CN106590817A (en) * | 2016-11-04 | 2017-04-26 | 金陵科技学院 | Lubricating oil containing oleic acid-modified superparamagnetic nanometer hollow beads and preparation method thereof |
| CN107941873A (en) * | 2017-08-04 | 2018-04-20 | 海南师范大学 | A kind of preparation and application of the hemoglobin electrochemical sensor based on nanocomposite |
| CN108653732A (en) * | 2018-04-24 | 2018-10-16 | 江苏大学 | PH response type ferriferrous oxide nano grains and the preparation method and application thereof |
-
2021
- 2021-01-07 CN CN202110018770.9A patent/CN112663089B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502858A (en) * | 2011-10-24 | 2012-06-20 | 中国科学院理化技术研究所 | Preparation method of polyacrylic-acid modified water-soluble ferrite nano-cluster |
| CN104436199A (en) * | 2014-08-16 | 2015-03-25 | 金陵科技学院 | Preparation method of porous ferroferric oxide composite nanometre microspheres efficiently loaded with pharmorubicin |
| CN106590817A (en) * | 2016-11-04 | 2017-04-26 | 金陵科技学院 | Lubricating oil containing oleic acid-modified superparamagnetic nanometer hollow beads and preparation method thereof |
| CN107941873A (en) * | 2017-08-04 | 2018-04-20 | 海南师范大学 | A kind of preparation and application of the hemoglobin electrochemical sensor based on nanocomposite |
| CN108653732A (en) * | 2018-04-24 | 2018-10-16 | 江苏大学 | PH response type ferriferrous oxide nano grains and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| NA ZHENG ET AL: "Direct electrochemistry and electrocatalysis of hemoglobin immobilized in a magnetic nanoparticles-chitosan film", 《CONTENTS LISTS AVAILABLE AT SCIENCEDIRECT》, vol. 79, 12 May 2009 (2009-05-12), pages 780 * |
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