CN115945195A - Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof - Google Patents
Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof Download PDFInfo
- Publication number
- CN115945195A CN115945195A CN202210844384.XA CN202210844384A CN115945195A CN 115945195 A CN115945195 A CN 115945195A CN 202210844384 A CN202210844384 A CN 202210844384A CN 115945195 A CN115945195 A CN 115945195A
- Authority
- CN
- China
- Prior art keywords
- nanoenzyme
- diatomic
- hydrogen peroxide
- iron
- mixture
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- -1 5-cyclopentadienyl Chemical group 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- AXYSDZQJEIAXBL-UHFFFAOYSA-N bis(oxomethylidene)iron Chemical class O=C=[Fe]=C=O AXYSDZQJEIAXBL-UHFFFAOYSA-N 0.000 claims description 2
- YMBYDCYFUDVJSS-UHFFFAOYSA-N carbon monoxide;cyclopentane;iron Chemical class [Fe].[O+]#[C-].[O+]#[C-].[CH]1[CH][CH][CH][CH]1 YMBYDCYFUDVJSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims 1
- 102000016938 Catalase Human genes 0.000 abstract description 15
- 108010053835 Catalase Proteins 0.000 abstract description 15
- 102000004190 Enzymes Human genes 0.000 abstract description 10
- 108090000790 Enzymes Proteins 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000004075 alteration Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- RMLYXMMBIZLGAQ-UHFFFAOYSA-N (-)-monatin Natural products C1=CC=C2C(CC(O)(CC(N)C(O)=O)C(O)=O)=CNC2=C1 RMLYXMMBIZLGAQ-UHFFFAOYSA-N 0.000 description 3
- RMLYXMMBIZLGAQ-HZMBPMFUSA-N (2s,4s)-4-amino-2-hydroxy-2-(1h-indol-3-ylmethyl)pentanedioic acid Chemical compound C1=CC=C2C(C[C@](O)(C[C@H](N)C(O)=O)C(O)=O)=CNC2=C1 RMLYXMMBIZLGAQ-HZMBPMFUSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and a preparation method thereof; aims to provide diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and a preparation method thereof, and opens up a path for reasonably designing an enzyme substitute with high activity, high selectivity and high stability for certain harsh reactions and replacing catalase in industrial application; the technical scheme comprises the following steps: 1) Grinding a certain amount of bimetallic iron ligand, 2-methylimidazole and zinc compound uniformly; 2) Transferring the mixture into an agate ball milling tank, adding a small amount of ammonium salt and a solvent, quickly and uniformly mixing, and then carrying out high-speed ball milling for a certain time; 3) Finally, washing, drying and calcining by using a small amount of solvent to obtain diatomic nanoenzyme; belongs to the technical field of material science and engineering.
Description
Technical Field
The invention belongs to the technical field of material science and engineering, and particularly relates to diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide.
Background
Catalase is an enzyme that accelerates the disproportionation of hydrogen peroxide into water and oxygen, and has the characteristics of low toxicity, high selectivity and ultrahigh catalytic activity, and is widely used in textile industry, food industry, environmental management and biomedicine. However, catalase is easily decreased by pH, temperature and substrate concentration. In addition, the practical application of catalase is greatly hindered by the problems of high manufacturing difficulty, low stability, difficult storage, high cost and the like. Therefore, there is a need to develop an artificial enzyme having high activity and solving the limitation of catalase. The nano enzyme is an inorganic nano material, has basic enzyme-like characteristics, and can be used for overcoming the limitations of high cost, difficult storage, low stability and difficult manufacture of biological enzymes. Unfortunately, despite significant advances in nanoenzyme development, due to the diversity of surface configurations and crystalline nanostructures, selectivity and activity are often much lower than native enzymes.
In recent years, M-N with catalytic centers similar to those of natural metalloenzymes which have been highly evolved x Monatomic catalysts of (M: transition metal) sites have shown great potential as substitutes for natural metalloenzymes. Recently, monatin nanoenzymes like catalase show excellent performance in the healthcare-related field. Unfortunately, industrial applications must have the requirements of higher activity, higher stability, oxidation resistance, acid and alkali resistance, recyclability, and ease of mass production compared to medical-related application requirements, so there are few examples of industrial applications of hydrogen peroxide monatomic nanoenzymes at present.
Notably, there is a long range of interaction between adjacent monatomic sites in monatomic catalysts, and due to synergistic effects, paired diatomic catalysis is generally more effective than monatomic catalysts where the atoms are individually isolated. Therefore, the production of diatomic nanoenzymes, which is low cost, easy to synthesize, scalable and environmentally friendly, has great potential to replace catalase in industrial applications.
Disclosure of Invention
The monatomic nanoenzyme has M-N similarity with highly evolved natural metalloenzyme x The catalytic center of the site, shows highly similar properties to biological enzymes. Diatomic nanoenzymes, however, typically exhibit synergy between adjacent atomsHas more excellent catalytic effect than monoatomic nano-enzyme and even biological enzyme, and has great potential to replace the industrial application of the biological enzyme. The invention aims to provide diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and a preparation method thereof, and opens up a path for reasonably designing enzyme substitutes with high activity, high selectivity and high stability to be used for certain harsh reactions and replacing catalase in industrial application.
Therefore, the technical scheme provided by the invention is as follows:
a diatomic nanoenzyme for efficiently decomposing hydrogen peroxide comprises the following steps:
1) The bimetallic iron ligand, 2-methylimidazole and zinc compound are mixed according to the mass ratio: 0.01-0.02:1-3:0.5-1, grinding the uniformly mixed mixture;
2) Transferring the mixture prepared in the step 1) into an agate ball-milling tank, adding ammonium salt accounting for 0.3-2% of the mass of the mixture, quickly and uniformly mixing the mixture with a solvent, and then carrying out high-speed ball-milling for 0.5-24 hours;
3) Finally, washing, drying and calcining for 0.5-24 hours by using a small amount of solvent to obtain the diatomic nanoenzyme.
Furthermore, the diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and the preparation method thereof are characterized in that the bimetallic iron ligand is one or a mixture of M-tetraphenylporphine-M-iron oxide dimer, ferrocenyl ferrocene dimer, cyclopentadienyl dicarbonyl iron dimer and (eta 5-cyclopentadienyl) dicarbonyl iron dimer.
Furthermore, the diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and the preparation method thereof are characterized in that the zinc compound is one or a mixture of zinc chloride, zinc nitrate, zinc oxide, zinc oxalate and zinc sulfate.
Further, the diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and the preparation method thereof are characterized in that the ammonium salt is one or a combination of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium iodide.
Further, the solvent is one or a combination of several of methanol, ethanol, N-dimethylformamide, petroleum ether, isopropanol and acetone.
Further, the diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and the preparation method thereof are characterized in that the rotating speed of the high-speed ball milling for a certain time is 300-800 r/min.
Further, the diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and the preparation method thereof are characterized in that the calcining conditions are 100-1200 ℃, the heating rate is 1-30 ℃/min, the heat preservation time is 0.1-20 hours, and the calcining atmosphere is inert.
Drawings
FIG. 1 is a schematic view of a spherical aberration electron microscope of the diatomic iron nanoenzyme prepared in example 1;
FIG. 2 is a spherical aberration electron microscope image of the monatomic iron nanoenzyme prepared in comparative example 1;
FIG. 3 is a graph showing the effect of the monatomic iron nanoenzyme, the diatomic iron nanoenzyme and the catalase described in comparative example 1 and examples 1-4 on the decomposition of hydrogen peroxide;
fig. 4 is a comparison of the hydrogen peroxide decomposition capacities of the diatomic iron nanoenzyme, the monoatomic iron nanoenzyme, and the catalase in comparative example 1 and example 1 at pH =3 (under strong acid) and pH =11 (under strong base);
FIG. 5 is a diagram of a kilogram-scale diatomic iron nanoenzyme precursor prepared in example 2;
FIG. 6 is a spherical aberration electron microscope image of kilogram-scale diatomic iron nanoenzymes prepared in example 2.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the scope shown in the examples.
Example 1
Zinc oxide (0.5 g), 2-methylimidazole (2 g), and cyclopentadienyl iron dicarbonyl dimer (0.01 g) were mixed in a mortar for 3 minutes until homogeneous. Then the mixture is poured into an agate ball milling tank, ammonium nitrate (15 mg) and N, N-dimethylformamide (450 uL) are added and mixed evenly, and after adding agate ball milling beads and covering a cover, the mixture is placed into a ball mill to be milled for 2 hours at the rotating speed of 500 rpm. After the ball milling was completed, the solid was poured out and simply ground into fine particles with a mortar, and centrifuged and washed three times with 3mL of methanol per gram of the solid, and then placed in an oven to be dried. Finally, the dried solid is simply ground into fine particles and placed in a tube furnace to be heated to 900 ℃ at the speed of 5 ℃/min for 3 hours in the flowing atmosphere of nitrogen. And naturally cooling to room temperature to obtain the diatomic iron nanoenzyme. FIG. 1 is a spherical aberration electron microscope image of the prepared diatomic iron nanoenzyme, from which it can be seen that iron atoms are dispersed in a pair-wise state.
Example 2
Zinc oxide (50 g), 2-methylimidazole (200 g), and cyclopentadienyl iron dicarbonyl dimer (1 g) were mixed in a mortar for 3 minutes until homogeneous. Then, the mixture was poured into an agate jar, ammonium nitrate (1.5 g) and N, N-dimethylformamide (45 mL) were added and mixed, and the mixture was subjected to ball milling with agate beads covered with a lid and placed in a ball mill at 500rpm for 2 hours. After the ball milling was completed, the solid was poured out and simply ground into fine particles with a mortar, and centrifuged and washed three times with 3mL of methanol per gram of the solid, and then placed in an oven to be dried. And obtaining kilogram-level diatomic iron nanoenzyme precursor as shown in figure 5. Finally, the dried solid is simply ground into fine particles and placed in a tube furnace to be heated to 900 ℃ at the speed of 5 ℃/min for 3 hours in the flowing atmosphere of nitrogen. After natural cooling to room temperature, kilogram-level diatomic iron nanoenzyme can be obtained. As shown in FIG. 6 kg diatomic iron nanoenzyme spherical aberration electron microscope image, it was found that the iron atoms were distributed in pairs. The method is easy to be produced in an enlarged way and has huge industrial application prospect.
Example 3
Zinc nitrate (0.5 g), 2-methylimidazole (1 g), and ferrocene carbyl ferrocene dimer (0.01 g) were mixed in a mortar for 3 minutes to homogeneity. Then, the mixture was poured into an agate jar, ammonium chloride (15 mg) and methanol (450 uL) were added and mixed, and after adding agate beads and covering the jar with a lid, the mixture was placed in a ball mill and ball-milled at 400rpm for 4 hours. After the ball milling was completed, the solid was poured out and simply ground into fine particles with a mortar, and centrifuged and washed three times with 5mL of methanol per gram of the solid, and then placed in an oven to be dried. Finally, the dried solid is simply ground into fine particles, and the fine particles are placed in a tube furnace to be heated to 900 ℃ at the speed of 10 ℃/min and kept for 5 hours in the flowing atmosphere of argon. And naturally cooling to room temperature to obtain the diatomic iron nanoenzyme.
Example 4
Zinc carbonate (1 g), 2-methylimidazole (3 g), and M-tetraphenylporphyrin-M-iron oxide dimer (0.02 g) were mixed in a mortar for 5 minutes to homogeneity. Then, it was poured into an agate jar, ammonium carbonate (30 mg) and hexanol (900 uL) were added and mixed, and after adding agate beads and covering the jar with a lid, the mixture was ball-milled in a ball mill at 600rpm for 2 hours. After the ball milling was completed, the solid was poured out and simply ground into fine particles with a mortar, and centrifuged and washed three times with 5mL of methanol per gram of the solid, and then placed in an oven to be dried. Finally, the dried solid is simply ground into fine particles and placed in a tube furnace to be heated to 900 ℃ at the speed of 2 ℃/min for 2 hours in the flowing atmosphere of argon. And naturally cooling to room temperature to obtain the diatomic iron nanoenzyme.
Comparative example 1
Zinc oxide (0.5 g), 2-methylimidazole (2 g), and iron acetylacetonate (0.02 g) were mixed in a mortar for 3 minutes until homogeneous. Then the mixture is poured into an agate ball milling tank, ammonium nitrate (15 mg) and N, N-dimethylformamide (450 uL) are added and mixed evenly, and after adding agate ball milling beads and covering a cover, the mixture is placed into a ball mill to be milled for 2 hours at the rotating speed of 500 rpm. After the ball milling was completed, the solid was poured out and simply ground into fine particles with a mortar, and centrifuged and washed three times with 3mL of methanol per gram of the solid, and then placed in an oven to be dried. Finally, the dried solid is simply ground into fine particles and placed in a tube furnace to be heated to 900 ℃ at the speed of 5 ℃/min for 3 hours in the flowing atmosphere of nitrogen. And naturally cooling to room temperature to obtain the monatomic iron nanoenzyme. FIG. 2 is a spherical aberration electron micrograph of the prepared monatomic iron nanoenzyme, from which it can be seen that iron atoms are dispersed in the form of isolated single atoms, in sharp contrast to the paired appearance of iron atoms in example 1.
Diatomic iron nanoenzymes prepared in examples 1-4, monatomic iron nanoenzyme prepared in comparative example 1, and catalase purchased were used for hydrogen peroxide decomposition to compare their catalytic performance, and as shown in fig. 3, 3 parts of 10mL hydrogen peroxide with a concentration of 10% were taken, 5mg of diatomic iron nanoenzyme, monatomic iron nanoenzyme, and catalase purchased were added, respectively, and the volume of oxygen generated and the decomposition rate were determined by a drainage method and timing. Comparison shows that when the same mass of catalyst is added, the catalytic activity of the diatomic iron nanoenzyme in all the examples is obviously superior to that of the monatomic iron nanoenzyme and catalase. In addition, the catalytic activities of the diatomic iron nanoenzymes prepared in the examples 1 and 2 are close, which shows that the catalytic effect is not affected by the kilogram-level scale-up production in the example 2, and the method is proved to be easy to scale-up production. As shown in fig. 4, in order to compare the hydrogen peroxide decomposition capacities at pH =3 (strong acid) and pH =11 (strong base) of the diatomic iron nanoenzyme prepared in example 1 and the monatin iron nanoenzyme and catalase prepared in comparative example 1, it was found that the hydrogen peroxide decomposition capacity of catalase is sharply decreased under the conditions of strong acid and strong base, the hydrogen peroxide decomposition capacity of monatin nanoenzyme is also greatly decreased under the conditions of strong acid and strong base, and the hydrogen peroxide decomposition capacity of diatomic nanoenzyme is almost unchanged, which sufficiently demonstrates the high efficiency and superiority of diatomic nanoenzyme.
Claims (7)
1. A diatomic nanoenzyme for efficiently decomposing hydrogen peroxide is characterized by comprising the following steps:
1) The bimetallic iron ligand, 2-methylimidazole and zinc compound are mixed according to the mass ratio: 0.01-0.02:1-3:0.5-1 grinding the uniformly mixed mixture;
2) Transferring the mixture prepared in the step 1) into an agate ball milling tank, adding ammonium salt with the mass of 0.3-2% of that of the mixture, quickly and uniformly mixing the mixture with a solvent, and then carrying out high-speed ball milling for 0.5-24 hours;
3) And finally, washing by using a solvent, drying and calcining to obtain the diatomic nanoenzyme.
2. The diatomic nanoenzyme for efficient decomposition of hydrogen peroxide and its preparation method of claim 1, wherein said bimetallic iron ligand is one or a mixture of M-tetraphenylporphin-M-iron oxide dimer, dicylocene dimer, cyclopentadienyl dicarbonyl iron dimer and (η 5-cyclopentadienyl) dicarbonyl iron dimer.
3. The diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and the preparation method thereof as claimed in claim 1, wherein the zinc compound is one or a mixture of zinc chloride, zinc nitrate, zinc oxide, zinc oxalate and zinc sulfate.
4. The diatomic nanoenzyme for decomposing hydrogen peroxide with high efficiency and the preparation method thereof as claimed in claim 1, wherein said ammonium salt is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium iodide.
5. The diatomic nanoenzyme for efficiently decomposing hydrogen peroxide and the preparation method thereof according to claim 1, wherein the solvent is one or a combination of methanol, ethanol, N-dimethylformamide, petroleum ether, isopropanol and acetone.
6. The diatomic nanoenzyme for efficiently decomposing hydrogen peroxide as recited in claim 1, wherein the high speed ball milling is performed at a speed of 300-800 rpm.
7. The diatomic nanoenzyme for efficiently decomposing hydrogen peroxide as claimed in claim 1, wherein the calcination conditions are 100-1200 ℃, the temperature rise rate is 1-30 ℃/min, the holding time is 0.1-20 hours, and the calcination atmosphere is inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210844384.XA CN115945195A (en) | 2022-07-15 | 2022-07-15 | Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210844384.XA CN115945195A (en) | 2022-07-15 | 2022-07-15 | Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115945195A true CN115945195A (en) | 2023-04-11 |
Family
ID=87297270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210844384.XA Pending CN115945195A (en) | 2022-07-15 | 2022-07-15 | Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115945195A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116510777A (en) * | 2023-07-04 | 2023-08-01 | 江苏省农业科学院 | Plant microenvironment response type diatomic nanoenzyme and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999020678A1 (en) * | 1997-10-20 | 1999-04-29 | Basf Aktiengesellschaft | Method for producing carbon monoxide copolymers by heterogeneous catalysis |
| CN110586102A (en) * | 2019-08-21 | 2019-12-20 | 中山大学 | Preparation method of heteroatom-like catalyst |
| CN112221530A (en) * | 2020-11-13 | 2021-01-15 | 青岛科技大学 | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst |
| CN113270596A (en) * | 2021-04-16 | 2021-08-17 | 西安理工大学 | Preparation method of catalyst with Fe @ Co diatomic active sites |
-
2022
- 2022-07-15 CN CN202210844384.XA patent/CN115945195A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999020678A1 (en) * | 1997-10-20 | 1999-04-29 | Basf Aktiengesellschaft | Method for producing carbon monoxide copolymers by heterogeneous catalysis |
| CN110586102A (en) * | 2019-08-21 | 2019-12-20 | 中山大学 | Preparation method of heteroatom-like catalyst |
| CN112221530A (en) * | 2020-11-13 | 2021-01-15 | 青岛科技大学 | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst |
| CN113270596A (en) * | 2021-04-16 | 2021-08-17 | 西安理工大学 | Preparation method of catalyst with Fe @ Co diatomic active sites |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116510777A (en) * | 2023-07-04 | 2023-08-01 | 江苏省农业科学院 | Plant microenvironment response type diatomic nanoenzyme and preparation method and application thereof |
| CN116510777B (en) * | 2023-07-04 | 2023-09-12 | 江苏省农业科学院 | Plant microenvironment response type diatomic nanoenzyme and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106944057A (en) | A kind of preparation method of monoatomic metal carbon composite catalytic agent for electrocatalytic reaction | |
| CN108660473B (en) | A kind of electrolytic seawater catalyst for preparing hydrogen and its synthetic method based on MXene Yu transition metal carbide composite nanostructure | |
| CN112973754A (en) | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material | |
| CN112916009A (en) | Preparation method of biomass-derived porous carbon-limited-domain monoatomic metal composite material | |
| CN107308933A (en) | A kind of application of high dispersive noble metal catalyst in electrochemistry evolving hydrogen reaction | |
| CN109675595B (en) | Tungsten carbide/porous carbon composite material, preparation method thereof and application thereof in electrochemical hydrogen production | |
| CN110882725B (en) | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof | |
| CN110947388B (en) | Graphene aerogel supported nickel catalyst and preparation method and application thereof | |
| CN101417243B (en) | High specific surface area tungsten carbide microspheres and load type catalyst and their preparation methods | |
| CN108479834A (en) | A kind of fischer-tropsch synthetic catalyst and preparation method thereof | |
| CN111375432A (en) | Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof | |
| CN115945195A (en) | Diatomic nanoenzyme capable of efficiently decomposing hydrogen peroxide and preparation method thereof | |
| CN108011110A (en) | A kind of transition metal of high-specific surface area-nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application | |
| KR102188587B1 (en) | Method of synthesizing transition metal single-atom catalysts | |
| CN109331860A (en) | A kind of low platinum alloy compound nanometer photocatalyst and its preparation method and application for air cleaning | |
| CN110026213B (en) | Formic acid hydrogen production catalyst and preparation method and application thereof | |
| CN110937628A (en) | TiO with oxygen vacancy2Method for producing a material | |
| CN114887641A (en) | Single-atom catalyst with nitrogen-doped lignin carbon dots as carrier and application thereof | |
| CN108654660B (en) | Vanadium carbide/carbon nanotube composite material, preparation method and application thereof in aspect of hydrogen production by water splitting | |
| Xing et al. | Anchoring Bi2S3 quantum dots on flower-like TiO2 nanostructures to boost photoredox coupling of H2 evolution and oxidative organic transformation | |
| CN114471658A (en) | Temperature-controlled bifunctional atomic-level dispersed metal g-C3N4Method for preparing photocatalyst | |
| KR101932575B1 (en) | SHAPE-CONTROLLED Pt NANOCUBES AND METHOD OF MANUFACTURE THEREOF | |
| CN107999081B (en) | Carbon-coated structure nano iron-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
| CN113262807A (en) | Directionally anchoring Pt monoatomic atoms to N-AC (nitrogen-alternating current) through limited-area interface1/N-AC2Method for compounding materials | |
| CN114160155A (en) | Nanoscale Co3O4Preparation method and application of @ Pt |
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 |