CN113582352B - Application of immobilized laccase in degradation of organic phenol - Google Patents
Application of immobilized laccase in degradation of organic phenol Download PDFInfo
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- CN113582352B CN113582352B CN202110861091.8A CN202110861091A CN113582352B CN 113582352 B CN113582352 B CN 113582352B CN 202110861091 A CN202110861091 A CN 202110861091A CN 113582352 B CN113582352 B CN 113582352B
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- 108010029541 Laccase Proteins 0.000 title claims description 45
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 21
- 230000015556 catabolic process Effects 0.000 title claims description 16
- 238000006731 degradation reaction Methods 0.000 title claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 30
- 150000003624 transition metals Chemical class 0.000 claims abstract description 30
- 230000005415 magnetization Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 150000003839 salts Chemical class 0.000 claims description 44
- 239000002131 composite material Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 230000000593 degrading effect Effects 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000012258 culturing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000002135 nanosheet Substances 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 238000003756 stirring Methods 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 18
- 108010093096 Immobilized Enzymes Proteins 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
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- 239000007864 aqueous solution Substances 0.000 description 7
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- 230000007935 neutral effect Effects 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002444 silanisation Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000000872 buffer Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000008176 lyophilized powder Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 241000222355 Trametes versicolor Species 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/0004—Oxidoreductases (1.)
- C12N9/0055—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
- C12N9/0057—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3)
- C12N9/0061—Laccase (1.10.3.2)
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- C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
- C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
- C12Y110/03002—Laccase (1.10.3.2)
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a modified magnetic transition metal carbonitride and a preparation method and application thereof, wherein the component of the modified magnetic transition metal carbonitride is MXene @ LDH @ Fe 3 O 4 ‑NH 2 (ii) a The weight percentage content is as follows: MXene 20-55%, LDH 15-50%, fe 3 O 4 20％‑34％，NH 2 0.1% -10%; the saturation magnetization is 18-28emu/g. LDH grows in situ on the single-layer two-dimensional nanosheet MXene to form a 2D/2D heterogeneous hybrid structure, so that the interlayer spacing can be increased, the charge transfer can be accelerated, and the single-layer two-dimensional nanosheet MXene has a larger comparative area and can expose more active sites.
Description
Technical Field
The invention belongs to the technical field of functional materials and environmental protection, and particularly relates to a preparation method and application of modified magnetic transition metal carbonitride.
Background
With the rapid development of global economy, more and more phenolic compounds are widely applied to chemical production. During the synthesis, extraction and use of the phenolic compounds, the phenolic compounds are inevitably released into the environment to cause pollution. The organic phenol in the environment can not only directly harm the health of human bodies, but also can affect the immune system, the nervous system, the endocrine system and the like of human bodies through the enrichment of food chains, so that the establishment of an efficient method for degrading the organic phenol pollutants is slow.
Laccase as an environment-friendly copper-containing polyphenol oxidase is widely derived from plants, animals and microorganisms, has strong redox capacity and low requirement on specificity of a substrate, and is widely applied to the fields of food processing, drug synthesis, printing and dyeing industry, biological detection and the like. Under the condition of oxygen, laccase transfers electrons through the center of a trinuclear copper cluster formed by 4 copper ions in a synergistic manner, electrons on hydroxyl groups of phenolic compounds are removed, free radicals are formed, meanwhile, one molecule of oxygen is reduced into water, the catalysis efficiency is high, a non-toxic product is generated, and the laccase has the advantages of strong pH tolerance, high temperature resistance, wide substrate range and the like, and is suitable for being applied to industrial production. However, the free enzyme is sensitive to environmental conditions and is difficult to recover and reuse from the reaction solution after the reaction is completed, which not only increases the treatment cost but also hinders the commercial application of laccase. The immobilized enzyme technology is an enzyme application technology developed in the last ten years and has wide application prospects in the aspects of industrial production, chemical analysis, medicine and the like. Compared with free enzyme, the immobilized enzyme overcomes the defects of the free enzyme while keeping the characteristics of high efficiency, specificity and mild enzyme catalytic reaction, has the advantages of high storage stability, easy separation and recovery, repeated use, continuous and controllable operation, simple and convenient process and the like, and can take high-efficiency catalysis and low cost into consideration in industrial production.
MXene is a novel two-dimensional layered transition metal carbonitride, generally prepared by selectively etching a main group element A layer from a corresponding MAX phase, and has a chemical general formula of M n+1 X n T x Wherein M represents a transition metal, X represents C, N element, T x Represents surface functional groups such as-H, -F, -OH and the like, and has the characteristics of good metal conductivity, hydrophilicity, mechanical property, adjustable surface chemical environment and the like. Double isThe layered metal hydroxide (LDH) is a layered material with brucite-like layers with positive charges and anions between charge compensation layers, and has the advantages of large specific surface area, strong chemical stability, adjustable metal components, exchangeable anions and the like. As the surface of the MXene nanosheet is rich in functional groups, the MXene nanosheet is beneficial to anchoring of metal ions and nucleation of LDH, the LDH nanosheet is vertically arranged on the surface of the MXene nanosheet to form a 2D/2D heterogeneous hybrid structure, the interlayer spacing can be increased, charge transfer is accelerated, and the MXene nanosheet has a wide application prospect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a modified magnetic transition metal carbonitride.
The technical problem to be solved by the invention is to provide a preparation method of the modified magnetic transition metal carbonitride.
The technical problem to be solved by the invention is to provide the application of the modified magnetic transition metal carbonitride.
In order to solve the first technical problem, the invention discloses a modified magnetic transition metal carbonitride, which comprises MXene @ LDH @ Fe 3 O 4 -NH 2 。
Wherein the modified magnetic transition metal carbonitride comprises the following components in percentage by mass: MXene 20-55%, LDH 15-50%, fe 3 O 4 20％-34％，NH 2 0.1% -10%; preferably, the weight percentage of the components is MXene 24%, LDH 48%, fe 3 O 4 27％，NH 2 0.37％。
Wherein the saturation magnetization of the modified magnetic transition metal carbonitride is 18-28emu/g; preferably, the saturation magnetization of the modified magnetic transition metal carbonitride is 20-26emu/g; further preferably, the saturation magnetization of the modified magnetic transition metal carbonitride is 22-24emu/g; still more preferably, the saturation magnetization of the modified magnetic transition metal carbonitride is 23.08emu/g.
In order to solve the second technical problem, the invention discloses a method for preparing the modified magnetic transition metal carbonitride, which comprises the following steps:
(1) Reacting acid, lithium fluoride and MAX to obtain MXene;
(2) Reacting MXene with double metal salt under alkaline condition to obtain MXene @ LDH composite material;
(3) Reacting MXene @ LDH composite material with iron salt under alkaline condition to obtain MXene @ LDH @ Fe 3 O 4 A composite material;
(4) Mixing MXene @ LDH @ Fe 3 O 4 And (3) reacting the composite material with a silane coupling agent to obtain the composite material.
In the step (1), the acid is hydrochloric acid; preferably, the acid is concentrated hydrochloric acid; further preferably, the acid is concentrated 10-12M hydrochloric acid; even more preferably, the acid is 12M concentrated hydrochloric acid.
In the step (1), the MAX phase is Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC、Mo 3 AlC 2 And Ti 3 SiC 2 Any one or a combination of several of them.
In step (1), the ratio of the amount of the acid, the lithium fluoride and the MAX phase is 20mL: (1.6-2) g: (0.5-1.5) g; preferably, the ratio of the amount of acid, lithium fluoride and MAX phase is 20mL: (1.6-2) g:1g of the total weight of the composition.
In the step (1), the reaction temperature is 20-60 ℃; preferably, the temperature of the reaction is 40 ℃.
In the step (1), the reaction time is more than 3 h; preferably, the reaction time is more than 6 h; further preferably, the reaction time is 12 hours or more; even more preferably, the reaction time is more than 24 h; still more preferably, the reaction time is 24-48h.
In the step (1), collecting an upper-layer colloidal solution after the reaction is finished to obtain MXene; preferably, after the reaction is finished, centrifuging, washing, precipitating, dispersing and centrifuging, and collecting an upper layer colloidal solution to obtain MXene.
In the step (2), the bimetallic salt is a combination of a first metal salt and a second metal salt; the first metal salt is any one of Mg salt, co salt, ni salt, zn salt and Cu; the second metal salt is one of Al salt, fe salt and Cr salt; preferably, the molar ratio of the first metal salt to the second metal salt is (0.4-4): 1; further preferably, the molar ratio of the first metal salt to the second metal salt is (1.4-3): 1.
in the step (2), the dosage ratio of MXene to the bimetallic salt is 100mL: (0.25-2) mmol; preferably, the ratio of the MXene to the bimetallic salt is 100mL: (0.75-1.5) mmol.
In the step (2), the reaction further comprises urea; preferably, the molar ratio of the bimetallic salt to urea is 1: (2-4.5); further preferably, the molar ratio of the bimetallic salt to urea is 1: (3-3.5).
In the step (2), the reaction temperature is 20-30 ℃; preferably, the temperature of the reaction is room temperature.
In the step (2), the reaction time is more than 0.5 h; preferably, the reaction time is more than 1h; further preferably, the reaction time is 1-2h.
In the step (2), after the reaction is finished, a suspension mixed solution is obtained, the pH value is adjusted, and the reaction is continued.
Wherein the solution for adjusting the pH is a sodium hydroxide solution and/or a sodium carbonate solution, and the solvent is water; preferably, the solution for adjusting the pH is a sodium hydroxide and sodium carbonate solution; further preferably, the molar ratio of sodium hydroxide to sodium carbonate is 3: (3-12); even more preferably, the molar ratio of sodium hydroxide to sodium carbonate is 3: (5-9); still further preferably, the molar ratio of sodium hydroxide to sodium carbonate is 3:7.5.
wherein, the pH adjustment is to add the solution with the adjusted pH into the suspension mixed solution, adjust the pH and continue the reaction; preferably, the volume ratio of the pH adjusting solution to the suspension mixed solution is 1: (5-15); further preferably, the volume ratio of the pH-adjusted solution to the suspension mixture is 1:10.
wherein the temperature of the continuous reaction is 20-30 ℃; preferably, the temperature for the continued reaction is room temperature.
Wherein the continuous reaction time is more than 0.5 h; preferably, the time for continuing the reaction is more than 1h; further preferably, the time for continuing the reaction is 1 to 2 hours.
Standing after the continuous reaction is finished, and obtaining a precipitate which is an MXene @ LDH composite material; preferably, the standing time is more than 1h; further preferably, the standing time is more than 6 h; still more preferably, the standing time is 12 hours or more; still more preferably, the standing time is 24-48h.
In the step (3), the ferric salt is ferrous salt and/or ferric salt; preferably, the iron salt is a ferrous salt and a ferric salt; further preferably, the mass ratio of the ferrous salt to the ferric salt is 1: (1.5-3); preferably, the ferrous salt is ferrous chloride; preferably, the ferric salt is ferric chloride.
In the step (3), the mass ratio of MXene @ LDH composite material to ferric salt is 1: (0.6-2.6); preferably, the mass ratio of the MXene @ LDH composite material to the iron salt is 1:1.6.
in the step (3), the solvent for the reaction is water.
Wherein the dosage ratio of the MXene @ LDH composite material to the solvent is 0.3g: (10-40) mL; preferably, the dosage ratio of the MXene @ LDH composite material to the solvent is 0.3g:25mL.
In the step (3), the pH value of the alkaline condition is 9-11; preferably, the alkalinity adjusting substance is any one or a combination of more of NaOH, ammonia water and urea.
In the step (3), the reaction temperature is 60-100 ℃; preferably, the temperature of the reaction is 70-90 ℃; further preferably, the temperature of the reaction is 80 ℃.
In the step (3), the reaction time is more than 0.2 h; preferably, the reaction time is more than 0.5 h; further preferably, the reaction time is 0.5-1.5h; still further preferably, the reaction time is 1h.
In the step (4), adding acidic MXene @ LDH @ Fe 3 O 4 Adding a silane coupling agent into the composite material solution; preferably, acid MXene @ LDH@Fe 3 O 4 After the composite material solution is subjected to ultrasonic treatment, adding a silane coupling agent; further preferably, the time of the ultrasound is 10-30min.
Wherein the acidic pH is 2-6; preferably, the acidic pH is 4-5; further preferably, the pH is adjusted with glacial acetic acid and/or hydrochloric acid.
Wherein the solvent of the composite material solution is ethanol and/or water; preferably, the solvent of the composite material is ethanol and water; further preferably, the volume ratio of ethanol to water is 1: (0.5-1.5); still further preferably, the volume ratio of ethanol to water is 1:1.
wherein, MXene @ LDH @ Fe 3 O 4 MXene @ LDH @ Fe in composite material solution 3 O 4 The dosage ratio of the composite material to the solvent is (0.2-1.2) g:100mL; preferably MXene @ LDH @ Fe 3 O 4 The dosage ratio of the composite material to the solvent is (0.6-0.8) g:100mL.
In the step (4), MXene @ LDH @ Fe 3 O 4 The dosage ratio of the composite material to the silane coupling agent is 1g: (2-4) mL.
In the step (4), the silane coupling agent is any one or a combination of gamma-Aminopropyltriethoxysilane (APTES), gamma-Aminopropyltrimethoxysilane (APTMS) and 3-glycidyloxypropyltrimethoxysilane (KH-560).
In the step (4), the reaction temperature is 40-80 ℃; preferably, the temperature of the reaction is 50-70 ℃; further preferably, the temperature of the reaction is 60 ℃.
In the step (4), the reaction time is more than 1h; preferably, the reaction time is more than 5h; further preferably, the reaction time is 9 hours or more; still further preferably, the reaction time is 9-11h; most preferably, the reaction time is 10h.
In order to solve the third technical problem, the invention discloses an application of the immobilized laccase in degrading organic phenol, wherein the immobilized laccase takes the modified magnetic transition metal carbonitride as an immobilized carrier.
Wherein the application comprises the following steps:
s1: activating the modified magnetic transition metal carbonitride, and then mixing the activated modified magnetic transition metal carbonitride with laccase for culture to obtain immobilized laccase;
s2: mixing the immobilized laccase with a substance containing organic phenol for degradation;
preferably, in step S1, the modified magnetic transition metal carbonitride is activated to prepare a suspension, and then mixed with laccase for culture to obtain the immobilized laccase; further preferably, the suspension is formulated by a buffer; still more preferably, the amount of the activated modified magnetic transition metal carbonitride in the suspension is 1-5mg/mL of buffer.
In step S1, the activation is performed with a glutaraldehyde solution.
In step S1, the pH value of the culture is 1-8; preferably, the pH of the culture is 3-6; further preferably, the pH of the culture is 4 to 5.
In the step S1, the dosage of the laccase is 100-500mg/g modified magnetic transition metal carbonitride; further preferably, the dosage of the laccase is 200-400mg/g modified magnetic transition metal carbonitride; even more preferably, the laccase is present in an amount of 300mg/g modified magnetic transition metal carbonitride.
In step S1, the temperature of the culture is 25-30 ℃.
In the step S1, the culture time is more than 0.5 h; further preferably, the culturing time is 1-8h; still more preferably, the time of the cultivation is 3 hours.
In the step S2, the dosage ratio of the immobilized laccase to the organic phenol is (1-9) mg:0.05mg; preferably, the dosage ratio of the immobilized laccase to the organic phenol is (4-6) mg:0.05mg; further preferably, the dosage ratio of the immobilized laccase to the organic phenol is 5mg:0.05mg.
In the step S2, the substance containing organic phenol is a solution containing 2,4-dichlorophenol; preferably, the organic phenol-containing material is 2,4-dichlorophenol solution, and the concentration of 2,4-dichlorophenol is 5-25mg/mL.
In the step S2, the degradation time is more than 0.5 h; preferably, the degradation time is 0.5-8.5h; further preferably, the time for degradation is 1-8h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) LDH grows in situ on the single-layer two-dimensional nanosheet MXene to form a 2D/2D heterogeneous hybrid structure, so that the interlayer spacing can be increased, the charge transfer can be accelerated, and the comparative area is large and more active sites can be exposed.
(2) MXene @ LDH shows co-deposition of Fe 3 O 4 High specific surface area of two-dimensional nanosheet and Fe 3 O 4 The magnetic response capability of the composite material is complementary in advantages, and the surface of the composite material modified by amino silanization has abundant amino functional groups and can be used for enzyme immobilization.
(3) The immobilized enzyme can catalyze phenolic organic pollutants difficult to degrade in water, can be quickly collected with low energy consumption through a magnetic field, is used for recycling for many times, is safe and non-toxic, and is a green and safe water treatment agent.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is a scanning electron micrograph (a) of the MAX phase and (b) (SEM) of the two-dimensional nanomaterial MXene prepared in example 1.
FIG. 2 is a transmission electron micrograph (TEM, 500nm scale) of the two-dimensional nanomaterial MXene prepared in example 1.
FIG. 3 is a transmission electron micrograph (TEM, scale 100 nm) of MXene @ LDH material prepared in example 1.
FIG. 4 is MXene @ LDH (a) MXene @ LDH @ Fe 3 O 4 (b) And MXene @ LDH @ Fe 3 O 4 -NH 2 (c) An infrared spectrum of (1).
FIG. 5 is an XRD pattern of MXene (a) MXene @ LDH (b).
FIG. 6 is MXene @ LDH @ Fe 3 O 4 Magnetic hysteresis loop diagram of (1).
FIG. 7 is a graph of temperature stability tests for free laccase and immobilized laccase.
FIG. 8 is a graph of pH stability tests for free laccase and immobilized laccase.
FIG. 9 is a graph of the reusability of different immobilized laccases.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The laccase enzyme described in the examples below is from Coriolus versicolor, purchased from Sigma-Aldrich (China, cat # 38429), and has an enzyme activity of greater than 500U/g, with 1 enzyme activity unit (U) being defined as the amount of enzyme required to convert 1. Mu.M catechol per 1 minute at pH 5.0 and 25 ℃.
Example 1: MXene @ LDH @ Fe 3 O 4 -NH 2 Preparation of
(1) Preparation of MXene: weighing 1.6g of LiF and 20mL of 12M concentrated hydrochloric acid, adding the mixture into a 100mL polytetrafluoroethylene beaker, stirring at room temperature for 5min, uniformly mixing, adding 1g of titanium aluminum carbide powder, stirring at 40 ℃ for reacting for 24h, centrifuging the obtained product, and washing with deionized water until the pH value is neutral to obtain clay-like precipitate. Adding water to the precipitate in N 2 And carrying out ice-bath ultrasonic dispersion (20min, 240W) under protection, centrifuging at the rotating speed of 4000rpm for 30min after ultrasonic treatment, and collecting an upper-layer colloidal solution to obtain single-few-layer MXene.
(2) Preparation of MXene @ LDH: 3:1:9
0.261g of Ni (NO) was weighed 2 ·6H 2 O(0.9mmol)、0.242g Fe(NO) 3 ·9H 2 O (0.6 mmol) and 0.27g urea (4.5 mmol) are added into 100mL of the colloidal solution, the mixture is evenly dispersed by ultrasonic for 5min, magnetons are added, and the mixture is stirred on a magnetic stirrer for reaction for 1h. 0.12g of sodium hydroxide and 0.795g of anhydrous sodium carbonate are weighed, 10mL of deionized water is added for dissolution, the solution is dripped into the suspension mixed solution, the stirring reaction at room temperature is continued for 1h, and the standing reaction is carried out at room temperature for 24h after the reaction is finished. And (3) putting the obtained product into a 50mL centrifuge tube, centrifugally washing the product for 3 times by using deionized water, and freeze-drying the product in a freeze dryer to obtain MXene @ LDH black powder.
(3)MXene@LDH@Fe 3 O 4 The preparation of (1):
weighing 0.3g MXene @ LDH powder, 0.351g ferric trichloride and 0.129g ferrous chloride, adding 25mL deionized water for dissolving, transferring into a round bottom flask, introducing nitrogen, stirring at 80 ℃ in an oil bath, adjusting pH to 10 with 1M sodium hydroxide solution, continuously stirring for reaction for 1h, separating the obtained product with a magnet, washing and precipitating with deionized water until the supernatant is neutral, and drying in a freeze dryer to obtain MXene @ LDH @ Fe 3 O 4 A composite material.
(4)MXene@LDH@Fe 3 O 4 Amino silanization of (a):
weighing 0.75gMXene @ LDH @ Fe 3 O 4 Adding 10mL of deionized water into the composite material, performing ultrasonic dispersion for 10min, and introducing N 2 The reaction system was mechanically stirred in an oil bath at 60 ℃ to adjust the pH =4 with 0.01M dilute hydrochloric acid, stirred and activated for 1 hour, and then centrifuged. Adding 100mL ethanol water solution (volume ratio of ethanol to water is 1:1), adjusting pH =4 with glacial acetic acid, adding 1mL LAPTES, and introducing N 2 Mechanically stirring and reacting for 10h in an oil bath at 60 ℃, washing the product with deionized water for 3-5 times, and then drying in vacuum to obtain MXene @ LDH @ Fe 3 O 4 -NH 2 。
Fig. 1 is a scanning electron micrograph (a) of the MAX phase and a Scanning Electron Micrograph (SEM) of the two-dimensional nanomaterial MXene prepared in example 1 (b). The MAX phase in the graph a shows a compact lamellar structure, and the MAX phase in the graph b shows that the material is wrinkled and bent at the edge or curled in the whole sheet layer, and shows a typical two-dimensional lamellar structure, and the transverse dimension is about 50-100 mu m, which indicates that a single few-layer MXene can be successfully prepared by the method of the invention.
Fig. 2 is a Transmission Electron Micrograph (TEM) of the two-dimensional nanomaterial MXene prepared in example 1. The figure shows a monolithic layer with irregular arrangement, indicating that a single minor layer MXene can be successfully prepared using the method of the present invention.
Figure 3 is a Transmission Electron Micrograph (TEM) of mxene @ ldh material prepared in example 1. The figure shows that loosely-packed LDH nanosheet networks with the thickness of 2-5 nm grow on the surfaces of single and few layers of MXene nanosheets, and the MXene @ LDH can be successfully prepared by the method.
FIG. 4 shows MXene @ LDH and MXene @ LDH @ Fe 3 O 4 And MXene @ LDH @ Fe 3 O 4 -NH 2 An infrared spectrum of (1). At 3350cm -1 The absorption peak corresponds to the stretching vibration of hydrophilic O-H at 1634cm -1 、1037cm -1 And 1037cm -1 The peaks at positions correspond to tensile vibrations of the N-H bond, the C-N bond and the Si-O bond, indicating successful modification by the silane coupling agent.
FIG. 5 shows LDH, MXene @ LDH @ Fe 3 O 4 XRD pattern of (a). For LDH, the diffraction peaks corresponding to 2 theta =11.9, 22.2, 34.6 and 38.9 are (003), (006), (009), (015) planes respectively, and in MXene @ LDH, the characteristic peaks of the LDH can be obviously seen, but the (002) diffraction peak of the MXene is weaker, and is easily overlapped by the signal of the LDH, and in MXene @ LDH @ Fe 3 O 4 In the case of MXene and LDH, characteristic peaks were observed, but the diffraction peak intensity was weak, indicating that the degree of crystallization was low, MXene @ LDH @ Fe 3 O 4 The material is present in an amorphous form.
FIG. 6 is MXene @ LDH @ Fe 3 O 4 The hysteresis loop of (1) shows MXene @ LDH @ Fe 3 O 4 Shows superparamagnetism, the saturation magnetization is 23.08eum/g, and the separation of the carrier can be realized under the action of an external magnetic field.
Comparative example 1: MXene @ Fe 3 O 4 -NH 2 Preparation of
(1) Preparation of MXene: weighing 1.6g of LiF and 20mL of 12M concentrated hydrochloric acid, adding the mixture into a 100mL polytetrafluoroethylene beaker, stirring at room temperature for 5min, uniformly mixing, adding 1g of titanium aluminum carbide powder, stirring at 40 ℃ for reacting for 24h, centrifuging the obtained product, and washing with deionized water until the pH value is neutral to obtain clay-like precipitate. Adding water to the precipitate in N 2 Ice-bath ultrasonic dispersion is carried out under protection (20min, 240W), centrifugation is carried out for 30min at the rotating speed of 4000rpm after ultrasonic treatment, and an upper layer colloidal solution is collected to obtain single-few-layer MXene.
(2)MXene@Fe 3 O 4 The preparation of (1):
0.3g of MXene powder, 0.351g of ferric chloride and 0.129g of ferrous chloride are weighed, added with 25mL of deionized water for dissolving, transferred into a round bottom flask, and introduced with nitrogenStirring with oil bath at 80 deg.C, adjusting pH to 10 with 1M sodium hydroxide solution, stirring for 1 hr, separating the obtained product with magnet, washing the precipitate with deionized water until the supernatant is neutral, and drying in freeze dryer to obtain MXene @ Fe 3 O 4 A composite material.
(3)MXene@Fe 3 O 4 Amino silanization of (a):
weighing 0.75g MXene @ Fe 3 O 4 Adding 10mL of deionized water into the composite material, performing ultrasonic dispersion for 10min, and introducing N 2 The reaction system was mechanically stirred in an oil bath at 60 ℃ to adjust the pH =4 with 0.01M dilute hydrochloric acid, stirred and activated for 1 hour, and then centrifuged. Adding 100mL ethanol water solution (volume ratio of ethanol to water is 1:1), adjusting pH =4 with glacial acetic acid, adding 1mL LAPTES, and introducing N 2 Mechanically stirring and reacting for 10h in an oil bath at 60 ℃, washing the product with deionized water for 3-5 times, and then drying in vacuum to obtain MXene @ Fe 3 O 4 -NH 2 。
Comparative example 2: LDH @ Fe 3 O 4 -NH 2 Preparation of
(1) Preparation of LDH:
0.261g of Ni (NO) was weighed 2 ·6H 2 O(0.9mmol)、0.242g Fe(NO) 3 ·9H 2 Dissolving O (0.6 mmol) and 0.27g urea (4.5 mmol) in 20mL degassed ultrapure water, performing ultrasonic treatment for 5-10 min to disperse uniformly, adding magnetons, and stirring on a magnetic stirrer for reaction for 1h. 0.12g of sodium hydroxide and 0.795g of anhydrous sodium carbonate are weighed, 10mL of deionized water is added for dissolution, the solution is dripped into the suspension mixed solution, the stirring reaction at room temperature is continued for 1h, and the standing reaction is carried out at room temperature for 24h after the reaction is finished. And putting the obtained product into a 50mL centrifuge tube, performing centrifugal washing for 3 times by using deionized water, and performing freeze-drying in a freeze-drying machine to obtain LDH brown yellow powder.
(2)LDH@Fe 3 O 4 The preparation of (1):
weighing 0.3g of LDH powder, 0.351g of ferric chloride and 0.129g of ferrous chloride, adding 25mL of deionized water for dissolving, transferring to a round bottom flask, introducing nitrogen, stirring in an oil bath at 80 ℃, adjusting the pH to 10 by using 1M sodium hydroxide solution, continuously stirring for reacting for 1h, separating the obtained product by using a magnet, and removingWashing the precipitate with ionized water until the supernatant is neutral, and drying in a freeze dryer to obtain LDH @ Fe 3 O 4 A composite material.
(3)LDH@Fe 3 O 4 Amino silanization of (1):
weighing 0.75gLDH @ Fe 3 O 4 Adding 10mL of deionized water into the composite material, performing ultrasonic dispersion for 10min, and introducing N 2 The reaction system was mechanically stirred in an oil bath at 60 ℃ to adjust the pH =4 with 0.01M diluted hydrochloric acid, stirred and activated for 1 hour, and then centrifuged. Adding 100mL ethanol water solution (volume ratio of ethanol to water is 1:1), adjusting pH =4 with glacial acetic acid, adding 1mL LAPTES, and introducing N 2 Mechanically stirring and reacting for 10h in an oil bath at 60 ℃, washing the product with deionized water for 3-5 times, and then drying in vacuum to obtain LDH @ Fe 3 O 4 -NH 2 。
Example 2: MXene @ LDH @ Fe 3 O 4 -NH 2 Preparation of
(1) Preparation of MXene:
weighing 1.8g of LiF and 20mL of 12M concentrated hydrochloric acid, adding into a 100mL polytetrafluoroethylene beaker, stirring at room temperature for 5min, uniformly mixing, adding 1g of titanium aluminum carbide powder, stirring at 50 ℃ for reaction for 24h, centrifuging the obtained product, and washing with deionized water until the pH value is neutral to obtain clay-like precipitate. Adding water to the precipitate in N 2 And carrying out ice-bath ultrasonic dispersion (20min, 240W) under protection, centrifuging at the rotating speed of 4000rpm for 30min after ultrasonic treatment, and collecting an upper-layer colloidal solution to obtain single-few-layer MXene.
(2) Preparation of MXene @ LDH:
weighing 0.128g Mg (NO) 3 ) 2 ·6H 2 O(0.5mmol)，0.089g Al(NO 3 ) 3 ·9H 2 O (0.25 mmol) and 0.1g urea (2.5 mmol) are added into 100mL of the colloidal solution, the mixture is evenly dispersed by ultrasonic for 5min, and magnetons are added and stirred on a magnetic stirrer for reaction for 1h. 0.12g of sodium hydroxide and 0.795g of anhydrous sodium carbonate are weighed, 10mL of deionized water is added for dissolution, the solution is dripped into the suspension mixed solution, the stirring reaction at room temperature is continued for 1h, and the standing reaction is carried out at room temperature for 24h after the reaction is finished. Placing the obtained product into a 50mL centrifuge tube, centrifugally washing with deionized water for 3 times, and freezing in a freeze dryerDrying to obtain MXene @ LDH black powder.
(3)MXene@LDH@Fe 3 O 4 The preparation of (1):
weighing 0.3g MXene @ LDH powder, 0.351g ferric trichloride and 0.129g ferrous chloride, adding 25mL deionized water for dissolving, transferring into a round bottom flask, introducing nitrogen, stirring at 80 ℃ in an oil bath, adjusting pH to 10 with 1M sodium hydroxide solution, continuously stirring for reaction for 1h, separating the obtained product with a magnet, washing and precipitating with deionized water until the supernatant is neutral, and drying in a freeze dryer to obtain MXene @ LDH @ Fe 3 O 4 A composite material.
(4)MXene@LDH@Fe 3 O 4 Amino silanization of (a):
weighing 0.75gMXene @ LDH @ Fe 3 O 4 Adding 10mL of deionized water into the composite material, performing ultrasonic dispersion for 10min, and introducing N 2 The reaction system was mechanically stirred in an oil bath at 60 ℃ to adjust the pH =4 with 0.01M diluted hydrochloric acid, stirred and activated for 1 hour, and then centrifuged. Adding 100mL ethanol water solution (volume ratio of ethanol to water is 1:1), adjusting pH =4 with glacial acetic acid, adding 1mL LAPTES, and introducing N 2 Mechanically stirring and reacting for 10h in an oil bath at 60 ℃, washing the product with deionized water for 3-5 times, and then drying in vacuum to obtain MXene @ LDH @ Fe 3 O 4 -NH 2 。
Example 3: MXene @ LDH @ Fe 3 O 4 -NH 2 Organic phenol degrading performance as immobilized enzyme carrier
(1) Immobilized laccase: 5mg of MXene @ LDH @ Fe prepared in example 1 were weighed 3 O 4 -NH 2 5mL of 2% glutaraldehyde solution was added, the mixture was reacted for 2 hours in a shaker at 25 ℃ at 200rpm, and the carrier was recovered by magnetic separation and washed 3 times with deionized water. 5mL of citric acid-disodium hydrogen phosphate (pH =4.0,0.1M) buffer solution is added to prepare 1mg/mL of suspension, 1.5mg of laccase freeze-dried powder and 1-0.5 mL of LABTS solution are added, the mixture is cultured for 3h in a shaking table at 25 ℃, and the immobilized enzyme is separated and recovered by a magnet.
(2) Degrading organic phenol: mixing 1.5mg of non-immobilized laccase and 5mg of immobilized enzyme prepared in the step (1) with 5mL of 2,4-dichlorophenol aqueous solution with the concentration of 10mg/L respectively, adding 0.5mL of LABTS (1 mmol) aqueous solution as a mediator substance, and performing reaction and degradation for 8h in a shaking table at the temperature of 25 ℃ at the rpm of 200rpm. And (3) measuring the content of the residual 2,4-dichlorophenol by a high performance liquid phase method.
(3) And (3) repeating the step (2) to carry out repeated tests, washing the immobilized enzyme after reaction for 3 times by using a citric acid-disodium hydrogen phosphate (pH =4.0,0.1M) buffer solution, adding 5mL of 2,4-dichlorophenol aqueous solution with the concentration of 10mg/L, adding 0.5mLABTS (1 mmol) serving as a mediator substance, and carrying out reaction degradation for 8 hours in a shaking table at the temperature of 25 ℃ at the speed of 200rpm. This process was repeated 7 times.
FIG. 7 is a graph of temperature stability test for free laccase and immobilized laccase, and FIG. 8 is a graph of pH stability test for free laccase and immobilized laccase. As can be seen, the immobilized laccase is more tolerant in the strong acid and strong alkali range and the high temperature range.
Comparative example 3: MXene @ Fe 3 O 4 -NH 2 Organic phenol degrading performance as immobilized enzyme carrier
(1) Immobilized laccase: weighing 5mgMXene @ Fe 3 O 4 -NH 2 5mL of 2% glutaraldehyde solution was added, the mixture was reacted for 2 hours in a shaker at 25 ℃ at 200rpm, and the carrier was recovered by magnetic separation and washed 3 times with deionized water. 5mL of citric acid-disodium hydrogen phosphate (pH =4,0.1M) buffer was added to prepare a 1mg/mL suspension, 1.5mg of laccase lyophilized powder was added thereto, the mixture was cultured in a shaker at 25 ℃ for 3 hours, and the immobilized enzyme was separated and recovered by a magnet.
(2) Degrading organic phenol: mixing the immobilized enzyme prepared in the step (1) with 5mL of 2,4-dichlorophenol solution with the concentration of 10mg/L, adding 0.5mL of LABTS (1 mmol) aqueous solution as a mediator substance, and performing reaction and degradation for 8h in a shaking table at the temperature of 25 ℃ at the speed of 200rpm. And (3) determining the content of the residual 2,4-dichlorophenol by a high performance liquid chromatography method.
(3) And (3) repeating the step (2) to carry out repeated tests, washing the immobilized enzyme after reaction for 3 times by using a citric acid-disodium hydrogen phosphate (pH =4.0,0.1M) buffer solution, adding 5mL of 2,4-dichlorophenol aqueous solution with the concentration of 10mg/L, adding 0.5mLABTS (1 mmol) serving as a mediator substance, and carrying out reaction degradation for 8 hours in a shaking table at the temperature of 25 ℃ at the speed of 200rpm. This process was repeated 7 times.
Comparative example 4: LDH @ Fe 3 O 4 -NH 2 Organic phenol degrading performance as immobilized enzyme carrier
(1) Immobilized laccase: weighing 5mgLDH @ Fe 3 O 4 -NH 2 5mL of 2% glutaraldehyde solution was added, the mixture was reacted for 2 hours in a shaker at 25 ℃ at 200rpm, and the carrier was recovered by magnetic separation and washed 3 times with deionized water. 5mL of citric acid-disodium hydrogenphosphate (pH =4,0.1M) buffer was added to prepare a 1mg/mL suspension, 1.5mg of laccase lyophilized powder was added, the mixture was cultured in a shaker at 25 ℃ for 3 hours, and the immobilized enzyme was separated and recovered by a magnet.
(2) Degrading organic phenol: mixing the immobilized enzyme prepared in the step (1) with 5mL of 2,4-dichlorophenol solution with the concentration of 10mg/L, adding 0.5mL of LABTS (1 mmol) aqueous solution as a mediator substance, and performing reaction and degradation for 8h in a shaking table at the temperature of 25 ℃ at the speed of 200rpm. And (3) determining the content of the residual 2,4-dichlorophenol by a high performance liquid chromatography method.
(3) And (3) repeating the step (2) to carry out repeated tests, washing the immobilized enzyme after reaction for 3 times by using a citric acid-disodium hydrogen phosphate (pH =4.0,0.1M) buffer solution, adding 5mL of 2,4-dichlorophenol aqueous solution with the concentration of 10mg/L, adding 0.5mLABTS (1 mmol) serving as a mediator substance, and carrying out reaction degradation for 8 hours in a shaking table at the temperature of 25 ℃ at the speed of 200rpm. This process was repeated 7 times.
FIG. 9 is a graph of the reusability of different immobilized laccases. FIG. 9 shows that the initial degradation efficiency of three groups of immobilized enzymes can reach more than 90% in the recycling process, and after 7 times of recycling, the three groups of immobilized enzymes have LDH @ Fe 3 O 4 -lac，MXene@LDH@Fe 3 O 4 -lac and MXene @ LDH @ Fe 3 O 4 The-lac degradation efficiency dropped to 35.02%.11%, 44.11% and 51.68%, respectively. Wherein LDH @ Fe 3 O 4 The degradation efficiency of the-lac group is highest in the first two reuses, but the catalytic efficiency gradually decreases with the increase of the repetition times, and the decrease rate is larger than that of the other two groups. It can thus be seen that MXene @ LDH @ Fe is present in the course of repeated catalytic cycles 3 O 4 -lac is more advantageous.
The present invention provides a modified magnetic transition metal carbonitride, a method for preparing the same, and a method for applying the same, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (9)
1. The application of the immobilized laccase in degrading organic phenol is characterized in that the immobilized laccase takes modified magnetic transition metal carbonitride as an immobilized carrier, and the component of the modified magnetic transition metal carbonitride is MXene @ LDH @ Fe 3 O 4 -NH 2 (ii) a The weight percentage content is as follows: MXene 20-55%, LDH 15-50%, fe 3 O 4 20％-34％，NH 2 0.1 to 10 percent; the saturation magnetization is 20-26emu/g.
2. The use according to claim 1, wherein the method for preparing the modified magnetic transition metal carbonitride comprises the following steps:
(1) Reacting acid, lithium fluoride and MAX to obtain MXene;
(2) Reacting MXene with double metal salt under alkaline condition to obtain MXene @ LDH composite material;
(3) Reacting MXene @ LDH composite material with iron salt under alkaline condition to obtain MXene @ LDH @ Fe 3 O 4 A composite material;
(4) Mixing MXene @ LDH @ Fe 3 O 4 And (3) reacting the composite material with a silane coupling agent to obtain the composite material.
3. The use according to claim 2, wherein in step (1), the MAX phase is Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC、Mo 3 AlC 2 And Ti 3 SiC 2 Any one or combination of several of them;
wherein the dosage ratio of the acid, the lithium fluoride and the MAX phase is 20mL: (1.6-2) g: (0.5-1.5) g.
4. The use according to claim 2, wherein in step (2), the bimetallic salt is a combination of a first metal salt and a second metal salt; the first metal salt is any one of Mg salt, co salt, ni salt, zn salt and Cu; the second metal salt is one of Al salt, fe salt and Cr salt; the molar ratio of the first metal salt to the second metal salt is (0.4-4): 1;
wherein the dosage ratio of MXene to the double metal salt is 100mL: (0.25-2) mmol;
wherein the reaction further comprises urea; the molar ratio of the bimetallic salt to the urea is 1: (2-4.5).
5. The application of claim 3, wherein in the step (3), the mass ratio of MXene @ LDH composite material to iron salt is 1: (0.6-2.6);
wherein the solvent of the reaction is water; the dosage ratio of the MXene @ LDH composite material to the solvent is 0.3g: (10-40) mL.
6. The use of claim 3, wherein in step (4), MXene @ LDH @ Fe 3 O 4 The dosage ratio of the composite material to the silane coupling agent is 1g: (2-4) mL.
7. The application according to claim 1, characterized in that it comprises the following steps:
s1: activating the modified magnetic transition metal carbonitride, and then mixing and culturing the activated modified magnetic transition metal carbonitride with laccase to obtain immobilized laccase;
s2: and mixing the immobilized laccase with a substance containing organic phenol for degradation.
8. The use according to claim 7, wherein in step S1, the activation is carried out by using a glutaraldehyde solution;
the dosage of the laccase is 100-500mg/g modified magnetic transition metal carbonitride.
9. The use according to claim 7, wherein in step S2, the amount ratio of the immobilized laccase to the organic phenol is (1-9) mg:0.05mg.
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