CN116083411A - Heterogeneous photo-enzyme coupling catalyst, preparation method and application thereof - Google Patents

Heterogeneous photo-enzyme coupling catalyst, preparation method and application thereof Download PDF

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CN116083411A
CN116083411A CN202310291770.5A CN202310291770A CN116083411A CN 116083411 A CN116083411 A CN 116083411A CN 202310291770 A CN202310291770 A CN 202310291770A CN 116083411 A CN116083411 A CN 116083411A
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transition metal
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tetraazacyclotetradecane
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enzyme
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CN116083411B (en
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王彦霞
于洋
黄胜利
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Beijing Institute of Technology BIT
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    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/0004—Oxidoreductases (1.)
    • C12N9/0012—Oxidoreductases (1.) acting on nitrogen containing compounds as donors (1.4, 1.5, 1.6, 1.7)
    • C12N9/0036—Oxidoreductases (1.) acting on nitrogen containing compounds as donors (1.4, 1.5, 1.6, 1.7) acting on NADH or NADPH (1.6)
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
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Abstract

The invention relates to a heterogeneous photo-enzyme coupling catalyst, a preparation method and application thereof, belonging to the technical field of photo-enzyme coupling catalysis. In the catalyst, the oxidoreductase is doped in the transition metal polypyridine complex, and carboxylate groups on the transition metal polypyridine complex doped with the oxidoreductase are coordinated with metal ions to form a transition metal-MOF/oxidoreductase complex in situ; wherein the transition metal is Ru or Ir; the metal ions are zinc ions or nickel ions. The heterogeneous photo-enzyme coupling catalyst is formed in situ by doping the oxidoreductase into the Ru or Ir containing transition metal polypyridine complex and then complexing the carboxylate groups on the Ru or Ir containing transition metal polypyridine complex with metal ions. The catalyst has higher stability and catalytic activity.

Description

Heterogeneous photo-enzyme coupling catalyst, preparation method and application thereof
Technical Field
The invention relates to a heterogeneous photo-enzyme coupling catalyst, a preparation method and application thereof, belonging to the technical field of photo-enzyme coupling catalysis.
Background
The photo-enzyme coupling catalytic system aims at coupling the unique activity of the photo-catalytic reaction and the specificity of the biological enzyme catalysis, and simulating the photosynthesis in the nature to realize the efficient and green synthesis of functional molecules by solar driven enzyme catalysis. The research in the field is mainly focused on simply connecting a small molecular photocatalyst and an enzyme in series to form a homogeneous photo-enzyme coupled catalytic system. Ru (or Ir) transition metal polypyridine complex photocatalysts gradually have reports that the complex absorbs more strongly in the visible light region, does not undergo side reactions under illumination, forms an excited state with nearly 100% efficiency, has longer service life in the excited state, and can promote enzyme reaction through direct or indirect electron transfer.
However, existing photo-enzyme coupling catalysts based on Ru (or Ir) transition metals are mostly homogeneous catalysts, with poor stability. In addition, the oxidoreductase is an enzyme capable of catalyzing oxidation-reduction reaction between two molecules, and a metal-organic frameworks (MOFs) porous material integrates the advantages of adjustable structure, high porosity, high specific surface, good thermal stability, good chemical stability and the like, and no report on the formation of a heterogeneous photo-enzyme coupling catalyst by coupling the MOFs containing Ru (or Ir) with the oxidoreductase exists at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a heterogeneous photo-enzyme coupling catalyst, a preparation method and applications thereof. The heterogeneous photo-enzyme coupling catalyst is formed in situ by doping the oxidoreductase into the Ru or Ir containing transition metal polypyridine complex and then complexing the carboxylate groups on the Ru or Ir containing transition metal polypyridine complex with metal ions.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A heterogeneous photo-enzyme coupled catalyst in which an oxidoreductase is doped in a transition metal polypyridine complex, carboxylate groups on the transition metal polypyridine complex doped with the oxidoreductase being coordinated with metal ions to form a transition metal-MOF/oxidoreductase complex in situ; wherein the transition metal is Ru or Ir; the metal ions are zinc ions or nickel ions.
Preferably, the load of the oxidoreductase is 5% -10% of the total mass of the heterogeneous photo-enzyme coupling catalyst.
Preferably, the oxidoreductase is reductase 3GR7 or reductase 1Z48.
The preparation method of the heterogeneous photo-enzyme coupling catalyst comprises the following steps:
(1) Preparing a transition metal polypyridine complex by reacting the transition metal complex with 4,4' - ([ 2,2' -bipyridine ] -5,5' -diyl) dibenzoic acid; wherein the transition metal is Ru or Ir;
(2) Reacting 1,4,8, 11-tetraazacyclotetradecane with inorganic metal salt to prepare 1,4,8, 11-tetraazacyclotetradecane metal compound; wherein the inorganic metal salt is zinc salt or nickel salt;
(3) Dissolving a transition metal polypyridine complex in a mixed solution of sodium hydroxide aqueous solution and methanol, and adding oxidoreductase to obtain a solution A; dissolving 1,4,8, 11-tetraazacyclotetradecane metal compound in water with the purity higher than that of deionized water (water with the purity higher than or equal to that of deionized water, such as deionized water, ultrapure water and the like) to obtain a solution B; dropwise adding the solution A into the solution B, standing overnight, carrying out solid-liquid separation, and collecting solids to obtain a heterogeneous photo-enzyme coupling catalyst; wherein the dosage ratio of the transition metal polypyridine complex to the sodium hydroxide aqueous solution to the methanol is 10 mg: 100. mu L-130 mu L: 50. mu L-80 mu L, and the concentration of the sodium hydroxide aqueous solution is 5 mg/mL-15 mg/mL.
Preferably, in step (1), the transition metal complex is dissolved in Dimethylacetamide (DMA) and then 4,4'- ([ 2,2' -bipyridine) is added]5,5' -diyl) dibenzoic acid (bpydba) is stirred and reacted for 16h to 24h at 130 ℃ to 145 ℃ under the atmosphere of protective gas, after the reaction is finished, dimethyl acetamide is dried in a rotating way, methanol is added for dissolution, filtration is carried out, ethyl acetate and normal hexane with the volume ratio of 1:1 to 1:3 are added into filtrate, solid is collected, and vacuum drying is carried out, so that the transition metal polypyridine complex (M (bpy) is obtained 2 bpydba or M (ppy) 2 bpydba). More preferably, the transition metal complex is cis-dichlorobis (2, 2' -bipyridine) ruthenium (Ru (bpy) 2 Cl 2 ) Or dichlorotetrakis [ 2- (2-pyridyl) phenyl ]]Diiridium (III) ([ Ir (ppy)) 2 Cl 2 ] 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Transition metal complexes and 4,4'- ([ 2,2' -bipyridyl)]The molar ratio of the 5,5' -diyl) dibenzoic acid is 1:1-1:1.5.
Preferably, in the step (2), 1,4,8, 11-tetraazacyclotetradecane is dissolved in ethanol to obtain an ethanol solution of 1,4,8, 11-tetraazacyclotetradecane, and inorganic metal salt is dissolved in ethanol to obtain an ethanol solution of inorganic metal salt; and (3) dropwise adding an ethanol solution of inorganic metal salt into an ethanol solution of 1,4,8, 11-tetraazacyclotetradecane, stirring at 30-40 ℃ for reaction for 24-48 hours after the dropwise adding, concentrating ethanol after the reaction is finished, adding diethyl ether for precipitation to obtain a product, and carrying out vacuum drying to obtain the 1,4,8, 11-tetraazacyclotetradecane metal compound. More preferably, the molar ratio of the 1,4,8, 11-tetraazacyclotetradecane to the inorganic metal salt is 1:1-1:1.2. The inorganic metal salt is Zn (NO) 3 ) 2 ·6H 2 O or Ni (NO) 3 ) 2 ·6H 2 O。
Preferably, in the step (3), the ratio of the amount of the transition metal polypyridine complex, the aqueous sodium hydroxide solution, the methanol, the oxidoreductase and the 1,4,8, 11-tetraazacyclotetradecane metal compound is 10 mg: 100. mu L-130 mu L: 50. mu L-80 mu L:1 mg-2 mg:4 mg.
The use of a heterogeneous photo-enzyme coupled catalyst according to the invention for use in an oxidoreductase catalyzed reaction.
Advantageous effects
The invention provides a heterogeneous photo-enzyme coupling catalyst, wherein the oxidoreductase is doped in Ru or Ir-containing transition metal polypyridine complex, and carboxylate on the transition metal polypyridine complex is coordinated with metal zinc or nickel ions to form a transition metal-MOF/oxidoreductase complex in situ. The catalyst has higher stability and catalytic activity.
The invention provides a preparation method of a heterogeneous photo-enzyme coupling catalyst, which comprises the steps of firstly, coordinating 4,4' - ([ 2,2' -bipyridine ] -5,5' -diyl) dibenzoic acid ligand with transition metal, then mixing with oxidoreductase in a sodium hydroxide/methanol system with a specific proportion, and then coordinating with a 1,4,8, 11-tetraazacyclotetradecane zinc or nickel compound to form a photosensitive MOFs/enzyme composite system in situ at room temperature.
The invention provides application of a heterogeneous photo-enzyme coupled catalyst, which is used for oxidation-reduction enzyme catalytic reaction and has the advantages of high catalytic activity and high conversion rate. The catalyst is recycled for multiple times and still has high substrate conversion rate, which indicates that the catalyst has higher stability.
Drawings
FIG. 1 is a powder X-ray diffraction (PXRD) pattern of the end products of comparative example 1 and example 1.
FIG. 2 is a chart of infrared spectroscopic testing of the end product of example 1.
FIG. 3 shows the results of the photocatalytic performance test of the end products of comparative example 1 and example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the following examples or comparative examples:
(1) Powder X-ray diffraction (PXRD) test: the test instrument is Shimadzu XRD-6000.
(2) Infrared spectrum testing: the test instrument was Shimadzu IRAffinity-1S.
(3) Photocatalytic performance test:
to a rubber stopper-sealed glass vial, PBS solution (10 mM, pH=7.0), reaction substrate 2-cyclohexen-1-one (to give a final concentration of 1 mM), triethanolamine (100. Mu.L), the final product of example or comparative example (1.5 mg), nicotinamide Adenine Dinucleotide (NAD) (1 mM) were added in this order to give a total volume of the reaction system of 3 mL. Continuously vacuumizing and filling argon into a reaction bottle, repeatedly circulating for ten times to build an anaerobic environment, placing the reaction bottle on ice, irradiating a sample 2 h by using a xenon lamp (a light source for removing ultraviolet light), extracting a reaction liquid by using ethyl acetate after the illumination is finished, and researching a photocatalysis effect by using Gas Chromatography (GC).
Comparative example 1
（1）Ru(bpy) 2 Construction of bpydba
Ru (bpy) was added at room temperature 2 (oTf) 2 (0.5 mmol,355 mg) was dissolved in 40 mL DMA and added to the Schlemk flask, followed by the addition ofEquimolar 4,4'- ([ 2,2' -bipyridine)]-5,5' -diyl) dibenzoic acid (bpydba) (0.5 mmol,198 mg), after three air changes, the air in the reaction system was replaced with nitrogen, the reaction temperature was raised to 130 ℃, magnetic stirring was performed for 24 and h, DMA was dried, dissolved in methanol, insoluble matter was filtered, and ethyl acetate was used: n-hexane (volume ratio of 3:1) is used as a precipitator, a product is precipitated, and Ru (bpy) is obtained by vacuum drying 2 bpydba。
(2) Construction of 1,4,8, 11-tetraazacyclotetradecane Zinc (II)
1,4,8, 11-tetraazacyclotetradecane (1 mmol,200 mg) and 20 mL ethanol were added to a one-necked flask, and dissolved with stirring, while equimolar Zn (NO) 3 ) 2 ·6H 2 O (1 mmol,297 mg) was dissolved in 20 mL ethanol, and then the solution was dropwise added to a one-necked flask, the temperature was raised to 40℃and the solution was magnetically stirred for 24. 24h, the ethanol was concentrated, the product was precipitated with diethyl ether, and then the solution was dried in vacuo to give 1,4,8, 11-tetraazacyclotetradecane zinc (II).
(3) Construction of Ru-MOFs
10 mg Ru (bpy) was weighed out 2 bpydba was dissolved in a mixture of 100. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 80. Mu.L of methanol to give solution A, while 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to give solution B, which was added dropwise to the solution B, and left standing overnight to give the final Ru-MOFs product.
Example 1
Steps (1) - (2) are the same as comparative example 1.
(3) Construction of Ru-MOFs/enzyme composite System
10 mg Ru (bpy) was weighed out 2 bpydba was dissolved in a mixture of 100. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 80. Mu.L of methanol, while 2 mg of reductase 3GR7 was added to obtain solution A, while 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to obtain solution B, which was dropwise added to the solution B and allowed to stand overnight to obtain the final product, namely, ru-MOFs/enzyme complex.
The powder X-ray diffraction (PXRD) test results of comparative example 1 and the final product in this example are shown in FIG. 1, and the infrared spectrum test results of the final product in this example are shown in FIG. 2, and the results confirm successful construction of Ru-MOFs/enzyme complex system.
The results of the photocatalytic performance test of the end products of comparative example 1 and this example are shown in FIG. 3, and the photocatalytic effect of the Ru-MOFs/enzyme complex is better than that of Ru-MOFs, and the substrate conversion is improved from 5% to 70% because the enzyme and Ru-MOFs are synergistic, promoting an improvement in conversion.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 70 percent.
Example 2
（1）Ru(bpy) 2 Construction of bpydba
Ru (bpy) was added at room temperature 2 (oTf) 2 (0.5 mmol,355 mg) was dissolved in 50 mL DMA and added to a Schlenk flask followed by equimolar 4,4'- ([ 2,2' -bipyridine)]-5,5' -diyl) dibenzoic acid (bpydba) (0.5 mmol,198 mg), after three air changes, the air in the reaction system was replaced with nitrogen, the reaction temperature was raised to 145 ℃, magnetic stirring was performed for 16. 16h, DMA was dried, dissolved in methanol, insoluble matter was filtered, and ethyl acetate was used: n-hexane (volume ratio of 3:1) is used as a precipitator, a product is precipitated, and Ru (bpy) is obtained by vacuum drying 2 bpydba。
(2) Construction of 1,4,8, 11-tetraazacyclotetradecane Nickel (II)
1,4,8, 11-tetraazacyclotetradecane (1 mmol,200 mg) and 10 mL ethanol were added to a one-necked flask, and dissolved with stirring, while equimolar Ni (NO) 3 ) 2 ·6H 2 O (1 mmol,297 mg) was dissolved in 10 mL ethanol, and then was dropwise added to a one-necked flask, the temperature was raised to 30℃and the mixture was magnetically stirred for 48: 48h, the ethanol was concentrated, the product was precipitated with diethyl ether, and then dried in vacuo to give 1,4,8, 11-tetraazacyclotetradecane nickel (II).
(3) Construction of Ru-MOFs/enzyme composite System
10 mg Ru (bpy) was weighed out 2 bpydba was dissolved in 130. Mu.L of aqueous sodium hydroxide (10 mg/mL) and50. mu L of methanol mixed solution is added with 1 mg reductase 1Z48 to obtain solution A, 4 mg of 1,4,8, 11-tetraazacyclotetradecane nickel (II) is dissolved in 60 mu L of deionized water to obtain solution B, the solution A is dropwise added into the solution B, and the mixture is left to stand overnight to obtain a heterogeneous photo-enzyme coupling catalyst which is recorded as Ru-MOFs/enzyme complex.
The end product described in this example was tested by PXRD and IR spectroscopy to confirm successful construction of Ru-MOFs/enzyme complex systems.
The results of the photocatalytic performance test of the final product in this example showed a substrate conversion of about 65%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 65 percent.
Example 3
（1）Ir(ppy) 2 Construction of bpydba
At room temperature, ir (ppy) 2 Cl 2 ] 2 (0.5 mmol,547 mg) was dissolved in 40 mL DMA and added to a Schlenk flask followed by equimolar 4,4'- ([ 2,2' -bipyridine)]5,5' -Di) dibenzoic acid (bpydba) (1 mmol,396 mg), after three air changes, the air in the reaction system was replaced with nitrogen, the reaction temperature was raised to 135 ℃, magnetic stirring was performed for 20 and h, DMA was dried, dissolved in methanol, insoluble matter was filtered, and ethyl acetate was used: n-hexane (volume ratio 3:1) was used as precipitant to precipitate the product, which was dried in vacuo to give Ir (ppy) 2 bpydba。
(2) Construction of 1,4,8, 11-tetraazacyclotetradecane Zinc (II)
1,4,8, 11-tetraazacyclotetradecane (1 mmol,200 mg) and 15 mL ethanol were added to a one-necked flask, and dissolved with stirring, while equimolar Zn (NO) 3 ) 2 ·6H 2 O (1 mmol,297 mg) was dissolved in 15 mL ethanol, and then the solution was dropwise added to a one-necked flask, the temperature was raised to 35℃and the solution was magnetically stirred for 30 h, the ethanol was concentrated, the product was precipitated with diethyl ether, and then the solution was dried in vacuo to give 1,4,8, 11-tetraazacyclotetradecane zinc (II).
(4) Construction of Ir-MOFs/enzyme composite System
Weigh 10 mg Ir (ppy) 2 bpydba was dissolved in a mixture of 120. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 60. Mu.L of methanol, 1.5 mg reductase 3GR7 was added to the mixture to obtain solution A, and 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to obtain solution B, which was added dropwise to the solution B and allowed to stand overnight to obtain a heterogeneous photo-enzyme coupling catalyst, designated Ir-MOFs/enzyme complex as the final product.
The results of the PXRD and IR spectrum tests of the final product described in this example confirm the successful construction of Ir-MOFs/enzyme complex systems.
The results of the photocatalytic performance test of the final product in this example show a substrate conversion of about 70%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 70 percent.
Example 4
（1）Ir(ppy) 2 Construction of bpydba
At room temperature, ir (ppy) 2 Cl 2 ] 2 (0.5 mmol,547 mg) was dissolved in 45 mL DMA and added to a Schlenk flask followed by equimolar 4,4'- ([ 2,2' -bipyridine)]5,5' -Diyl) dibenzoic acid (bpydba) (1 mmol,396 mg), after three air changes, the air in the reaction system was replaced with nitrogen, the reaction temperature was raised to 140 ℃, magnetic stirring was performed for 22 and h, DMA was dried, dissolved in methanol, insoluble matter was filtered, and ethyl acetate was used: n-hexane (volume ratio 3:1) was used as precipitant to precipitate the product, which was dried in vacuo to give Ir (ppy) 2 bpydba。
(2) Construction of 1,4,8, 11-tetraazacyclotetradecane Nickel (II)
1,4,8, 11-tetraazacyclotetradecane (1 mmol,200 mg) and 20 mL ethanol were added to a one-necked flask, and dissolved with stirring, while equimolar Ni (NO) 3 ) 2 ·6H 2 O (1 mmol,297 mg) was dissolved in 20 mL ethanol and then dropped dropwise into a one-neck flask, the temperature was raised to 40℃and after magnetic stirring was carried out for 24h, ethanol was concentrated and the product was precipitated with diethyl etherVacuum drying to obtain 1,4,8, 11-tetraazacyclotetradecane nickel (II).
(4) Construction of Ir-MOFs/enzyme composite System
Weigh 10 mg Ir (ppy) 2 bpydba was dissolved in a mixture of 110. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 70. Mu.L of methanol, while 2 mg of reductase 1Z48 was added to obtain solution A, while 4 mg of 1,4,8, 11-tetraazacyclotetradec nickel (II) was dissolved in 60. Mu.L of deionized water to obtain solution B, which was added dropwise to the solution B and allowed to stand overnight to obtain the final product, a heterogeneous photo-enzyme coupling catalyst designated Ir-MOFs/enzyme complex.
The results of the PXRD and IR spectrum tests of the final product described in this example confirm the successful construction of Ir-MOFs/enzyme complex systems.
The results of the photocatalytic performance test of the final product in this example showed a substrate conversion of about 65%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 65 percent.
Example 5
In this example, reductase 3GR7 was replaced with reductase 1Z48, and the remainder was the same as in example 1.
The results of the photocatalytic performance test of the final product in this example showed a substrate conversion of about 65%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 65 percent.
Example 6
In this example, reductase 1Z48 was replaced with reductase 3GR7, and the remainder was the same as in example 2.
The results of the photocatalytic performance test of the final product in this example show a substrate conversion of about 70%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 70 percent.
Example 7
In this example, reductase 3GR7 was replaced with reductase 1Z48, and the remainder was the same as in example 3.
The results of the photocatalytic performance test of the final product in this example showed a substrate conversion of about 65%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 65 percent.
Example 8
In this example, reductase 1Z48 was replaced with reductase 3GR7, and the remainder was the same as in example 4.
The results of the photocatalytic performance test of the final product in this example show a substrate conversion of about 70%.
The catalyst is recovered to repeatedly perform photocatalysis performance test, and after 5 times of circulation, the substrate conversion rate can be maintained at about 70 percent.
Comparative example 2
（1）Ru(bpy) 2 Construction of bpydc
Ru (bpy) was added at room temperature 2 (oTf) 2 (0.5 mmol,355 mg) was dissolved in 40 mL of DMA, and then added to a Schlenk reaction flask, and then equimolar 2,2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc) (0.5 mmol,122 mg) was added, after three air changes, the air in the reaction system was replaced with nitrogen, the reaction temperature was raised to 130 ℃, and after magnetic stirring for 24h, after spinning the DMA, dissolved in methanol, insoluble materials were filtered, and ethyl acetate was used: n-hexane (volume ratio of 3:1) is used as a precipitator, a product is precipitated, and Ru (bpy) is obtained by vacuum drying 2 bpydc。
(2) Construction of 1,4,8, 11-tetraazacyclotetradecane Zinc (II)
1,4,8, 11-tetraazacyclotetradecane (1 mmol,200 mg) and 20 mL ethanol were added to a one-necked flask, and dissolved with stirring, while equimolar Zn (NO) 3 ) 2 ·6H 2 O (1 mmol,297 mg) was dissolved in 20 mL ethanol, and then the solution was dropwise added to a one-necked flask, the temperature was raised to 40℃and the solution was magnetically stirred for 24. 24h, the ethanol was concentrated, the product was precipitated with diethyl ether, and then the solution was dried in vacuo to give 1,4,8, 11-tetraazacyclotetradecane zinc (II).
(3) Construction of Ru-MOFs
10 mg Ru (bpy) was weighed out 2 bpydc dissolved in 100mu.L of aqueous sodium hydroxide (10 mg/mL) to give solution A, while 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to give solution B, and the solution A was dropwise added to the solution B and allowed to stand overnight to give Ru-MOFs. The solutions A and B were diluted 1-2 times respectively and mixed, and left standing overnight, so that Ru-MOFs were also formed.
Construction of Ru-MOFs/enzyme composite System
10 mg Ru (bpy) was weighed out 2 bpydc was dissolved in 100. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 2 mg reductase 3GR7 was added to the solution to give solution A, and simultaneously 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to give solution B, which was added dropwise to the solution B and allowed to stand overnight to give the final Ru-MOFs/enzyme complex.
The Ru-MOFs/enzyme complex formed in this comparative example had poor stability in water and thus could not be used in photocatalytic studies because the coordination ability of carboxylate was reduced due to electron withdrawing action of Ru after the 2,2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc) was incorporated into Ru molecules, and thus the MOFs formed were unstable, whereas in examples 1-2, 4'- ([ 2,2' -bipyridine) was incorporated into the complex]5,5' -diyl) dibenzoic acid (bpydba) is incorporated into Ru molecules, and is based on Ru (bpy) because the presence of a benzene ring eases the electron-withdrawing properties of Ru 2 MOFs ratio formed by bpydba is based on Ru (bpy) 2 The MOFs formed by bpydc are stable.
Comparative example 3
Steps (1) - (2) are the same as comparative example 1.
(3) 10 mg Ru (bpy) was weighed out 2 bpydba was dissolved in a mixture of 100. Mu.L of aqueous sodium hydroxide (10 mg/mL) and 80. Mu.L of DMSO (or DMF) to give solution A, while 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) was dissolved in 60. Mu.L of deionized water to give solution B, and the solution A was dropwise added to the solution B and allowed to stand overnight to give no Ru-MOFs/enzyme complex.
Comparative example 4
Steps (1) - (2) are the same as comparative example 1.
(3) 10 mg Ru (bpy) was weighed out 2 bpydba was dissolved in 80. Mu.L sodium hydroxide waterA solution A was obtained by mixing the solution (10 mg/mL) with 40. Mu.L of DMSO (or DMF), and simultaneously, a solution B was obtained by dissolving 4 mg of 1,4,8, 11-tetraazacyclotetradecane zinc (II) in 60. Mu.L of deionized water, and the solution A was dropwise added to the solution B, and the mixture was allowed to stand overnight, whereby Ru-MOFs/enzyme complex could not be obtained. This is because Ru (bpy) is used in an unsuitable amount of aqueous sodium hydroxide and methanol 2 bpydba is poorly soluble and therefore cannot coordinate with zinc (II) 1,4,8, 11-tetraazacyclotetradecane to form MOFs.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.

Claims (10)

1. A heterogeneous photo-enzyme coupled catalyst characterized by: in the catalyst, the oxidoreductase is doped in the transition metal polypyridine complex, and carboxylate groups on the transition metal polypyridine complex doped with the oxidoreductase are coordinated with metal ions to form a transition metal-MOF/oxidoreductase complex in situ; wherein the transition metal is Ru or Ir; the metal ions are zinc ions or nickel ions.
2. A heterogeneous photo-enzyme coupling catalyst according to claim 1, wherein: the load of the oxidoreductase is 5% -10% of the total mass of the heterogeneous photo-enzyme coupling catalyst.
3. A heterogeneous photo-enzyme coupling catalyst according to claim 1 or 2, characterized in that: the oxidoreductase is reductase 3GR7 or reductase 1Z48.
4. A method for preparing the heterogeneous photo-enzyme coupling catalyst according to any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) Preparing a transition metal polypyridine complex by reacting the transition metal complex with 4,4' - ([ 2,2' -bipyridine ] -5,5' -diyl) dibenzoic acid; wherein the transition metal is Ru or Ir;
(2) Reacting 1,4,8, 11-tetraazacyclotetradecane with inorganic metal salt to prepare 1,4,8, 11-tetraazacyclotetradecane metal compound; wherein the inorganic metal salt is zinc salt or nickel salt;
(3) Dissolving a transition metal polypyridine complex in a mixed solution of sodium hydroxide aqueous solution and methanol, and adding oxidoreductase to obtain a solution A; dissolving 1,4,8, 11-tetraazacyclotetradecane metal compound in water with the purity higher than that of deionized water to obtain solution B; dropwise adding the solution A into the solution B, standing overnight, carrying out solid-liquid separation, and collecting solids to obtain a heterogeneous photo-enzyme coupling catalyst; wherein the dosage ratio of the transition metal polypyridine complex to the sodium hydroxide aqueous solution to the methanol is 10 mg: 100. mu L-130 mu L: 50. mu L-80 mu L, and the concentration of the sodium hydroxide aqueous solution is 5 mg/mL-15 mg/mL.
5. The method for preparing a heterogeneous photo-enzyme coupling catalyst according to claim 4, wherein: in the step (1), a transition metal complex is dissolved in DMA, then 4,4' - ([ 2,2' -bipyridine ] -5,5' -diyl) dibenzoic acid is added, stirring reaction is carried out for 16 h-24 h at 130-145 ℃ under the atmosphere of protective gas, after the reaction is finished, an organic solvent is dried by spin, methanol is added for dissolution, filtration is carried out, ethyl acetate and n-hexane with the volume ratio of 1:1-1:3 are added into filtrate, solids are collected, and vacuum drying is carried out, so that the transition metal polypyridine complex is obtained.
6. The method for preparing a heterogeneous photo-enzyme coupling catalyst according to claim 5, wherein: the transition metal complex is cis-dichloro bis (2, 2' -bipyridine) ruthenium or dichloro tetrakis [ 2- (2-pyridyl) phenyl ] iridium (III); the molar ratio of the transition metal complex to the 4,4' - ([ 2,2' -bipyridine ] -5,5' -diyl) dibenzoic acid is 1:1-1:1.5.
7. The method for preparing a heterogeneous photo-enzyme coupling catalyst according to claim 4, wherein: in the step (2), 1,4,8, 11-tetraazacyclotetradecane is dissolved in ethanol to obtain an ethanol solution of 1,4,8, 11-tetraazacyclotetradecane, and inorganic metal salt is dissolved in ethanol to obtain an ethanol solution of inorganic metal salt; and (3) dropwise adding an ethanol solution of inorganic metal salt into an ethanol solution of 1,4,8, 11-tetraazacyclotetradecane, stirring at 30-40 ℃ for reaction for 24-48 hours after the dropwise adding, concentrating ethanol after the reaction is finished, adding diethyl ether for precipitation to obtain a product, and carrying out vacuum drying to obtain the 1,4,8, 11-tetraazacyclotetradecane metal compound.
8. The method for preparing a heterogeneous photo-enzyme coupling catalyst according to claim 7, wherein: the molar ratio of the 1,4,8, 11-tetraazacyclotetradecane to the inorganic metal salt is 1:1-1:1.2; the inorganic metal salt is Zn (NO) 3 ) 2 ·6H 2 O or Ni (NO) 3 ) 2 ·6H 2 O。
9. The method for preparing a heterogeneous photo-enzyme coupling catalyst according to claim 4, wherein: in the step (3), the dosage ratio of the transition metal polypyridine complex, the sodium hydroxide aqueous solution, the methanol, the oxidoreductase and the 1,4,8, 11-tetraazacyclotetradecane metal compound is 10 mg: 100. mu L-130 mu L: 50. mu L-80 mu L:1 mg-2 mg:4 mg.
10. Use of a heterogeneous photo-enzyme coupled catalyst according to any one of claims 1 to 3, characterized in that: the heterogeneous photo-enzyme coupled catalyst is used in an oxidoreductase catalyzed reaction.
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