CN114515581B - Doped CdS photocatalyst and catalytic conversion of CO by same 2 Application in (a) - Google Patents
Doped CdS photocatalyst and catalytic conversion of CO by same 2 Application in (a) Download PDFInfo
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- CN114515581B CN114515581B CN202210196806.7A CN202210196806A CN114515581B CN 114515581 B CN114515581 B CN 114515581B CN 202210196806 A CN202210196806 A CN 202210196806A CN 114515581 B CN114515581 B CN 114515581B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 62
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- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 claims abstract description 43
- BOPGDPNILDQYTO-NNYOXOHSSA-N nicotinamide-adenine dinucleotide Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 BOPGDPNILDQYTO-NNYOXOHSSA-N 0.000 claims abstract description 43
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
- C07H19/16—Purine radicals
- C07H19/20—Purine radicals with the saccharide radical esterified by phosphoric or polyphosphoric acids
- C07H19/207—Purine radicals with the saccharide radical esterified by phosphoric or polyphosphoric acids the phosphoric or polyphosphoric acids being esterified by a further hydroxylic compound, e.g. flavine adenine dinucleotide or nicotinamide-adenine dinucleotide
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Abstract
The invention relates to a doped CdS photocatalyst, which is a CdS photocatalyst doped with Fe, in, ce, cu or Te element and is used for preparing NAD + Catalytic reduction to NADH. The invention also relates to a photo-enzyme coupling catalytic conversion CO based on the doped CdS photocatalyst 2 Comprising: (1) The photo-enzyme coupling double-function catalytic composite material is formed by coupling a doped CdS photocatalyst and a carrier immobilized oxidoreductase; (2) NAD is reacted under the action of doped CdS photocatalyst + Catalytic reduction to NADH; (3) CO under the action of oxidoreductase using NADH as a coenzyme 2 Conversion of CO by enzymatic catalysis 2 Is a high added value compound such as formic acid or formaldehyde. The invention solves the problem of enzyme catalysis of CO 2 The regeneration of coenzyme NADH in the approach of synthesizing important compounds is difficult, the repeated recycling of free enzyme is difficult, and the like, and simultaneously the enzyme reaction is effectively improvedIs stable.
Description
Technical Field
The invention belongs to the field of chemical-biological catalysis, and relates to a doped CdS photocatalyst and a catalytic conversion method thereof for CO 2 In particular to a doped CdS photocatalyst and a catalyst based on the same for catalytic conversion of CO 2 The photo-enzyme coupling double-function catalytic composite material and the preparation and the application thereof.
Background
Enzymatic catalysis of CO 2 The synthesis of 1, 3-dihydroxyacetone or compounds such as ethylene glycol or glycolic acid involves oxidoreductases such as formate dehydrogenase (FateDH), formaldehyde dehydrogenase (FaldDH) and ethylene glycol dehydrogenase, which require NAD (P) H as a coenzyme to function. NADH is expensive and can be catalyzed by photocatalysis + Reducing NADH for cyclic utilization, and reducing production cost. At present, most of photocatalysts used for photocatalytic NADH regeneration are CdS, g-C 3 N 4 、TiO 2 Porphyrins and porphyrin derivatives. However, their practical application is severely limited by weak absorption of visible light, high recombination rate of photo-generated electrons and holes, low photocatalytic conversion efficiency, and the like.
And the free enzyme is difficult to recycle. MOF (metal organic framework material) is a porous material, ZIF-8 is one of MOF materials, and can be used for enzyme immobilization. Existing enzymes catalyze CO 2 The important compound synthesizing way has the problems of difficult regeneration of coenzyme NADH, difficult recycling of free enzyme and the like, and needs to be solved.
Disclosure of Invention
One of the purposes of the present invention is to catalyze CO against enzymes 2 The compound is synthesized by using NAD (P) H as a coenzyme to play a role, and the coenzyme NAD (P) H is relatively expensive, difficult to regenerate and difficult to reuse as a free enzyme.
It is a second object of the present invention to provide a method for catalytic conversion of CO 2 Photo-enzyme coupling double-function catalytic composite materialThe preparation method of the photo-enzyme coupling bifunctional catalytic composite material is based on the doped CdS photocatalyst and the carrier immobilized oxidoreductase, and has higher coenzyme NADH regeneration efficiency and CO 2 Conversion rate.
The invention also aims to provide a method for catalytically converting CO by the photo-enzyme coupling bifunctional catalytic composite material 2 Is used in the field of applications.
To this end, a first aspect of the present invention provides a doped CdS photocatalyst, which is a CdS photocatalyst doped with Fe, in, ce, cu or Te elements; preferably, the doped CdS photocatalyst is used to convert NAD + Catalytic reduction to NADH.
In a second aspect, the present invention provides a method for preparing the doped CdS photocatalyst according to the first aspect, which includes:
step A, na 2 S·9H 2 O、Cd(NO 3 ) 2 ·4H 2 O and the hydrate containing doping elements are respectively dissolved in deionized water to respectively form respective corresponding aqueous solutions;
step B, stirring and leading the mixture to Na under the inert gas atmosphere 2 S·9H 2 Cd (NO) was added dropwise to the aqueous O solution 3 ) 2 ·4H 2 O aqueous solution, after the reaction, obtaining CdS photocatalyst crude dispersion liquid;
step C, stirring, and dropwise adding an aqueous solution containing a hydrate of an element to be doped into the CdS photocatalyst crude product dispersion liquid in an inert gas atmosphere, and reacting to obtain a doped CdS photocatalyst crude product dispersion liquid;
step D, centrifuging and washing the crude dispersion liquid of the doped CdS photocatalyst to remove the raw materials which are not solid, and then drying to obtain the doped CdS photocatalyst;
preferably, the hydrate containing the doping element comprises FeCl 3 .6H 2 O、In(NO 3 ) 3 ·H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and Na 2 TeO 3 ·5H 2 One or more of O.
According to the invention, in step B, na 2 S·9H 2 S and Cd (NO) in O 3 ) 2 ·4H 2 The molar ratio of Cd in O was 1:1.
According to the invention, in step C, the molar ratio of Cd element to doped element is 1 (0.05-1).
In some embodiments of the invention, in step B, the temperature of the reaction is 25-80 ℃.
In some embodiments of the invention, in step C, the temperature of the reaction is 25-80 ℃; the reaction time was 30min.
In a third aspect the invention provides a method for the catalytic conversion of CO 2 The photo-enzyme coupling double-function catalytic composite material is formed by coupling a doped CdS photocatalyst prepared by the first aspect of the invention or the doped CdS photocatalyst prepared by the preparation method of the second aspect of the invention with carrier immobilized oxidoreductase.
According to the invention, the doped CdS photocatalyst is used for NAD + Catalytic reduction to NADH; the oxidoreductase enzyme converts CO 2 The high-value-added compound is converted into the high-value-added compound through enzyme catalysis; preferably, the high value-added compound includes formic acid or formaldehyde.
In some embodiments of the invention, the oxidoreductase is an oxidoreductase that utilizes NADH as a coenzyme; preferably, the oxidoreductase using NADH as a coenzyme comprises formate dehydrogenase (FateDH) and/or formaldehyde dehydrogenase; and/or the carrier is a MOF material; preferably, the MOF material is ZIF-8.
According to a fourth aspect of the present invention, there is provided a method for preparing a photo-enzyme coupled bifunctional catalytic composite material according to the third aspect of the present invention, comprising:
step A, fixing the oxidoreductase in a carrier to obtain a carrier-immobilized oxidoreductase;
and step B, coupling the carrier immobilized oxidoreductase with the doped CdS photocatalyst by a hydrothermal synthesis method to form the photo-enzyme coupling dual-function catalytic composite material.
Fifth aspect of the inventionProvides a photo-enzyme coupling catalytic conversion method for CO based on doped CdS photocatalyst 2 Comprising:
(1) According to a third aspect of the invention for the catalytic conversion of CO 2 Is prepared by the photo-enzyme coupling double-function catalytic composite material or the preparation method in the fourth aspect of the invention and is used for catalytic conversion of CO 2 Is prepared from the photo-enzyme coupled double-function catalytic composite material;
(2) NAD is reacted under the action of doped CdS photocatalyst + Catalytic reduction to NADH;
(3) CO under the action of oxidoreductase using NADH as a coenzyme 2 Conversion of CO by enzymatic catalysis 2 Is a high added value compound; preferably, the high value-added compound includes formic acid or formaldehyde.
In a sixth aspect, the invention provides a photo-enzyme coupled bifunctional catalytic composite material according to the third aspect or a photo-enzyme coupled bifunctional catalytic composite material prepared by a preparation method according to the fourth aspect of the invention for catalytic conversion of CO 2 Comprises the following steps of CO under the action of the photo-enzyme coupling dual-function catalytic composite material 2 The high-value-added compound is converted into the high-value-added compound through enzyme catalysis; preferably, the high value-added compound includes formic acid or formaldehyde.
According to the invention, the application comprises: the photo-enzyme coupling bifunctional catalytic composite material is put into a catalyst containing an electron carrier, an electron donor and NAD + In the system of (2), under the irradiation of light, stirring at uniform speed, firstly, under the action of doped CdS photocatalyst, NAD is added + Catalytic reduction to NADH, and CO reaction with oxidoreductase 2 The high-value-added compound is converted into the high-value-added compound through enzyme catalysis; preferably, the electron mediator includes Mbpy; and/or the electron donor comprises TEOA and/or EDTA.
The invention provides a photocatalyst coupling catalytic conversion method for CO based on Fe, in, ce, cu or Te element doped CdS photocatalyst 2 Is disclosed. The method mainly comprises three parts: (1) Under the condition of visible light irradiation, using CdS doped with Fe, in, ce, cu or Te element as catalyst to make NAD + Catalytic reactionReducing to NADH; (2) An MOF material such as ZIF-8 is used as a carrier for immobilizing enzyme, an oxidoreductase such as formate dehydrogenase (FateDH) or formaldehyde dehydrogenase which takes NADH as a coenzyme is immobilized in the carrier ZIF-8, and the ZIF-8 containing the oxidoreductase and CdS doped with Fe, in, ce, cu or Te elements are coupled into a double-function composite material through a hydrothermal synthesis method; (3) Under the action of a photo-enzyme coupling dual-function composite material, using NADH generated by photocatalysis as coenzyme of oxidoreductase to carry out CO 2 Conversion of CO by enzymatic catalysis 2 Is a compound such as formic acid or formaldehyde, thereby realizing the photo-enzyme coupling catalysis of CO 2 Synthesizing a compound with high added value.
The system can realize the photocatalysis NADH regeneration and enzyme immobilization recycling and the enzyme catalysis of CO 2 The invention solves the problem of enzyme catalysis of CO in the synthesis of important compounds 2 The problem of regeneration of coenzyme NADH in the way of synthesizing important compounds is solved, the problem that free enzyme is difficult to recycle is solved, the efficient conversion of CO2 into high-value compounds by photo-enzyme coupling is realized, the stability of enzyme reaction is effectively improved by enzyme immobilization, and a new idea is provided for synthesizing multi-carbon compounds from 1C compounds. The system organically combines two green catalytic process technologies of photo-enzyme, and opens up a new way for green synthesis technology of multi-carbon compounds.
Drawings
The invention is described in further detail below with reference to the accompanying drawings:
FIG. 1 is a reaction scheme of a CdS photocatalyst doped with Fe, in, ce, cu or Te elements for catalyzing NADH regeneration.
FIG. 2 is a graph of the results of SEM and TEM characterization of the material, a is a graph of the results of SEM and TEM of ZIF-8, b is a graph of the results of SEM and TEM of CdS, c is a graph of the results of SEM and TEM of CdS doped with 10% in, and d is a graph of the results of CdS@ZIF-8& FDH of 10% in. Wherein the large graph is an SEM result graph, and the small graph at the upper right is a TEM result graph.
FIG. 3 is a graph showing the result of laser scanning copolymerization Jiao Biaozheng of ZIF-8&E.
FIG. 4 is a graph showing the result of laser scanning copolymerization Jiao Biaozheng of 10% in-CdS@ZIF-8&E.
FIG. 5 is a graph showing XPS characterization results of an In-doped CdS@ZIF-8& FDH photo-enzyme coupling material, wherein a is a Cd 3d spectrum, b is an S2 p spectrum, c is an In 3d spectrum, and d is a Zn 2p spectrum.
Detailed Description
In order that the invention may be readily understood, the invention will be described in detail below with reference to the accompanying drawings. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
I terminology
The term NAD as used in the present invention + "NADH" refers to oxidized coenzyme I, "NADPH" refers to reduced coenzyme II, "EDTA" refers to ethylenediamine tetraacetic acid, "TEOA" refers to triethanolamine, "MOF" refers to a metal organic framework material, "ZIF-8" refers to a zeolitic imidazolate framework material, "Mbpy" refers to Cp.Rh (bpy) Cl (Cp.pentamethylcyclodiene, bpy refers to 2, 2-bipyridine), and "PVP" refers to polyvinylpyrrolidone.
The term "water" as used herein refers to deionized water, distilled water or ultrapure water unless otherwise specified or defined.
II. Embodiment
In the enzymatic catalysis of CO 2 The invention provides a method for coupling and catalyzing CO conversion based on Fe, in, ce, cu or Te element doped photo-enzyme, which is based on the problems that the oxidation-reduction enzyme is involved in synthesizing formic acid, formaldehyde or 1, 3-dihydroxyacetone or glycol and other compounds, most of the oxidation-reduction enzyme needs NAD (P) H as coenzyme to act, NAD (P) H is relatively expensive, and free enzyme is unfavorable for recycling 2 A system which can be the same asRealizes the photocatalytic NADH regeneration and enzyme immobilization recycling and enzyme catalysis of CO 2 Important compounds are synthesized.
To achieve the above technical solution, according to a first aspect of the present invention, there is provided a doped CdS photocatalyst, which is a CdS photocatalyst doped with Fe, in, ce, cu or Te element, preferably a CdS photocatalyst doped with 5-100% (molar ratio) Fe, in, ce, cu or Te element.
In the invention, the doped CdS photocatalyst is used for preparing NAD + Catalytic reduction to NADH; research shows that the CdS photocatalyst doped with Fe, in, ce, cu or Te element can more effectively convert NAD + Catalytic reduction to NADH.
In a second aspect, the present invention provides a method for preparing the doped CdS photocatalyst according to the first aspect, which includes:
step A, na 2 S·9H 2 O、Cd(NO 3 ) 2 ·4H 2 O and the hydrate containing doping elements are respectively dissolved in deionized water to respectively form respective corresponding aqueous solutions;
step B, na 2 S·9H 2 The O solution is stirred by a magnetic stirrer at 25-80 ℃ and is added to Na under the atmosphere of inert gas (such as nitrogen) 2 S·9H 2 Cd (NO) was added dropwise to the aqueous O solution 3 ) 2 ·4H 2 O aqueous solution, after the reaction, obtaining CdS photocatalyst crude dispersion liquid;
step C, dropwise adding an aqueous solution containing a hydrate of an element to be doped into the CdS photocatalyst crude product dispersion liquid in an inert gas (such as nitrogen) atmosphere, placing the mixture at 25-80 ℃, stirring the mixture by a magnetic stirrer for reaction for 30min, and fixing the shape to obtain the doped CdS photocatalyst crude product dispersion liquid;
and D, centrifuging and washing the crude dispersion liquid of the doped CdS photocatalyst for 3-4 times, removing the raw materials which are not solid, and then drying in vacuum to obtain the doped CdS photocatalyst.
In some embodiments of the invention, the dopant element-containing hydrate comprises FeCl 3 .6H 2 O、In(NO 3 ) 3 ·H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and Na 2 TeO 3 ·5H 2 One or more of O; preferably, the hydrate containing the doping element comprises FeCl 3 .6H 2 O、In(NO 3 ) 3 ·H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O or Na 2 TeO 3 ·5H 2 O; correspondingly, the obtained doped CdS photocatalyst is a CdS photocatalyst doped with Fe, in, ce, cu or Te elements.
According to the invention, in step B, na 2 S·9H 2 S element and Cd (NO in O 3 ) 2 ·4H 2 The molar ratio of Cd element in O is 1:1.
According to the invention, in step C, the molar ratio of Cd element to doped element is 1 (0.05-1).
Based on the above, it is easy to understand that Na during the preparation of doped CdS photocatalyst 2 S·9H 2 S element and Cd (NO in O 3 ) 2 ·4H 2 The molar ratio of Cd element in O to doped element is 1:1 (0.05-1), thus obtaining CdS photocatalyst doped with 5-100% (molar ratio) Fe, in, ce, cu or Te element.
It will be appreciated by those skilled in the art that in step B, na 2 S·9H 2 O aqueous solution and Cd (NO) 3 ) 2 ·4H 2 O aqueous solution, the two are mixed to react to form CdS, the solution becomes turbid from clear and transparent in the reaction process, solid particles are separated out, and CdS is formed, and the CdS is called as a fixed shape in the invention.
In the step C, the crude dispersion of the CdS photocatalyst and the aqueous solution containing the hydrate of the element to be doped are mixed and react to form the doped CdS photocatalyst, and the dispersion maintains a turbid state and is correspondingly called as a 'fixed shape' in the invention.
In a third aspect the invention provides a method for the catalytic conversion of CO 2 Is a photo-enzyme coupled bifunctional catalytic composite material prepared by the first method of the inventionThe doped CdS photocatalyst or the doped CdS photocatalyst prepared by the preparation method of the second aspect of the invention is formed by coupling a carrier immobilized oxidoreductase. Thus, in the present invention, it is used for catalytic conversion of CO 2 The photo-enzyme coupling dual-function catalytic composite material of (1) can be understood as that the doped CdS photocatalyst is coupled with the oxidoreductase through a carrier, namely, the photo-enzyme coupling dual-function catalytic composite material is used for catalytic conversion of CO 2 The photo-enzyme coupling dual-function catalytic composite material is formed by loading and coupling a doped CdS photocatalyst on a carrier loaded with oxidoreductase, and is also expressed as a doped CdS photocatalyst @ carrier in the invention&An oxidoreductase.
According to the invention, the doped CdS photocatalyst is used for NAD + Catalytic reduction to NADH; the oxidoreductase enzyme converts CO 2 The high-value-added compound is converted into the high-value-added compound through enzyme catalysis; preferably, the high value-added compound includes formic acid or formaldehyde.
In some embodiments of the invention, the oxidoreductase is an oxidoreductase that utilizes NADH as a coenzyme; preferably, the oxidoreductase using NADH as a coenzyme comprises formate dehydrogenase (FateDH) and/or formaldehyde dehydrogenase.
In some preferred embodiments of the invention, the carrier is a MOF material, preferably ZIF-8; correspondingly, for the catalytic conversion of CO 2 The photo-enzyme coupled bifunctional catalytic composite material can be expressed as doped CdS@ZIF-8&E, wherein E is an oxidoreductase.
In a fourth aspect, the present invention provides a method for preparing a photo-enzyme coupled bifunctional catalytic composite according to the third aspect of the present invention, which can also be understood as providing a method for preparing a photo-enzyme coupled composite doped with a CdS photocatalyst of Fe, in, ce, cu or Te element, comprising:
step A, fixing the oxidoreductase in a carrier to obtain a carrier-immobilized oxidoreductase;
and step B, coupling the carrier immobilized oxidoreductase with the doped CdS photocatalyst by a hydrothermal synthesis method to form the photo-enzyme coupling dual-function catalytic composite material.
Specifically, the carrier is a MOF material (for example, ZIF-8), the doped CdS photocatalyst is a CdS photocatalyst doped with Fe, in, ce, cu or Te elements, and the preparation method of the photo-enzyme coupling bifunctional catalytic composite material comprises the following steps:
step T1, sequentially adding oxidoreductase and Zn (NO) into a 2-methylimidazole solution placed on a magnetic stirrer at 25-30 DEG C 3 ) 2 ·6H 2 O aqueous solution and polyvinylpyrrolidone (PVP) solution, and obtaining ZIF-8 after reaction&E a multi-enzyme immobilization material solution;
step T2, adding a doped CdS photocatalyst crude product dispersion liquid into the ZIF-8&E multienzyme fixing material solution, and stirring for 30min to obtain a doped CdS@ZIF-8&E photoenzyme coupling dual-function catalytic composite material crude product dispersion liquid;
step T3, for doped CdS@ZIF-8&E, carrying out low-temperature centrifugation (0-4 ℃) treatment on the crude dispersion liquid of the photo-enzyme coupling dual-function catalytic composite material, washing with water, removing unfixed raw materials, and then drying under vacuum condition to obtain the catalyst for catalytic conversion of CO 2 Is doped with CdS@ZIF-8&E photo-enzyme coupling double-function catalytic composite material.
The preparation method of the photo-enzyme coupling bifunctional catalytic composite material is characterized by comprising the following steps of:
(1) In step T1, the molar concentration of 2-methylimidazole was 1.25M, zn (NO 3 ) 2 ·6H 2 The molar concentration of O is 0.31M, and the mass concentration of PVP is 0.08mg/mL; the oxidoreductase is preferably a formate dehydrogenase.
(2) In step T2, cd 2+ (CdS) and Zn 2+ [Zn(NO 3 ) 2 ·6H 2 O]The molar ratio of (2-10) to 1, that is, the coupling ratio of CdS to ZIF-8 is (2-10) to 1.
In the invention, the synthetic material can be characterized by a laser scanning confocal method, and the enzyme is proved to be immobilized in a carrier.
In the invention, the synthesized material can be characterized by one or more of Scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), X-ray diffraction (XRD), fourier transform infrared spectrophotometer (FT-IR), X-ray photoelectron spectroscopy (XPS) and the like, and the successful synthesis of the material is proved.
In a fifth aspect, the present invention provides a photocatalyst-based photocatalytic CO conversion coupled with doped CdS 2 Comprising:
(1) According to a third aspect of the invention for the catalytic conversion of CO 2 Is prepared by the photo-enzyme coupling double-function catalytic composite material or the preparation method in the fourth aspect of the invention and is used for catalytic conversion of CO 2 Is prepared from the photo-enzyme coupled double-function catalytic composite material; the composite material is loaded with oxidation-reduction enzyme [ formate dehydrogenase (FateDH) and/or formaldehyde dehydrogenase (Formaldehyde dehydrogenase) by CdS photocatalyst doped with Fe, in, ce, cu or Te element]Is formed on and coupled to a carrier (e.g., MOF material, preferably ZIF-8);
(2) Under the action of CdS photocatalyst doped with Fe, in, ce, cu or Te element, NAD is reacted + Catalytic reduction to NADH;
(3) Under the action of a photo-enzyme coupling dual-function composite material, using NADH generated by photocatalysis as coenzyme of oxidoreductase to carry out CO 2 Conversion of CO by enzymatic catalysis 2 Is a compound such as formic acid or formaldehyde, thereby realizing the photo-enzyme coupling catalysis of CO 2 Synthesizing a compound with high added value.
In a sixth aspect, the invention provides a photo-enzyme coupled bifunctional catalytic composite material according to the third aspect of the invention or a photo-enzyme coupled bifunctional catalytic composite material prepared by a preparation method according to the fourth aspect of the invention for catalytic conversion of CO 2 Comprises the following steps of CO under the action of the photo-enzyme coupling dual-function catalytic composite material 2 The high-value-added compound is converted into the high-value-added compound through enzyme catalysis; preferably, the high value-added compound includes formic acid or formaldehyde.
Based on the above, the application can also be understood as the catalytic conversion of CO using the photo-enzyme coupled bifunctional catalytic composite material according to the third aspect of the present invention or the photo-enzyme coupled bifunctional catalytic composite material prepared by the preparation method according to the fourth aspect of the present invention 2 A method for preparing high added value compounds such as formic acid or formaldehyde.
According to the invention, the application comprises:
the photo-enzyme coupling bifunctional catalytic composite material is put into a catalyst containing an electron carrier, an electron donor and NAD + In the system of (2), under the irradiation of Xe lamp, stirring and reacting at uniform speed, firstly, under the action of doped CdS photocatalyst, NAD is reacted + Catalytic reduction to NADH, and CO reaction with oxidoreductase 2 The high added value compound is converted into the high added value compound through enzyme catalysis.
According to the invention, the CO is reacted under the action of the photo-enzyme coupling double-function catalytic composite material 2 The method for converting into high value-added compounds by enzyme catalysis is characterized in that:
(1) The molar concentration of the electron mediator is 0.15-0.30mM.
(2) The molar concentration of the electron donor is 0.25-0.50M.
(3) The NAD + The molar concentration of (C) is 0.2-1mM.
(4) The sodium bicarbonate replaces CO 2 As a carbon source substrate, the molar concentration is 3-100mM.
(5) The concentration of the photo-enzyme coupling bifunctional catalytic composite material is 1-4mg/mL.
(6) The wavelength lambda of the Xe lamp is more than or equal to 420nm.
(7) The temperature of the reaction is 20-40 ℃, and the reaction time is 18-40h.
In some embodiments of the invention, the electron mediator comprises Mbpy.
In other embodiments of the invention, the electron donor comprises TEOA and/or EDTA, preferably TEOA.
It will be appreciated by those skilled in the art that the above-described reaction of NAD with doped CdS photocatalyst + The catalytic reduction to NADH is understood to be the present invention provides a method for regenerating NADH, based on a coenzyme NADH regenerating system of a CdS photocatalyst doped with Fe, in, ce, cu or Te element, which comprises in particular the introduction of a CdS photocatalyst doped with Fe, in, ce, cu or Te element into a catalyst comprising an electron mediator, an electron donor and NAD + In the system (2), NAD is stirred at a constant speed under the irradiation of a Xe lamp + Catalytic reduction to NADH; preferably, during the reaction, the absorbance at 340nm is measured by sampling over a fixed period of time; further preferably, after the completion of the reaction, the photocatalyst is separated by centrifugation and reused.
It will be further appreciated by those skilled in the art that the above application can also be understood as utilizing the CdS@ZIF-8 doped with Fe, in, ce, cu or Te elements provided by the present invention&Catalytic conversion of CO by E-photo-enzyme coupling system 2 The preparation process of formic acid, formaldehyde and other high value added compound includes adding NAD into the system + Mbpy, electron donor, sodium bicarbonate, cdS@ZIF-8 doped with Fe, in, ce, cu or Te element&E, stirring and reacting the double-functional composite material with the photo-enzyme at uniform speed under the irradiation of an Xe lamp, and adding CO 2 Catalytic reduction to formic acid or formaldehyde and other compounds.
The detection method and the detection instrument in the invention are as follows:
(1) Absorbance of OD340 was measured using a micro-spectrophotometer (Thermo).
(2) The formate ion was detected using an ion chromatograph (Thermo).
III, examples
The present invention will be specifically described below by way of specific examples. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, are commercially available.
Example 1: preparation of electron mediator Mbpy
Weigh 61.806 mg [ Cp. Rhol ] 2 ] 2 Dispersing into 4mL of anhydrous methanol followed by the addition of 31.806 mg of 2, 2-bipyridine caused the suspension to become clear. After the solution became clear, an appropriate amount of anhydrous diethyl ether was added and Mbpy solid precipitated. The solid Mbpy was collected by centrifugation and purged with nitrogen to remove the remaining anhydrous diethyl ether and methanol.
Example 2: preparation of CdS photocatalyst doped with 10% Fe element (molar ratio)
Weigh 5mmol Na 2 S·9H 2 O，5mmol Cd(NO 3 ) 2 ·4H 2 O and 0.5mmol FeCl 3 .6H 2 O is respectively dissolved in 25mL of deionized water. Na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixing shape, dropwise adding FeCl under nitrogen atmosphere 3 .6H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape. Centrifuging the CdS photocatalyst doped with Fe element, washing with deionized water for 3 times to remove the raw material which is not solid, and drying under vacuum condition to obtain the CdS photocatalyst doped with 10% (molar ratio) Fe.
Example 3: preparation of CdS photocatalyst doped with 10% in element (molar ratio)
Weigh 5mmol Na 2 S·9H 2 O，5mmol Cd(NO 3 ) 2 ·4H 2 O and 0.5mmol In (NO) 3 ) 3 ·H 2 O was dissolved in 25mL deionized water, respectively. Na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixed shape, drop wise In (NO) under nitrogen atmosphere 3 ) 3 ·H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape. Centrifuging the CdS photocatalyst doped with the In element, washing the CdS photocatalyst with deionized water for 3 times to remove the raw material which is not solid, and then drying the raw material under vacuum condition to obtain the CdS photocatalyst doped with 10% (molar ratio) In.
Example 4: preparation of 10% Ce-doped CdS photocatalyst
Weigh 5mmol Na 2 S·9H 2 O，5mmol Cd(NO 3 ) 2 ·4H 2 O and 0.5mmol Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 25mL deionized water, respectively. Na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixed shape, dropwise adding Ce (NO 3 ) 3 ·6H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape. Centrifuging the CdS photocatalyst doped with Ce element and washing 3 times with deionized water to remove the unconsolidated matterThe shaped raw material is then dried under vacuum to produce a 10% (mole ratio) Ce doped CdS photocatalyst.
Example 5: preparation of CdS photocatalyst doped with 10% Cu element (molar ratio)
Weigh 5mmol Na 2 S·9H 2 O，5mmol Cd(NO 3 ) 2 ·4H 2 O and 0.5mmol Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 25mL deionized water, respectively. Na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixed shape, cu (NO) was added dropwise under nitrogen atmosphere 3 ) 2 ·3H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape. Centrifuging the CdS photocatalyst doped with Cu element, washing with deionized water for 3 times to remove the raw material which is not solid, and drying under vacuum condition to obtain the CdS photocatalyst doped with 10% (molar ratio) Cu.
Example 6: preparation of CdS photocatalyst doped with 10% Te element (molar ratio)
Weigh 5mmol Na 2 S·9H 2 O，5mmol Cd(NO 3 ) 2 ·4H 2 O and 0.5mmol Na 2 TeO 3 ·5H 2 O was dissolved in 25mL deionized water, respectively. Na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixing shape, adding Na dropwise under nitrogen atmosphere 2 TeO 3 ·5H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape. Centrifuging the CdS photocatalyst doped with Te element, washing with deionized water for 3 times to remove the raw material which is not solid, and drying under vacuum condition to obtain the CdS photocatalyst doped with 10% (molar ratio) Te.
Example 7: cdS photocatalyst doped with Fe, in, ce, cu or Te element for catalyzing NADH regeneration
1mg/mL of CdS photocatalyst doped with Fe, in, ce, cu or Te element and 1mM of NAD are added into 50mM of phosphoric acid buffer solution with pH of 8.0 + ，0.15mM Mbpy，0.2The total reaction system is 8mL by 5M TEOA, the reaction is carried out for 30min in a dark environment, then the reaction is carried out for 4h under the irradiation of Xe lamp with the wavelength lambda more than or equal to 420nm, the light absorption value of OD340 is detected by a micro-spectrophotometer (Thermo) at intervals of 30min, and the NADH regeneration reaction process is shown in figure 1. The NADH yield of the CdS photocatalyst doped with 10% in element reaches 89.21%.
Example 8: preparation of CdS@ZIF-8&E photo-enzyme coupling dual-function composite material doped with In element
Weigh 2.43mmol Na 2 S·9H 2 O，2.43mmol Cd(NO 3 ) 2 ·4H 2 O and 0.243mmol In (NO) 3 ) 3 ·H 2 O，0.31mmol Zn(NO 3 ) 2 ·6H 2 O,12.5mmol of 2-methylimidazole was dissolved in 10mL of deionized water, and 0.08mg of PVP solution was dissolved in 1mL of deionized water, respectively.
To a solution of 2-methylimidazole at 25℃on a magnetic stirrer, 8mg of formate dehydrogenase (FDH, sigma) was added followed by Zn (NO) 3 ) 2 ·6H 2 O solution and polyvinylpyrrolidone (PVP) solution to obtain ZIF-8&FDH (FDH, nail acid dehydrogenase) enzyme immobilization material solution;
na is mixed with 2 S·9H 2 The O solution was placed at 30℃and stirred with a magnetic stirrer, and Cd (NO) was added dropwise under nitrogen 3 ) 2 ·4H 2 O, fixed shape, drop wise In (NO) under nitrogen atmosphere 3 ) 3 ·H 2 O, placing at 30 ℃, stirring for 30min by a magnetic stirrer, and fixing the shape to obtain a CdS photocatalyst solution doped with 10% (molar ratio) In;
adding ZIF-8 into CdS photocatalyst solution doped with 10% (molar ratio) of In&Stirring the FDH enzyme immobilization material solution for 30min to obtain a bifunctional composite material CdS@ZIF-8 doped with 10% (molar ratio) In element&FDH. Wherein Cd is synthesized in the material 2+ With Zn 2+ The molar ratio of (2) is 8:1;
centrifuging the difunctional composite material In a low-temperature refrigerated centrifuge, washing the difunctional composite material with deionized water for 3 times to remove unfixed raw materials, and then drying the unfixed raw materials under vacuum conditions to obtain the CdS@ZIF-8& FDH photo-enzyme coupling difunctional composite material doped with 10% (molar ratio) In element.
Example 9: characterization of materials
SEM and TEM characterization was performed on the synthesized ZIF-8, cdS doped with 10% (mole ratio) In element and CdS@ZIF-8& FDH doped with 10% (mole ratio) In element, and the shape of the result In FIG. 2 is consistent with the shape of the four materials, which indicates that the four materials were successfully synthesized.
Fluorescein isothiocyanate has fluorescence absorption at 488 nm. After staining the FDH with fluorescein isothiocyanate, ZIF-8& FDH (FDH, nail dehydrogenase) and 10% (molar ratio) In doped CdS@ZIF-8& FDH material were synthesized using the synthesis procedure of example 8, followed by detection using a laser scanning confocal microscope (LCMS) at 488nm, two kinds of green fluorescence were found to appear, indicating that FDH was immobilized In ZIF-8, and that coupling of ZIF-8& FDH with 10% (molar ratio) In doped CdS did not result In leakage of enzyme (see FIGS. 3 and 4). Characterization of the doped elements of the In-doped cds@zif-8&E photo-enzymatic coupling material using an esclab 250 electron spectrometer (Thermo Fisher Scientific, USA) resulted In the observation of Cd, S, in, zn elements present, indicating successful synthesis of the doped coupling material (see fig. 5).
Example 10: cdS@ZIF-8 doped with In element&E photo-enzyme coupling system for catalyzing CO 2 Synthesis of formic acid
In 50mM phosphate buffer solution with pH of 8.0, 4mg/mL CdS@ZIF-8 doped with 10% (molar ratio) In element is added&FDH photo-enzyme coupling double-function composite material, 1mM NAD + ，100mM NaHCO 3 0.30mM Mbpy,0.50M TEOA, the total reaction system is 8mL, the reaction is carried out for 24h under the condition of 35 ℃ under the irradiation of Xe lamp with the wavelength lambda being more than or equal to 420nm, the yield of formic acid is detected by an ion chromatograph (Thermo), and the yield of the formic acid is 11.6mg/L.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (7)
1. For catalytic conversion of CO 2 The photo-enzyme coupling double-function catalytic composite material is formed by coupling a doped CdS photocatalyst and a carrier immobilized oxidoreductase;
the doped CdS photocatalyst is a CdS photocatalyst doped with Fe, in, ce, cu or Te element and is used for doping NAD + Catalytic reduction to NADH;
the oxidoreductase enzyme converts CO 2 Conversion to formic acid or formaldehyde by enzymatic catalysis;
the oxidoreductase is an oxidoreductase using NADH as a coenzyme;
the oxidoreductase using NADH as a coenzyme includes formate dehydrogenase FateDH and/or formaldehyde dehydrogenase; the carrier is ZIF-8;
the preparation method of the photo-enzyme coupling bifunctional catalytic composite material comprises the following steps:
step T1, sequentially adding oxidoreductase and Zn (NO) into a 2-methylimidazole solution placed on a magnetic stirrer at 25-30 DEG C 3 ) 2 ·6H 2 O aqueous solution and polyvinylpyrrolidone solution, and obtaining ZIF-8 after reaction&E a multi-enzyme immobilization material solution;
step T2, adding a doped CdS photocatalyst crude product dispersion liquid into the ZIF-8&E multienzyme fixing material solution, and stirring for 30min to obtain a doped CdS@ZIF-8&E photoelectroenzyme coupling dual-function catalytic composite material crude product dispersion liquid;
step T3, for doped CdS@ZIF-8 at 0 to-4deg.C&E, carrying out low-temperature centrifugal treatment on the crude dispersion liquid of the photo-enzyme coupling bifunctional catalytic composite material, washing with water to remove unfixed raw materials, and then drying under vacuum condition to obtain the catalyst for catalytic conversion of CO 2 Is doped with CdS@ZIF-8&E photo-enzyme couplingA bifunctional catalytic composite.
2. The photo-enzyme coupled bifunctional catalytic composite of claim 1, wherein the preparation method of the doped CdS photocatalyst comprises:
step A, na 2 S·9H 2 O、Cd(NO 3 ) 2 ·4H 2 O and the hydrate containing doping elements are respectively dissolved in deionized water to respectively form respective corresponding aqueous solutions;
step B, stirring and leading the mixture to Na under the inert gas atmosphere 2 S·9H 2 Cd (NO) was added dropwise to the aqueous O solution 3 ) 2 ·4H 2 O aqueous solution, after the reaction, obtaining CdS photocatalyst crude dispersion liquid;
step C, stirring, and dropwise adding an aqueous solution containing a hydrate of an element to be doped into the CdS photocatalyst crude product dispersion liquid in an inert gas atmosphere, and reacting to obtain a doped CdS photocatalyst crude product dispersion liquid;
step D, centrifuging and washing the crude dispersion liquid of the doped CdS photocatalyst to remove the raw materials which are not solid, and then drying to obtain the doped CdS photocatalyst;
the hydrate containing the doping element comprises FeCl 3 .6H 2 O、In(NO 3 ) 3 ·H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and Na 2 TeO 3 ·5H 2 One or more of O.
3. The photo-enzyme coupled bifunctional catalytic composite of claim 2, wherein in step B, na 2 S·9H 2 S and Cd (NO) in O 3 ) 2 ·4H 2 The molar ratio of Cd in O is 1:1; and/or, in the step C, the molar ratio of Cd element to doped element is 1 (0.05-1).
4. The photo-enzyme coupled bifunctional catalytic composite of claim 2, wherein in step B, the temperature of the reaction is 25-80 ℃; and/or, in step C, the temperature of the reaction is 25-80 ℃; the reaction time was 30min.
5. A method of preparing a photo-enzyme coupled bifunctional catalytic composite according to any one of claims 1-4, comprising:
step T1, sequentially adding oxidoreductase and Zn (NO) into a 2-methylimidazole solution placed on a magnetic stirrer at 25-30 DEG C 3 ) 2 ·6H 2 O aqueous solution and polyvinylpyrrolidone solution, and obtaining ZIF-8 after reaction&E a multi-enzyme immobilization material solution;
step T2, adding a doped CdS photocatalyst crude product dispersion liquid into the ZIF-8&E multienzyme fixing material solution, and stirring for 30min to obtain a doped CdS@ZIF-8&E photoelectroenzyme coupling dual-function catalytic composite material crude product dispersion liquid;
step T3, for doped CdS@ZIF-8 at 0 to-4deg.C&E, carrying out low-temperature centrifugal treatment on the crude dispersion liquid of the photo-enzyme coupling bifunctional catalytic composite material, washing with water to remove unfixed raw materials, and then drying under vacuum condition to obtain the catalyst for catalytic conversion of CO 2 Is doped with CdS@ZIF-8&E photo-enzyme coupling double-function catalytic composite material.
6. The photo-enzyme coupled bifunctional catalytic composite material of any one of claims 1-4 or the photo-enzyme coupled bifunctional catalytic composite material prepared by the preparation method of claim 5, for catalytic conversion of CO 2 Comprises the following steps of CO under the action of the photo-enzyme coupling dual-function catalytic composite material 2 Is enzymatically converted into formic acid or formaldehyde.
7. The application according to claim 6, characterized in that it comprises: the photo-enzyme coupling bifunctional catalytic composite material is put into a catalyst containing an electron carrier, an electron donor and NAD + In the system of (2), under the irradiation of light, stirring at uniform speed, firstly, under the action of doped CdS photocatalyst, NAD is added + Catalytic reduction toNADH, CO under the action of oxidoreductase 2 Conversion to formic acid or formaldehyde by enzymatic catalysis; the electron transfer body is Mbpy; mbpy is cp×rh (bpy) Cl, where cp×is pentamethylcyclodiene and bpy is 2, 2-bipyridine; and/or the electron donor comprises TEOA and/or EDTA.
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