CN114192173A - Photocatalyst for NADH regeneration and preparation method and application thereof - Google Patents
Photocatalyst for NADH regeneration and preparation method and application thereof Download PDFInfo
- Publication number
- CN114192173A CN114192173A CN202111310335.XA CN202111310335A CN114192173A CN 114192173 A CN114192173 A CN 114192173A CN 202111310335 A CN202111310335 A CN 202111310335A CN 114192173 A CN114192173 A CN 114192173A
- Authority
- CN
- China
- Prior art keywords
- tio
- photocatalyst
- mixture
- heterogeneous
- nadh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 93
- 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 title claims abstract description 70
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 title claims abstract description 69
- 238000011069 regeneration method Methods 0.000 title claims abstract description 56
- 230000008929 regeneration Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000005515 coenzyme Substances 0.000 claims description 33
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 28
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 15
- 235000014655 lactic acid Nutrition 0.000 claims description 14
- 239000004310 lactic acid Substances 0.000 claims description 14
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 150000004696 coordination complex Chemical class 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 48
- 239000010936 titanium Substances 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 230000003197 catalytic effect Effects 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000523 sample Substances 0.000 description 13
- 229950006238 nadide Drugs 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 239000003504 photosensitizing agent Substances 0.000 description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 102000004316 Oxidoreductases Human genes 0.000 description 3
- 108090000854 Oxidoreductases Proteins 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000006250 one-dimensional material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 102000003960 Ligases Human genes 0.000 description 2
- 108090000364 Ligases Proteins 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007871 hydride transfer reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010975 amethyst Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a photocatalyst for NADH regeneration and a preparation method and application thereof, belonging to the field of photocatalysis. The preparation method comprises the following steps: (1) mixing Ti3C2TxUniformly dispersing in HCl solution with the concentration of 0-5 mol/L to obtain a mixture A; (2) reacting the mixture A at the temperature of 180-200 ℃ for 10-12 h to obtain powder of a precipitate B; (3) uniformly dispersing all the powder in the step (2) in 0-5 mol/L HCl solution to obtain a mixture C; (4) the mixture C reacts for 20-24 h at the temperature of 180-200 ℃ to obtain Ti3C2/TiO2A heterogeneous photocatalyst. The photocatalyst has a unique layered structure and higher carrier mobility, expands the light absorption range of photochemical regeneration of NADH to a visible light region, has simple and easy process, and shows excellent performanceCatalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of photocatalyst preparation, and particularly relates to a photocatalyst for NADH regeneration, and a preparation method and application thereof.
Background
The application of biological enzyme is widely existed in the biochemical transformation process in nature. The biological enzyme catalytic factor has the advantages of high reaction rate, good compatibility, high stereoselectivity, mild reaction conditions, few byproducts and the like, and plays a vital role in the fields of chemical synthesis, new drug development and the like. Although the catalytic activity of the oxidoreductase as a most typical biological enzyme catalyst is high, the oxidoreductase also has the disadvantage that a coenzyme is required to show continuous and efficient reaction activity, namely, one molecule of coenzyme is required for each molecule of substrate catalyzed by the oxidoreductase. One of the most common coenzymes in nature is Nicotinamide Adenine Dinucleotide (NADH). In view of the high price, the method realizes the high-efficiency and low-cost regeneration of NADH coenzyme, and has very important significance in the enzyme catalysis industry. In order to solve this problem, a series of regeneration methods have been proposed, and the coenzyme regeneration methods can be classified into four types according to the mechanism of coenzyme regeneration: enzymatic, electrochemical, photochemical, and chemical methods. The light-driven coenzyme regeneration method is a method for realizing high-efficiency and rapid coenzyme in-situ regeneration by utilizing photosensitive materials to capture and utilize clean and sustainable solar energy. Under the background of increasingly exhausted energy, the light-driven regenerated coenzyme has wide development prospect.
In the light-driven coenzyme regeneration technology, a photosensitizer has the function of generating photoproduction electrons and holes under the excitation of illumination; the electron mediator is used as an electron shuttle between the photosensitizer and the NAD +, and transfers photo-generated electrons and hydrogen protons in water to the electron acceptor NAD +; the electron donor functions to allow the photosensitizer, which has lost electrons, to recover electrons to prevent the electrons from being transferred in the reverse direction, thereby reducing the electron-hole recombination rate. The core of the coenzyme light-driven regeneration lies in the preparation of high-performance photosensitizer. The common photosensitizer is a metal oxide photocatalyst, but the application of the photosensitizer in the industry is severely limited by the following defects: on the one hand, most metal oxides only absorb in the ultraviolet region, and do not absorb or have weak absorption in the visible region, so that the energy utilization rate is low, and the influence of ultraviolet rays on enzymes cannot be avoided. On the other hand, it is more important that the metal oxide semiconductor has a serious phase recombination of photogenerated electrons and photogenerated holes, so that the proportion of effective carriers which can reach the surface of the catalyst and participate in the reaction is low, and the photocatalytic efficiency is low. For example, commercial P25 (TiO)2) Although has the advantages of proper energy band potential, high chemical stability, higher photoelectric conversion efficiency and the like. However, due to TiO2The forbidden band width is 3.2eV, the forbidden band width is relatively wide, the specific surface area is small, the response range to visible light is narrow, the absorption is only carried out in an ultraviolet region, and the light energy utilization rate is low. And the recombination rate of the photoproduction electron-hole pairs is higher, so that the photocatalytic activity and the catalytic efficiency are reduced, and the industrial application of the photo-induced electron-hole pairs is limited. Meanwhile, the high-activity noble metal-doped metal oxide catalyst has the defects of complex preparation process, poor stability and high cost. Therefore, the photocatalyst which has the advantages of simple preparation process, no toxicity, low cost, high catalytic activity, good stability, low photon-generated carrier recombination efficiency and wide visible light absorption range is provided.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the Ti which has simple and nontoxic preparation process, low cost and meets the most suitable existing conditions of regenerative enzyme and synthetase3C2/TiO2Heterogeneous phase photocatalysisAn agent; the invention expands the light absorption range of the catalyst to the visible light region, improves the energy utilization rate, avoids the adverse effect of the participation of enzyme under ultraviolet light, and achieves higher photoresponse catalytic activity; the invention also relates to Ti3C2/TiO2The heterogeneous photocatalyst is applied to the aspects related to the regeneration of the photocatalytic coenzyme, and the yield of the regenerated coenzyme NADH is obviously improved.
In order to achieve the purpose, the invention adopts the technical scheme that: ti3C2/TiO2A method for preparing a heterogeneous photocatalyst, the method comprising the steps of:
(1) mixing Ti3C2TxUniformly dispersing in HCl solution with the concentration of 0-5 mol/L to obtain a mixture A;
(2) reacting the mixture A at the temperature of 180-200 ℃ for 10-12 h, cooling to obtain a precipitate B, washing the precipitate B with water, performing suction filtration, and performing vacuum drying to obtain powder;
(3) uniformly dispersing all the powder obtained in the step (2) in 0-5 mol/L HCl solution to obtain a mixture C;
(4) reacting the mixture C at the temperature of 180-200 ℃ for 20-24 h, cooling to obtain a precipitate D, washing the precipitate D with water, performing suction filtration, and performing vacuum drying to obtain the Ti3C2/TiO2A heterogeneous photocatalyst.
The object of the invention is to obtain a metal carbide (Ti)3C2) Starting from the design and synthesis of series MXene-based novel composite photocatalysts, the Ti of the invention3C2/TiO2The heterogeneous-phase photocatalyst is a novel graphene-like two-dimensional material, has a unique layered structure and high carrier mobility, and can reduce the photon-generated carrier recombination efficiency of the photocatalyst and expand the light absorption range of the photocatalyst to a visible light region. Wherein, Ti3C2/TiO2The hydrochloric acid concentration and the hydrothermal reaction time used in the preparation process of the heterogeneous photocatalyst have important influences on the morphology of the heterogeneous photocatalyst. (001) Ti was synthesized by using hydrochloric acid concentrations of 0mol/L, 0.25mol/L and 5mol/L, respectively3C2/TiO2Heterogeneous photocatalyst, Ti3C2/TiO2Heterogeneous photocatalyst and (111) Ti3C2/TiO2A heterogeneous photocatalyst. With noble metal-doped TiO2Compared with a one-dimensional material, the preparation method of the novel graphene-like two-dimensional material is simpler and has lower cost, and the graphene-like two-dimensional material is never used for the regeneration of NADH before.
As a preferred embodiment of the preparation process of the present invention, in the step (1), the volume of HCl solution and Ti are used3C2TxThe mass ratio of (A) to (B) is as follows: ti3C2Tx:15mL of HCl (100 mg); in the step (1), the concentration of the HCl solution is 0.25-5 mol/L mol/L.
More preferably, in step (1), the method for uniformly dispersing is as follows: stirring for 30min, and ultrasonic treating for 10 min.
In the step (2), the mixture A is reacted at the temperature of 180-200 ℃ for 10-11 h and cooled to obtain a precipitate B; in the step (2), the temperature of the vacuum drying is 60 ℃, and the time is 6 h.
As a preferable embodiment of the preparation method, in the step (3), the concentration of the HCl solution is 0.25-5 mol/L; the volume ratio of the mixture C to the mixture A is 1: 1.
More preferably, in step (3), the method for uniformly dispersing is as follows: stirring for 30min, and ultrasonic treating for 10 min.
In the step (4), the mixture C is reacted at the temperature of 200 ℃ for 20-22 h to obtain a precipitate D; in the step (4), the temperature of the vacuum drying is 60 ℃, and the time is 6 h.
As a preferred embodiment of the production process of the present invention, in the step (1), the concentration of the HCl solution is 0.25 mol/L; in the step (2), the mixture A is reacted for 10 hours at the temperature of 180 ℃ to obtain the precipitate B.
As a preferable embodiment of the production method of the present invention, in the step (3), the concentration of the HCl solution is 0.25 mol/L; in the step (4), the mixture C is reacted for 20 hours at the temperature of 200 ℃ to obtain the precipitate D.
As a more preferable embodiment of the production method of the present invention, in the solution A in the step (1), the concentration of the HCl solution is 0.25 mol/L; in the step (2), the hydrothermal reaction temperature is 180 ℃ and the time is 10 hours; in the step (3), the concentration of the HCl solution is 0.25 mol/L; in the step (4), the hydrothermal reaction temperature is 200 ℃ and the time is 20 hours.
When the concentration of the HCl solution and the hydrothermal reaction temperature and time are as above, the Ti is prepared3C2/TiO2The heterogeneous phase photocatalyst has better performance.
The present invention also provides a Ti as described in any of the above3C2/TiO2Ti prepared by preparation method of heterogeneous-phase photocatalyst3C2/TiO2A heterogeneous photocatalyst.
Ti produced by the above method3C2/TiO2The heterogeneous photocatalyst has a unique layered structure and high carrier mobility, the light absorption range of the heterogeneous photocatalyst is expanded to a visible light region, the energy utilization rate is improved, the adverse effect of enzyme participation under ultraviolet light is avoided, and the photon-generated carrier recombination efficiency of the photocatalyst can be reduced. With noble metal-doped TiO2Ti compares with one-dimensional material (traditional photocatalyst)3C2/TiO2The heterogeneous photocatalyst is simpler to prepare and lower in cost, and meets the optimal existence condition of regenerated enzyme and synthetase so as to achieve higher photoresponse catalytic activity.
The invention also provides the Ti3C2/TiO2Use of a heterogeneous phase photocatalyst in coenzyme NADH regeneration, said use comprising the steps of:
(1) adding the photocatalyst into coenzyme NAD +, an electron donor and a metal complex to obtain a mixture E;
(2) placing the mixture E in a reaction container, and reacting to obtain NADH under the conditions of introducing nitrogen gas, using visible light or ultraviolet light as a light source, wherein the irradiation distance is 15 cm-1 m, the temperature is 25-37 ℃, and the pH value is 6.5-7.5;
(3) shading the mixture E for 15min to obtain a blank sample, and then sampling every other hour until the eighth sample is obtained; and centrifuging the sample at 20 ℃ and 12000r/min for 15min, taking the supernatant, diluting by 10 times, measuring the light absorption value at 340nm, and calculating by using an NADH standard curve to obtain the NADH yield.
Ti of the invention3C2/TiO2The heterogeneous photocatalyst is used for regenerating coenzyme NADH, and can show excellent catalytic performance.
In the application of coenzyme NADH regeneration, an electron donor is an important link in a light-driven enzyme catalytic system, because electrons required by a product generated in the system are derived from the electron donor. Meanwhile, an electron donor is also an important factor influencing the catalytic efficiency of the system, electrons on a valence band of the photosensitizer after being excited by light are excited to jump to a conduction band to generate photoproduction electrons, the valence band generates electron holes, the electron holes need the electron donor to quench the holes, and the quenching efficiency influences the electron transfer efficiency and further influences the catalytic efficiency of the system. Finally, in a coenzyme-based photo-driven enzyme catalysis complex system, an electron donor provides electrons under the photo-induction through a photosensitizer, and the electrons are finally transferred to the enzyme to catalyze the oxidation-reduction reaction. The electron donor is a substance with reducibility, and can eliminate photoproduction holes in a reaction system in time and form an oxidation compound, so that the electron transfer efficiency is improved. The choice of electron donor requires that the oxidizing compound formed by itself after oxidation does not interfere with the proper functioning of the photochemical cycle, that the electron donor has a pKa value close to the pH of the system to provide the most efficient electron supply, and that a lower oxidation potential is required. Some common electron donors include lactic acid, ascorbic acid, Triethanolamine (TEOA), ethylenediaminetetraacetic acid (EDTA), and 2- (N-morpholino) ethanesulfonic acid (MES). The optimal electron donor is TEOA and EDTA, the electron donor can realize single electron oxidation, the catalytic efficiency of the system is improved, the generated oxidation intermediate has no influence on the system and has high stability, and besides, the Pka value of the electron donor is between 5 and 8, which accords with the catalytic pH value range of most enzyme reactions.
Metal complexes such as chiral diamine ligands of rhodium, bipyridyl ligands of rhodium [ Cp Rh (bpy) H2O]2+And [ Rh (dmbpy)2Cl2]+Rhodium, a carbophenanthrene ligand [ CpRh (Me) ]4phen)Cl]Cl and [ (. eta.5-C)5Me5)Rh(3,4,7,8-Me4-1,10-phen)Cl]Cl and the like as an electron mediator and a hydride transfer agent can not only help a photocatalyst to transfer electrons and increase the stability and activity of NADH, but also prevent inactive NADH isomers and (NAD)2And (4) generation of a dimer. The special technical scheme selects [ Cp + Rh (bpy) H]+From [ Cp + Rh (bpy) (H) by chemical or electrochemical processes2O)]2+Obtaining and regenerating. It is used as a hydride transfer reagent on NAD (P) +, yielding only the enzymatically active 1,4-NAD (P) H isomer.
As a preferred embodiment of the invention applied in coenzyme NADH regeneration, in step (1), the electron donor is one of EDTA-2Na, EDTA-4Na, TEOA and lactic acid; the metal complex is [ Cp Rh (bpy) (H)2O)]2(ii) a The mixture E comprises the following components in proportion: photocatalyst: coenzyme NAD +: electron donor: metal complex (30-45) mg:1 mmol: 0.15 mmol: 0.25 mmol.
Preferably, the metal complex may include not only [ Cp × rh (bpy)) (H2O)]2And may further include metal complexes commonly used in the art, not limited herein.
As a more preferred embodiment of the present invention in the coenzyme NADH regeneration application, in the step (1), the electron donor is EDTA-2 Na; in the step (1), the mixture E comprises the following components in proportion: photocatalyst: coenzyme NAD +: electron donor: metal complex 45mg:1 mmol: 0.15 mmol: 0.25 mmol. In the step (2), the light source is a 300W xenon lamp, the irradiation distance is 65cm, the pH value is 7, and the temperature is 30 ℃.
Compared with the electron acceptor, the EDTA-2Na is used as the electron donor to carry out coenzyme NADH regeneration reaction, and different types of photocatalysts show good performance. The mixture E comprises the following components in proportion: photocatalyst: coenzyme NAD +: electron donor: metal complex 45mg:1 mmol: 0.15 mmol: the best catalytic performance is shown at 0.25 mmol.
Compared with the prior art, the invention has the following beneficial effects:
(1)Ti3C2/TiO2the heterogeneous photocatalyst catalysis NADH regeneration construction process is simple and easy to implement, the operation complexity is low, and the activity of the synthesized material is stable. With TiO2Compared with one-dimensional materials, the yield of the regenerated coenzyme NADH is obviously improved.
(2)Ti3C2/TiO2The heterogeneous photocatalyst has a unique layered structure and higher carrier mobility, can reduce the photon-generated carrier recombination efficiency of the photocatalyst, and shows excellent catalytic performance when used for NADH regeneration;
(3)Ti3C2/TiO2the heterogeneous phase photocatalyst catalyzes the photochemical regeneration of NADH, and the light absorption range of the heterogeneous phase photocatalyst is expanded to a visible light region. The regeneration process can be carried out under the irradiation of a xenon lamp, the energy utilization rate is high, and the influence of ultraviolet light on enzyme is avoided;
(4) the regeneration process does not need the participation of enzyme and toxic electronic vector methyl amethyst, thereby not only reducing the cost, but also avoiding the defect that the regeneration enzyme and the synthetase are difficult to control due to different optimal existence conditions.
Drawings
FIG. 1 is a comparison of XRD patterns of inventive examples 1-4 and comparative example 2.
FIG. 2 is a graph comparing the IR spectra of examples 1-4 of the present invention and comparative example 2.
FIG. 3 is a graph showing the comparison of NADH yields in the case where the electron donor is EDTA-2Na in examples 1-4 of the present invention and comparative example 1.
FIG. 4 is a graph showing the comparison of NADH yields in the case where the electron donor is EDTA-4Na in examples 1-4 of the present invention and comparative example 1.
FIG. 5 is a graph showing the comparison of NADH yields in the conditions in which the electron donor is TEOA in examples 1-4 of the present invention and comparative example 1.
FIG. 6 is a graph showing the comparison of NADH yields in the case where the electron donor is lactic acid in examples 1 to 4 of the present invention and comparative example 1.
FIG. 7 is a graph showing the comparison of NADH yields in the case of EDTA-2Na, EDTA-4Na, TEOA, and lactic acid as electron donors in examples 1-4 of the present invention and comparative example 1, respectively.
FIG. 8 is a scanning electron micrograph of examples 1 to 4 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. The reagents used in the following examples are commercially available.
Example 1
Ti as an example of the present invention3C2/TiO2A method for preparing a heterogeneous photocatalyst, the method comprising the steps of: weighing 100mg of Ti3C2TxAdding into 15mL of HCl with the concentration of 0.25mol/L, stirring the mixture for 30min, and carrying out ultrasonic treatment for 10min to obtain a uniform mixture A. And then transferring the precipitate into a 100mL reaction kettle, reacting for 10h at 180 ℃ under a hydrothermal condition, cooling to obtain a precipitate B, washing with water, filtering by suction, and drying in vacuum at 60 ℃ for 6h to obtain powder. Adding the obtained sample powder into 15mL of HCl with the concentration of 0.25mol/L, stirring for 30min, and performing ultrasonic treatment for 10min to obtain a mixture C. Then transferring the mixture C into a 100mL reaction kettle, reacting for 20h at 200 ℃ under the hydrothermal condition, cooling to obtain a precipitate D, washing, filtering and vacuum-drying the precipitate D at 60 ℃ for 6h to obtain powder, namely Ti for NADH regeneration3C2/TiO2A heterogeneous photocatalyst;
ti prepared in this example3C2/TiO2The heterogeneous photocatalyst is used for NADH regeneration reaction, and the regeneration reaction comprises the following steps of taking a 300W xenon lamp as a light source (the irradiation distance is 65cm), and adding 45mg of Ti3C2/TiO2Adding the heterogeneous photocatalyst into 30mL EDTA-2Na, EDTA-4Na, TEOA, and lactic acid electron donor solution with concentration of 5mmol/L, respectively, stirring for 15min, performing ultrasonic treatment for 15min, and adding 0.25mmol of metal complex [ Cp Rh (bpy)) (H2O)]2Adding 1mmol of NAD + standard substance, and carrying out shading reaction for 15min at the temperature of 30 ℃ and the pH value of 7 under the condition of introducing nitrogen in the whole process to obtain a blank sample. Then sampling every hour until the eighth sample is taken, centrifuging the obtained sample at 20 ℃ and 12000r/min for 15min, and takingAnd (5) measuring the light absorption value at 340nm of the diluted supernatant by 10 times, and calculating the NADH yield through an NADH standard curve.
Ti obtained as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 7, the NADH yields are 82.1%, 77.5%, 39.7% and 31.3%, respectively.
Example 2
(001) Ti as an example of the present invention3C2/TiO2A method for preparing a heterogeneous photocatalyst, the method comprising the steps of: weighing 100mg of Ti3C2TxAdding into 15mL deionized water, stirring the mixture for 30min, and carrying out ultrasonic treatment for 10min to obtain a mixture A. And then transferring the precipitate into a 100mL reaction kettle, reacting for 10h at 180 ℃ under a hydrothermal condition, cooling to obtain a precipitate B, washing with water, filtering by suction, and drying in vacuum at 60 ℃ for 6h to obtain powder. And adding the obtained sample powder into 15mL of deionized water, stirring for 30min, and performing ultrasonic treatment for 10min to obtain a mixture C. Then transferring the mixture C into a 100mL reaction kettle, reacting for 20h at 200 ℃ under the hydrothermal condition, cooling to obtain a precipitate D, washing, filtering and vacuum-drying the precipitate D at 60 ℃ for 6h to obtain powder, namely (001) Ti for NADH regeneration3C2/TiO2A heterogeneous photocatalyst;
(001) Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction, and the catalyst except the catalyst is (001) Ti3C2/TiO2The heterogeneous photocatalyst is different from that of example 1, and other regeneration reaction conditions are the same as those of example 1.
(001) Ti prepared as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are 39.7%, 40.1%, 12.6% and 9.51%, respectively.
Example 3
As an embodiment of the inventionExample one of (111) Ti3C2/TiO2A method for preparing a heterogeneous photocatalyst, the method comprising the steps of: weighing 100mg of Ti3C2TxAdding into 15mL of HCl with the concentration of 5mol/L, stirring the mixture for 30min, and carrying out ultrasonic treatment for 10min to ensure that the mixture is uniform to obtain a mixture A. And then transferring the precipitate into a 100mL reaction kettle, reacting for 10h at 180 ℃ under a hydrothermal condition, cooling to obtain a precipitate B, washing with water, filtering by suction, and drying in vacuum at 60 ℃ for 6h to obtain powder. Adding the obtained sample powder into 15mL of HCl with the concentration of 5mol/L, stirring for 30min, and performing ultrasonic treatment for 10min to obtain a mixture C. Then transferring the mixture C into a 100mL reaction kettle, reacting for 20h at 200 ℃ under the hydrothermal condition, cooling to obtain a precipitate D, washing, filtering and vacuum-drying the precipitate D at 60 ℃ for 6h to obtain powder, namely (111) Ti for NADH regeneration3C2/TiO2A heterogeneous photocatalyst;
(111) Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction, except that the catalyst is (111) Ti3C2/TiO2The heterogeneous photocatalyst is different from that of example 1, and other regeneration reaction conditions are the same as those of example 1.
The above-obtained (111) Ti3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are 31.3%, 25.9%, 11.4% and 15.4%, respectively.
Example 4
72h treated Ti as an example of the invention3C2/TiO2A method for preparing a heterogeneous photocatalyst, the method comprising the steps of: adding the sample powder prepared by the method in example 1 into 15mL of HCl with the concentration of 0.25mol/L, stirring the mixture for 30min, carrying out ultrasonic treatment for 10min to make the mixture uniform, then transferring the mixture into a 100mL reaction kettle, reacting for 10h at 180 ℃ under a hydrothermal condition, cooling, washing the sample with water, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ for 6 h; the obtained sample powder was added to 15mStirring the mixture for 30min in HCl with the L concentration of 0.25mol/L, performing ultrasonic treatment for 10min to make the mixture uniform, transferring the mixture into a 100mL reaction kettle, reacting for 20h at 200 ℃ under the hydrothermal condition, cooling, washing the final sample with water, performing suction filtration, and performing vacuum drying for 6 h; the obtained powder is Ti after 72h treatment3C2/TiO2；
72h of treated Ti as prepared in this example3C2/TiO2Performing NADH regeneration reaction on the heterogeneous photocatalyst, and removing the catalyst by Ti after 72h treatment3C2/TiO2The heterogeneous photocatalyst is different from that of example 1, and other regeneration reaction conditions are the same as those of example 1.
The above-obtained 72 h-treated Ti3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are respectively 50.2%, 47.8%, 34.9% and 19.5%.
Example 5
Ti as an example of the present invention3C2/TiO2The preparation method of the heterogeneous photocatalyst is the same as that of the example 1 except that the hydrothermal condition of the step (2) is 190 ℃ for reaction for 12 hours, and the hydrothermal condition of the step (4) is 190 ℃ for reaction for 24 hours, which is different from that of the example 1.
Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst was subjected to NADH regeneration reaction under the same conditions as in example 1 except that the catalyst preparation conditions and the added mass were 40mg, which was different from example 1.
Ti obtained as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and a lactic acid electron donor, and the NADH yield is 39.7%, 30.4%, 19.6% and 16.3% respectively.
Example 6
Ti as an example of the present invention3C2/TiO2A method for preparing a heterogeneous photocatalyst, saidThe method is the same as the example 1 except that the hydrothermal condition of the step (2) is 200 ℃ for reaction for 11h, and the hydrothermal condition of the step (4) is 200 ℃ for reaction for 22h, which is different from the example 1.
Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst was subjected to NADH regeneration reaction under the same conditions as in example 1 except that the catalyst preparation conditions and the added mass were 45mg, which was different from example 1.
Ti obtained as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are respectively 46.3%, 38.2%, 22.7% and 19.4%.
Example 7
Ti as an example of the present invention3C2/TiO2The preparation method of the heterogeneous photocatalyst is the same as that of the example 1 except that the hydrothermal condition of the step (2) is 180 ℃ for 10 hours, and the hydrothermal condition of the step (4) is 180 ℃ for 20 hours, which is different from that of the example 1.
Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst was subjected to NADH regeneration reaction under the same conditions as in example 1 except that the catalyst preparation conditions and the added mass were 35mg, which was different from example 1.
Ti obtained as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are respectively 30.4%, 25.1%, 10.7% and 14.8%.
Example 8
Ti as an example of the present invention3C2/TiO2The preparation method of the heterogeneous photocatalyst is the same as that of the example 1 except that the hydrothermal condition of the step (2) is 190 ℃ for reaction for 10 hours, and the hydrothermal condition of the step (4) is 200 ℃ for reaction for 20 hours, and is different from that of the example 1.
Ti prepared in this example3C2/TiO2The heterogeneous photocatalyst was subjected to NADH regeneration reaction under the same conditions as in example 1 except that the catalyst preparation conditions and the added mass were 45mg, which was different from example 1.
Ti obtained as described above3C2/TiO2The heterogeneous photocatalyst is subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA and lactic acid electron donor, and as shown in FIG. 4, the NADH yields are respectively 48.9%, 40.1%, 26.7% and 21.5%.
Comparative example 1
Chemically pure TiO produced by Macklin as a comparative example of the invention2Carrying out NADH regeneration reaction, wherein the catalyst is commercial TiO2Otherwise, the conditions were the same as in examples 1 to 4.
The above commercial TiO2The catalyst was subjected to NADH regeneration reaction under the conditions of EDTA-2Na, EDTA-4Na, TEOA, and lactate electron donor, as shown in FIG. 4, to obtain NADH yields of 77.8%, 64.2%, 15.9%, and 24.1%, respectively.
Comparative example 2
Ti as a comparative example of the present invention3C2The method for preparing (1), the method comprising the steps of: weighing 100mg of Ti3C2TxAdding into 15mL of HCl with the concentration of 0.25mol/L, stirring the mixture for 30min, carrying out ultrasonic treatment for 10min to make the mixture uniform, then transferring the mixture into a 100mL reaction kettle, and reacting for 10h at 180 ℃ under hydrothermal conditions. After cooling, the sample is washed with water, filtered and dried in vacuum at 60 ℃ for 6 hours to obtain powder which is Ti3C2。
1) Analysis of material morphology and structure
As shown in FIG. 1, example 1 showed rutile TiO at 27.26 °, 53.69 °, 54.87 °2(PDF78-1510) characteristic peaks, anatase TiO appearing at 25.16 °2(PDF 21-1272) and a characteristic peak of a layer-like Ti is evident in the vicinity of 17.64 DEG3C2FIG. 8(a) and (e) show Ti prepared in example 13C2/TiO2The morphology of the heterogeneous phase photocatalyst. Example 2 samples without hydrochloric acid, corresponding mainly to anatase and lamellar Ti3C2FIG. 8(b) and (f) show (001) Ti prepared in example 23C2/TiO2The morphology of the heterogeneous phase photocatalyst. Example 3 sample with 5mol/L hydrochloric acid added, corresponding mainly to rutile and lamellar Ti3C2FIG. 8(c) and (g) show (111) Ti prepared in example 33C2/TiO2The morphology of the heterogeneous phase photocatalyst. With the prolonging of the hydrothermal process, the titanium dioxide nano-sheets continuously grow on the titanium carbide nano-sheets, and the Ti is treated for 72h3C2/TiO2The heterogeneous photocatalyst is simultaneously provided with Ti3C2And TiO2Has been predominantly TiO2Mainly, mainly TiO as shown in FIGS. 8(d) and (h)2This is due to the excessively long hydrothermal time of Ti3C2Conversion of nanosheets to TiO2Nanosheets. 1660cm in the IR spectrum shown in FIG. 2-1And 3500cm-1The broad peak at can be respectively attributed to adsorption on Ti3C2And TiO2The above-OH is a Ti-O stretching vibration peak, which further indicates that Ti-O stretching vibration exists because-OH adsorption exists on the surface of the titanium carbide. At 550cm-1The nearby peak is the stretching vibration peak of O-Ti-O, and the stronger the vibration amplitude of the peak is, the TiO is shown by the larger the vibration amplitude is2The higher the content of (b).
2) Analysis of catalytic Properties of NADH regeneration reaction
As can be seen from Table 1 and FIGS. 3 to 7, example 1 is superior to examples 2 and 3, indicating that Ti prepared with a hydrochloric acid concentration of 0.25mol/L is obtained3C2/TiO2Heterogeneous photocatalyst is (001) Ti3C2/TiO2And (111) Ti3C2/TiO2Has more excellent catalytic performance. Example 4 is superior to examples 2-3, although less than example 1, indicating that the catalyst of example 1 has significant catalytic performance even after aging. Example 1 is superior to examples 5 to 8, showing that the optimal conditions for the first hydrothermal reaction are 180 ℃ for 10 hours and the optimal conditions for the second hydrothermal reaction areThe addition amount of the catalyst is optimally 45mg after 20 hours at 200 ℃, and the most suitable electron donor is EDTA-2 Na. The performance of example 1 is superior to the commercial TiO of comparative example 12The yield of the regenerated coenzyme NADH is obviously improved.
TABLE 1 comparison of NADH yields in examples 1-8 with comparative examples 1-2
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. Ti3C2/TiO2The preparation method of the heterogeneous photocatalyst is characterized by comprising the following steps:
(1) mixing Ti3C2TxUniformly dispersing in HCl solution with the concentration of 0-5 mol/L to obtain a mixture A;
(2) reacting the mixture A at the temperature of 180-200 ℃ for 10-12 h, cooling to obtain a precipitate B, washing the precipitate B with water, performing suction filtration, and performing vacuum drying to obtain powder;
(3) uniformly dispersing the powder obtained in the step (2) in 0-5 mol/L HCl solution to obtain a mixture C;
(4) reacting the mixture C at the temperature of 180-200 ℃ for 20-24 h, cooling to obtain a precipitate D, washing the precipitate D with water, performing suction filtration, and performing vacuum drying to obtain the Ti3C2/TiO2A heterogeneous photocatalyst.
2. The Ti of claim 13C2/TiO2The preparation method of the heterogeneous photocatalyst is characterized in that in the step (1), the volume of HCl solution and Ti are3C2TxThe mass ratio of (A) to (B) is as follows: ti3C2Tx:15mL of HCl (100 mg); in the step (1), the concentration of the HCl solution is 0.25-5 mol/L.
3. The Ti of claim 13C2/TiO2The preparation method of the heterogeneous photocatalyst is characterized in that in the step (2), the mixture A reacts at the temperature of 180-200 ℃ for 10-11 h and is cooled to obtain a precipitate B; in the step (2), the temperature of the vacuum drying is 60 ℃, and the time is 6 h.
4. The Ti of claim 13C2/TiO2The preparation method of the heterogeneous photocatalyst is characterized in that in the step (3), the concentration of an HCl solution is 0.25-5 mol/L; the volume ratio of the mixture C to the mixture A is 1: 1.
5. The Ti of claim 13C2/TiO2The preparation method of the heterogeneous photocatalyst is characterized in that; in the step (4), reacting the mixture C at the temperature of 200 ℃ for 20-22 h to obtain a precipitate D; in the step (4), the temperature of the vacuum drying is 60 ℃, and the time is 6 h.
6. Ti according to any one of claims 1 to 53C2/TiO2Ti prepared by preparation method of heterogeneous-phase photocatalyst3C2/TiO2A heterogeneous photocatalyst.
7. Ti according to claim 63C2/TiO2The application of heterogeneous photocatalyst in coenzyme NADH regeneration.
8. The Ti of claim 73C2/TiO2The application of the heterogeneous phase photocatalyst in coenzyme NADH regeneration is characterized by comprising the following steps:
(1) ti according to claim 63C2/TiO2Adding the heterogeneous photocatalyst into coenzyme NAD +, an electron donor and a metal complex to obtain a mixture E;
(2) and introducing nitrogen into the mixture E in the whole process, taking visible light or ultraviolet light as a light source, irradiating for 15-100cm, and reacting at the temperature of 25-37 ℃ and the pH value of 6.5-7.5 to obtain NADH.
9. The Ti of claim 83C2/TiO2The application of the heterogeneous-phase photocatalyst in coenzyme NADH regeneration is characterized in that in the step (1), the electron donor is one of EDTA-2Na, EDTA-4Na, TEOA and lactic acid; the metal complex is [ Cp Rh (bpy) (H)2O)]2(ii) a The mixture E comprises the following components in proportion: photocatalyst: coenzyme NAD +: electron donor: metal complex (30-45) mg:1 mmol: 0.15 mmol: 0.25 mmol.
10. The Ti of claim 83C2/TiO2The application of the heterogeneous-phase photocatalyst in coenzyme NADH regeneration is characterized in that in the step (1), the mixture E comprises the following components in proportion: photocatalyst: coenzyme NAD +: electron donor: metal complex 45mg:1 mmol: 0.15 mmol: 0.25 mmol; in the step (2), the light source is a 300W xenon lamp, the irradiation distance is 65cm, the pH value is 7, and the temperature is 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111310335.XA CN114192173A (en) | 2021-11-05 | 2021-11-05 | Photocatalyst for NADH regeneration and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111310335.XA CN114192173A (en) | 2021-11-05 | 2021-11-05 | Photocatalyst for NADH regeneration and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114192173A true CN114192173A (en) | 2022-03-18 |
Family
ID=80647017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111310335.XA Pending CN114192173A (en) | 2021-11-05 | 2021-11-05 | Photocatalyst for NADH regeneration and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114192173A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597940A (en) * | 2004-08-03 | 2005-03-23 | 天津大学 | Photochemical process for regenerating coenzyme NADH |
| CN105197992A (en) * | 2015-09-10 | 2015-12-30 | 同济大学 | Preparation method of lamellar stacking titanium dioxide nanoparticles |
| CN111530485A (en) * | 2019-11-25 | 2020-08-14 | 中国石油大学(华东) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof |
| CN111568934A (en) * | 2020-04-28 | 2020-08-25 | 五邑大学 | Method for extracting moringa oleifera total flavonoids by using deep eutectic solvent |
| CN112456551A (en) * | 2020-12-03 | 2021-03-09 | 五邑大学 | In-situ growth TiO based on two-dimensional MXene2Heterogeneous composite material and preparation method and application thereof |
| AU2021101809A4 (en) * | 2021-04-08 | 2021-05-27 | Anhui University Of Technology | A Method For Catalyzing The Dehydrogenation of Formic Acid With Visible Light With PdAu Nanosheet Catalyst |
-
2021
- 2021-11-05 CN CN202111310335.XA patent/CN114192173A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597940A (en) * | 2004-08-03 | 2005-03-23 | 天津大学 | Photochemical process for regenerating coenzyme NADH |
| CN105197992A (en) * | 2015-09-10 | 2015-12-30 | 同济大学 | Preparation method of lamellar stacking titanium dioxide nanoparticles |
| CN111530485A (en) * | 2019-11-25 | 2020-08-14 | 中国石油大学(华东) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof |
| CN111568934A (en) * | 2020-04-28 | 2020-08-25 | 五邑大学 | Method for extracting moringa oleifera total flavonoids by using deep eutectic solvent |
| CN112456551A (en) * | 2020-12-03 | 2021-03-09 | 五邑大学 | In-situ growth TiO based on two-dimensional MXene2Heterogeneous composite material and preparation method and application thereof |
| AU2021101809A4 (en) * | 2021-04-08 | 2021-05-27 | Anhui University Of Technology | A Method For Catalyzing The Dehydrogenation of Formic Acid With Visible Light With PdAu Nanosheet Catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107649168B (en) | Method for degrading bisphenol A in water through photocatalysis and catalyst used by method | |
| CN113457711B (en) | Graphite-phase carbon nitride-loaded magnesium monoatomic composite material, preparation method thereof and method for preparing hydrogen peroxide through photocatalysis | |
| CN112569969A (en) | Synthesis and application method of BiOBr photocatalyst containing optically controlled oxygen vacancies | |
| CN113546661A (en) | Carbon-based single-atom photocatalyst and preparation method and application thereof | |
| CN106582888A (en) | TiO2-Pd-PPy compound photocatalyst and preparation method and application thereof | |
| KR20120026656A (en) | Novel visible light active graphene-porphyrin photocatalyst, method for regeneration of oxidoreductase cofactor and method for enzymatic production of formic acid from carbon dioxide using the same | |
| CN114950402A (en) | TiO 2 /CeO 2 Heterojunction photocatalyst and preparation method thereof | |
| CN109320532B (en) | Cadmium complex with function of catalyzing photo-degradation of azo dye and preparation method and application thereof | |
| CN113058601B (en) | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting | |
| CN107117683B (en) | Method for catalytically degrading low-concentration antibiotics In water body by using MOFs containing In-Co under visible light | |
| CN114192173A (en) | Photocatalyst for NADH regeneration and preparation method and application thereof | |
| CN116422378A (en) | Cu (copper) alloy 2 O-CuXbpy composite material CO 2 Preparation method and application of photoreduction catalyst | |
| CN108067229B (en) | Pd/BiVO4Composite nano photocatalyst and preparation method and application thereof | |
| CN110038636B (en) | AgI/Ag-Ce-2MI composite photocatalyst and preparation and application thereof | |
| CN116764658A (en) | g-C 3 N 4 Ag/AgCl composite photocatalyst and preparation method thereof | |
| CN114573086A (en) | Method for catalytically degrading low-concentration antibiotics in water body by SEP @ CTFs composite material under visible light | |
| CN113908873B (en) | Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst | |
| CN106902828B (en) | A kind of processing method of acetyl spiramycin antibiotic waste water | |
| CN1978054A (en) | Photocatalyst for preparing hydrogen by visible-light photocatalytic decomposing H2S and preparing method thereof | |
| CN115155618B (en) | ZnIn rich in Zn vacancy 2 S 4 Preparation method and application of photocatalyst | |
| CN114797906B (en) | BiOCl@Bi 2 S 3 In-situ synthesis method and application of composite material | |
| CN114870842B (en) | Immobilized Z-shaped Fe 2 O 3 /CuFe 2 O 4 I Cu photocatalyst composite film and preparation method and application thereof | |
| CN114849761B (en) | Photocatalytic material and preparation method and application thereof | |
| CN116003480A (en) | Method for photochemically regenerating coenzyme NADH | |
| CN116116450A (en) | Carbon-nitrogen photocatalyst rich in bulk defects and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |