CN113546661A - Carbon-based single-atom photocatalyst and preparation method and application thereof - Google Patents
Carbon-based single-atom photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 37
- 238000011069 regeneration method Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000005515 coenzyme Substances 0.000 claims abstract description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
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- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 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 2
- 239000000243 solution Substances 0.000 claims description 62
- 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 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
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- 238000001035 drying Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- BAWFJGJZGIEFAR-NNYOXOHSSA-O NAD(+) 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-O 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- -1 acetylacetone compound Chemical class 0.000 claims description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
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- 239000004202 carbamide Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- 239000004615 ingredient Substances 0.000 claims 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims 1
- 229940101270 nicotinamide adenine dinucleotide (nad) Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 46
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- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229950006238 nadide Drugs 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002953 phosphate buffered saline Substances 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 8
- 108090000854 Oxidoreductases Proteins 0.000 description 7
- 102000004316 Oxidoreductases Human genes 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 102000004190 Enzymes Human genes 0.000 description 6
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- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 6
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- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
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- 102000007698 Alcohol dehydrogenase Human genes 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 108090000698 Formate Dehydrogenases Proteins 0.000 description 1
- 240000000451 Zingiber zerumbet Species 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
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- 150000007974 melamines Chemical class 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- 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
Abstract
The invention belongs to the technical field of catalysts, relates to a novel carbon-based monatomic photocatalyst for coenzyme regeneration reaction, and particularly relates to a carbon-based monatomic photocatalyst as well as a preparation method and application thereof. The catalyst comprises an active metal component and a carrier, wherein the active metal component is loaded on the carrier in a monoatomic dispersion state; the active metal component is any one of Rh and Co; the carrier is a two-dimensional ultrathin graphite phase carbon nitride substrate. The preparation method is that a two-dimensional ultrathin carbon nitride substrate with good biocompatibility is used as a carrier, and Rh or Co based monatomic metal center is doped into a carrier framework to realize a novel carbon based monatomic photocatalyst; the preparation method has simple and feasible synthesis steps and high practical value. The prepared catalyst is applied to the photocatalytic NADH coenzyme regeneration reaction, and shows excellent regeneration efficiency and cyclic usability; realizes the coenzyme regeneration process without adding an electronic regulator.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to a novel carbon-based monatomic photocatalyst for coenzyme regeneration reaction, and particularly relates to a carbon-based monatomic photocatalyst as well as a preparation method and application thereof.
Background
In the past, nature has adopted biological enzymes to carry out biochemical transformation, and biological enzymes have the advantages of high reaction rate, good compatibility, high stereoselectivity, mild reaction conditions, few byproducts and the like, and play a vital role in the fields of chemical synthesis, new drug development and the like. The oxidoreductases, as a typical class of biological enzyme catalysts, have great potential in the application of conventional catalytic reactions, for example, the oxidoreductases have shown higher catalytic efficiency in the reactions of carbonyl reduction, oxidation of carbon-hydrogen bonds, cyclization of carbon-carbon double bonds, Baeyer-Villiger oxidation and the like. However, many oxidoreductases require a coenzyme in order to exhibit sustained and efficient reactivity (oxidoreductases require the participation of one molecule of coenzyme for every molecule of substrate catalyzed by the oxidoreductase). One of the most common coenzymes in nature is Nicotinamide Adenine Dinucleotide (NADH), and in view of the high price of NADH, the realization of efficient and low-cost regeneration of NADH has a very important meaning in the enzyme catalysis industry.
Usually the regeneration of NADH is an oxidation state NAD+By a reducing process of, i.e. NAD++2e-+H+→ NADH. The currently reported methods for regenerating NADH mainly include 6 major categories, which are respectively enzymatic (using formate dehydrogenase, etc.), chemical (using inorganic salts), electrochemical (direct cathodic reduction or using organometallic complexes as proton transport media), photocatalytic (using carbon nitride as photocatalyst), homogeneous catalyst regeneration (using complexes of Rh, Ru and Pt), heterogeneous catalyst regeneration (Pt/Al)2O3). The photochemical method takes renewable solar energy as an energy source, realizes high-efficiency conversion from light energy to chemical energy, shows higher NADH selectivity and yield, and is expected to realize high-efficiency low-cost regeneration of NADH and subsequent enzymatic conversion application thereof.
Under visible light, the photocatalyst absorbs light energy and generates photo-generated carriers, and photo-generated electrons are further transferred to NAD (NAD) under the action of an electron regulator+In the above, the reduced coenzyme NADH is formed by combining with hydrogen ions, i.e. the regeneration process of NADH, and the continuously regenerated NADH can be used for the activation of oxidoreductase to drive a series of enzyme biochemical reactions. The photocatalyst reported at present mainly contains metal oxygenAnd compounds, nitrides, metalloporphyrin complexes, xanthene dyes, and the like. For example, in documents d.yang, et al, ind.eng.chem.res.2017,56,6247-6255, zingiber zerumbet et al at tianjin university obtained quantum dot/carbon nitride composite material using melamine modified with cyanamide as precursor, the composite material has better visible light absorption capacity and charge separation efficiency, and can realize high-efficiency regeneration of NADH (NADH yield is about 40%), and then the continuous production of methanol can be realized by combining the light regeneration system with alcohol dehydrogenase. In the document x.ji, et al, adv.funct.mater.2018,28,1705083, a tensor researcher at the institute of the chinese academy of sciences constructed porphyrin/SiO2The integrated system of/Cp Rh (bpy) Cl successfully improves the NADH yield to 75 percent, and the regenerated NADH realizes the catalysis of CO by the biological enzyme through the coupling with formate dehydrogenase2Conversion to formic acid. Liu, et al, Energy environ, sci.2013,6,1486, markus antonietti, liu, germany, with carbon nitride as the photocatalyst and Cp × rh (bpy) as the electron mediator, achieve 100% regeneration of NADH under visible light irradiation. Alternatively, the photogenerated electrons can pass through carbon nitride and NAD without the mediation of an electron mediator+The pi-pi interaction between them is directly transited to realize partial regeneration of NADH, but its NADH yield is reduced to 50%, and the selectivity of 1,4-NADH is very low. In documents r.yadav, et al, j.am.chem.soc.2012,134,11455-11461, Jin-ok Baeg et al, korea, developed a composite photocatalyst of polyanthraquinone substituted porphyrin and graphene, with which high efficiency regeneration of NADH (NADH yield of about 45%) was achieved. On the basis, the generated NADH is combined with alcohol dehydrogenase to efficiently reduce benzophenone and derivatives to form corresponding chiral alcohol, and has higher stereoselectivity.
Although photocatalytic NADH regeneration systems have advanced to some extent in recent years, they also face a number of issues that are urgently to be broken through. For one, most oxidoreductases require NAD+NADH can show catalytic activity, the yield of NADH of the currently reported catalyst system is low, and the design of an efficient photocatalytic NADH regeneration system has very important significance; secondly, the current photocatalytic system requires additional electron modifiers (such as Cp Rh (bpy) Cl, etc.), and is developed without adding electron modifiersNAD of electronic modulators+The NADH photocatalytic regeneration system can avoid unnecessary energy loss and is beneficial to improving the practicability of NADH regeneration. Therefore, the development of a high-activity, electron mediator-free, photocatalytic coenzyme regeneration system has become an important research direction in this field.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a carbon-based single-atom photocatalyst as well as a preparation method and application thereof, the catalyst can realize an efficient coenzyme regeneration process without an electronic regulator under visible light, has excellent catalytic performance when being used for photocatalytic coenzyme regeneration reaction, can efficiently realize the complete regeneration of 1,4-NADH coenzyme under the condition of no electronic regulator, and has simple and feasible preparation process and better practical value.
The technical scheme of the invention is as follows:
a carbon-based monatomic photocatalyst comprising an active metal component and a carrier, the active metal component being supported on the carrier in a monoatomic dispersion state; the active metal component is any one of Rh and Co; the carrier is a two-dimensional ultrathin graphite phase carbon nitride substrate.
Furthermore, the content of the active metal component in the catalyst is 0.1-10.0 wt%.
Furthermore, the content of the active metal component in the catalyst is 0.1-5.0 wt%.
A preparation method of a carbon-based single-atom photocatalyst comprises the following steps:
(1) dispersing a crystal template, a carbon nitride precursor and a certain amount of active component metal salt into a solvent according to the mass ratio of 2-10, uniformly mixing, and heating and stirring the uniformly mixed solution at 25-90 ℃ for 1-6 h;
(2) rapidly cooling the mixture solution obtained in the step (1) to convert the solution into a solid phase, and then removing the solvent to obtain solid powder;
(3) roasting the solid powder at 400-600 ℃ for 2-6 h under the protection of inert atmosphere, washing the roasted solid powder with water to remove a crystal template, and drying at 50-120 ℃ for 4-16 h;
(4) and dispersing the dried sample into the solution again, adding a certain amount of 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, carrying out reflux stirring for 8-24 h at 25-120 ℃, carrying out centrifugal separation to obtain a solid sample, and drying for 4-16 h at 50-120 ℃ to finally obtain the carbon-based monatomic photocatalyst. In the step, 1,2,3,4, 5-pentamethylcyclopentadiene is adopted to carry out secondary modification on the active metal component.
Further, in the step (1), the molar ratio of the added active component metal salt to the carbon nitride precursor is 4-20; the concentration of the active metal component in the formed solution is 0.01-2 mol/L; the molar ratio of the 1,2,3,4, 5-pentamethylcyclopentadiene added in the step (4) to the active component metal salt is 0.5-2.0.
Further, the active component metal salt is in any form of acetate, nitrate, chloride and acetylacetone compound of the active metal component; the carbon nitride precursor is any one of cyanamide, dicyandiamide, melamine and urea; the crystal template is one or two of sodium chloride, potassium chloride and lithium chloride; the solvent is any one of water, absolute ethyl alcohol, methanol, acetone, toluene and tertiary butanol.
Further, an ultrasonic method is adopted in the step (1), so that the crystal template, the carbon nitride precursor and the active component metal salt are fully and uniformly mixed, and the ultrasonic time is 10-50 min; in the step (2), a freeze-drying method is adopted to remove the solvent so as to obtain uniform and light solid powder; in the step (3), the temperature is raised from room temperature or drying temperature to the required roasting temperature by adopting a temperature programming mode, the temperature raising rate is 0.5-10 ℃/min, and the roasting temperature is 550 ℃; the solution in the step (4) comprises methanol, ethanol and acetone; the centrifugal speed is 5000-12000 rpm/min, and the centrifugal time is 1-10 min.
The catalyst and the application of the catalyst prepared by the preparation method in photocatalysis NADH (nicotinamide adenine dinucleotide) coenzyme regeneration reaction.
Further, nicotinamide adenine dinucleotide in an oxidized state is reacted with a nicotinamide adenine dinucleotideNucleotide Acid (NAD)+) Adding the catalyst and the electronic sacrificial agent into a solvent, and stirring and reacting for 5-120 min at 25-40 ℃ under the irradiation condition of an LED lamp.
Further, the electron sacrificial agent is one of methanol, ethanol, isopropanol, triethanolamine, formic acid, ascorbic acid and EDTA; the solvent is a phosphate buffer solution, the phosphate buffer solution is a mixed solution of disodium hydrogen phosphate and sodium dihydrogen phosphate, and the pH value of the solution is 5.7-8.0; the active metal component of the catalyst added is NAD+The molar ratio of (a) to (b) is 0.1 to 5 mol%; the wavelength of the LED lamp is 300-500 nm.
After the reaction is finished, measuring the absorbance of the reaction solution at 340nm through UV-Vis, and analyzing the regeneration yield of NADH; wherein the absorption coefficient of NADH at 340nm is 6220M-1cm-1。
The invention has the beneficial effects that:
(1) the novel carbon-based single-atom photocatalyst provided by the invention has excellent regeneration efficiency and cyclic usability in the photocatalytic NADH coenzyme regeneration reaction; realizes the coenzyme regeneration process without adding an electronic regulator, and is beneficial to constructing a brand-new artificial-natural combined catalyst system.
(2) The catalyst takes a two-dimensional ultrathin carbon nitride substrate with good biocompatibility as a carrier, and the Rh or Co based monatomic metal center is doped into the carrier framework to realize a novel carbon based monatomic photocatalyst; the preparation method has simple and feasible synthesis steps and high practical value.
(3) The carbon-based single-atom photocatalyst prepared by the invention can be directly stored in the air atmosphere for a long time without inactivation, and in the application of photocatalytic coenzyme regeneration reaction, NAD+Conversion rate of (2)>98% and 1,4-NADH yield>90％。
Drawings
FIG. 1 is a SEM photograph of a No. 1 catalyst provided in example 1 of the present invention;
FIG. 2 is an SEM photograph of catalyst # 4 according to example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
For a further understanding of the invention, reference will now be made to the following description taken in conjunction with the accompanying drawings and examples.
Example 1
Weighing 2g of dicyandiamide to be dispersed in 50mL of water, and carrying out ultrasonic treatment for 10min to obtain a uniform solution; then 6g of NaCl and 0.5mM of cobalt acetate are added into the dicyandiamide solution and mixed evenly, and the evenly mixed solution is heated and stirred for 4 hours at 50 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 550 ℃ by programmed heating for 4h under the nitrogen atmosphere, and then carrying out heat preservation roasting for 4h to obtain a yellow powder sample; the powder sample was washed in pure water, NaCl was washed away, and then it was dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 50 ℃ for 10 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 80 ℃ for 8h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Co-CN), which is marked as a No. 1 catalyst.
Through the analysis of a spherical aberration electron microscope, as shown in fig. 1, it can be known that Co is in a monoatomic dispersion state in the catalyst # 1, and no nanoparticles exist.
Example 2
Weighing 2g of cyanamide, dispersing in 50mL of water, and carrying out ultrasonic treatment for 15min to obtain a uniform solution; then 6g of NaCl and 0.5mM of cobalt acetate are added into the cyanamide solution, the mixture is uniformly mixed, and the uniformly mixed solution is heated and stirred for 3 hours at the temperature of 40 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 500 ℃ by programming for 4h under the nitrogen atmosphere, and then carrying out heat preservation and roasting for 5h to obtain a yellow powder sample; the powder sample was washed in pure water, NaCl was washed away, and then it was dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 50 ℃ for 10 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 100 ℃ for 5h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Co-CN), which is marked as a No. 2 catalyst.
The analysis of a spherical aberration electron microscope shows that Co is in a monoatomic dispersion state in the 2# catalyst and no nanoparticles exist.
Example 3
Weighing 2g of melamine, dispersing the melamine in 50mL of water, and carrying out ultrasonic treatment for 20min to obtain a uniform solution; then 6g of NaCl and 0.5mM of cobalt acetate are added into the melamine solution, the mixture is uniformly mixed, and the uniformly mixed solution is heated and stirred for 2 hours at the temperature of 60 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 450 ℃ by programmed heating for 4h under the nitrogen atmosphere, and then carrying out heat preservation roasting for 6h to obtain a yellow powder sample; the powder sample was washed in pure water, NaCl was washed away, and then it was dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 50 ℃ for 10 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 100 ℃ for 4h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Co-CN), which is marked as 3# catalyst.
The analysis of a spherical aberration electron microscope shows that Co is in a monoatomic dispersion state in the 3# catalyst and no nanoparticles exist.
Example 4
Weighing 2g of dicyandiamide to be dispersed in 50mL of water, and carrying out ultrasonic treatment for 10min to obtain a uniform solution; then 6g of LiCl and 0.5mM of rhodium chloride are added into the dicyandiamide solution and mixed evenly, and the evenly mixed solution is heated and stirred for 4 hours at 25 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 550 ℃ by programmed heating for 4h under the nitrogen atmosphere, and then carrying out heat preservation roasting for 4h to obtain a yellow powder sample; the powder sample was washed in pure water, the LiCl was washed off and then dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 40 ℃ for 9 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 80 ℃ for 6h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Rh-CN), which is marked as No. 4 catalyst.
From the analysis by spherical aberration electron microscopy, as shown in fig. 2, Rh was found to be in a monoatomic dispersion state in the 4# catalyst without any nanoparticles present.
Example 5
Weighing 2g of cyanamide, dispersing in 50mL of water, and carrying out ultrasonic treatment for 25min to obtain a uniform solution; then 6g of LiCl and 0.5mM of rhodium chloride are added into the cyanamide solution and mixed evenly, and the evenly mixed solution is heated and stirred for 1h at 90 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 550 ℃ by programmed heating for 4h under the nitrogen atmosphere, and then carrying out heat preservation roasting for 2h to obtain a yellow powder sample; the powder sample was washed in pure water, the LiCl was washed off and then dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 30 ℃ for 15 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 80 ℃ for 12h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Rh-CN), which is marked as 5# catalyst.
The analysis of a spherical aberration electron microscope shows that Rh is in a monoatomic dispersion state in the 5# catalyst and does not exist any nano particles.
Example 6
Weighing 2g of melamine, dispersing the melamine in 50mL of water, and carrying out ultrasonic treatment for 30min to obtain a uniform solution; then 6g of LiCl and 0.5mM of cobalt acetate are added into the melamine solution, the mixture is uniformly mixed, and the uniformly mixed solution is heated and stirred for 2 hours at 50 ℃; then quenching by adopting liquid nitrogen to convert the solution into a solid phase; and (3) putting the frozen solid-phase solution into a plastic beaker, and transferring the solid-phase solution into a vacuum freeze dryer for drying so as to remove the solvent, thereby obtaining a powder sample. Putting the obtained powder sample into a quartz boat, raising the temperature to 550 ℃ by programmed heating for 4h under the nitrogen atmosphere, and then carrying out heat preservation roasting for 5h to obtain a yellow powder sample; the powder sample was washed in pure water, the LiCl was washed off and then dried in a vacuum oven. Re-dispersing the dried sample into a methanol solution, adding 0.25mM 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, and carrying out reflux stirring at 60 ℃ for 10 hours; and (3) obtaining a solid sample through centrifugal separation, drying the obtained sample at 50 ℃ for 14h, and finally obtaining the carbon-based monatomic photocatalyst (Cp-Rh-CN), which is marked as No. 6 catalyst.
The analysis of a spherical aberration electron microscope shows that Rh is in a monoatomic dispersion state in the No. 6 catalyst and does not exist any nano particles.
Application example 1
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 1 was weighed into the solution.And (3) carrying out photocatalytic reaction by magnetic stirring for 30min under the illumination condition. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of # 1 catalyst+Conversion rate is>99%, 1,4-NADH yield is>95％。
Application example 2
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 2 was weighed into the solution. And (3) carrying out photocatalytic reaction by magnetic stirring for 30min under the illumination condition. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of catalyst # 2+Conversion rate is>97%, 1,4-NADH yield>95％。
Application example 3
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 3 was weighed into the solution. And (3) carrying out photocatalytic reaction by magnetic stirring for 30min under the illumination condition. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of # 3 catalyst+Conversion rate is>90%, 1,4-NADH yield is>95％。
Application example 4
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 4 was weighed into the solution. Under the condition of illumination, the photocatalytic reaction is carried out by magnetic stirring for 15 min. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of 4# catalyst+Conversion rate is>99%, 1,4-NADH yield is>95％。
Application example 5
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 5 was weighed into the solution. And (3) carrying out photocatalytic reaction by magnetic stirring for 30min under the illumination condition. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of 5# catalyst+Conversion rate is>91%, 1,4-NADH yield>95％。
Application example 6
Coenzyme regeneration reaction is carried out under the irradiation of an LED lamp (450nm wavelength): the reaction system was 3mL of PBS buffer, pH 7.4. Measuring 120. mu.L of NAD+(1mM) was added to 2.88mL of phosphate buffered saline and 6mg of catalyst # 6 was weighed into the solution. And (3) carrying out photocatalytic reaction by magnetic stirring for 30min under the illumination condition. After the reaction, 500. mu.L of the reaction solution was measured, diluted 5 times with deionized water, and the absorbance at 340nm was measured by UV-Vis to calculate the 1,4-NADH yield. NAD of catalyst # 6+Conversion rate is>93%, 1,4-NADH yield>95％。
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or modification made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A carbon-based monatomic photocatalyst characterized by comprising an active metal component and a carrier, the active metal component being supported on the carrier in a monoatomic dispersion state; the active metal component is any one of Rh and Co; the carrier is a two-dimensional ultrathin graphite phase carbon nitride substrate.
2. The carbon-based monatomic photocatalyst according to claim 1, wherein the active metal component content in the catalyst is 0.1 to 10.0 wt%.
3. The carbon-based monatomic photocatalyst according to claim 2, wherein the active metal component content in the catalyst is 0.1 to 5.0 wt%.
4. A preparation method of a carbon-based single-atom photocatalyst is characterized by comprising the following steps:
(1) dispersing a crystal template, a carbon nitride precursor and a certain amount of active component metal salt into a solvent according to the mass ratio of 2-10, uniformly mixing, and heating and stirring the uniformly mixed solution at 25-90 ℃ for 1-6 h;
(2) rapidly cooling the mixture solution obtained in the step (1) to convert the solution into a solid phase, and then removing the solvent to obtain solid powder;
(3) roasting the solid powder for 2-6 h at 400-600 ℃ under the protection of inert atmosphere, then washing with water to remove a crystal template, and drying for 4-16 h at 50-120 ℃;
(4) and dispersing the dried sample into the solution again, adding a certain amount of 1,2,3,4, 5-pentamethylcyclopentadiene, uniformly mixing, carrying out reflux stirring for 8-24 h at 25-120 ℃, carrying out centrifugal separation to obtain a solid sample, and drying for 4-16 h at 50-120 ℃ to finally obtain the carbon-based monatomic photocatalyst.
5. The preparation method according to claim 4, wherein the molar ratio of the active component metal salt added in the step (1) to the carbon nitride precursor is 4-20; the concentration of the active metal component in the formed solution is 0.01-2 mol/L; the molar ratio of the 1,2,3,4, 5-pentamethylcyclopentadiene added in the step (4) to the active component metal salt is 0.5-2.0.
6. The method for preparing the active ingredient of claim 4, wherein the active ingredient metal salt is in the form of any one of acetate, nitrate, chloride and acetylacetone compound of the active metal ingredient; the carbon nitride precursor is any one of cyanamide, dicyandiamide, melamine and urea; the crystal template is one or two of sodium chloride, potassium chloride and lithium chloride; the solvent is any one of water, absolute ethyl alcohol, methanol, acetone, toluene and tertiary butanol.
7. The preparation method according to claim 4, characterized in that in the step (1), an ultrasonic method is adopted to fully and uniformly mix the crystal template, the carbon nitride precursor and the active component metal salt, and the ultrasonic time is 10-50 min; in the step (2), a freeze-drying method is adopted to remove the solvent so as to obtain uniform and light solid powder; in the step (3), the temperature is raised from room temperature or drying temperature to the required roasting temperature by adopting a temperature programming mode, the temperature raising rate is 0.5-10 ℃/min, and the roasting temperature is 550 ℃; the solution in the step (4) comprises methanol, ethanol and acetone; the centrifugal speed is 5000-12000 rpm/min, and the centrifugal time is 1-10 min.
8. Use of the catalyst according to any one of claims 1 to 3 or prepared by the preparation method according to any one of claims 4 to 7 for photocatalytic regeneration of NADH coenzyme.
9. Use according to claim 8, characterized in that Nicotinamide Adenine Dinucleotide (NAD) in the oxidized state is reacted+) Adding the catalyst and the electronic sacrificial agent into a solvent, and stirring and reacting for 5-120 min at 25-40 ℃ under the irradiation condition of an LED lamp.
10. The use of claim 9, wherein the electron sacrificial agent is one of methanol, ethanol, isopropanol, triethanolamine, formic acid, ascorbic acid, and EDTA; the solvent is phosphate buffer solution, and the phosphate buffer solution is the mixture of disodium hydrogen phosphate and sodium dihydrogen phosphateThe pH value of the solution is 5.7-8.0; the active metal component of the catalyst added is NAD+The molar ratio of (a) to (b) is 0.1 to 5 mol%; the wavelength of the LED lamp is 300-500 nm.
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