CN112892592B - Rhodium-based electron mediator [ Cp-Rh (bpy) H 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 Method of surfacing - Google Patents
Rhodium-based electron mediator [ Cp-Rh (bpy) H 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 Method of surfacing Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 67
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 54
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical class CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- -1 bipyridine amide Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- OQVVVVYHNKQXHR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-3-carboxylic acid Chemical group OC(=O)C1=CC=CN=C1C1=CC=CC=N1 OQVVVVYHNKQXHR-UHFFFAOYSA-N 0.000 claims description 3
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- USDIXFQHPLIMKB-UHFFFAOYSA-N C[Rh+]C1C=CC=C1 Chemical class C[Rh+]C1C=CC=C1 USDIXFQHPLIMKB-UHFFFAOYSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 abstract description 22
- 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 abstract description 21
- 239000000463 material Substances 0.000 abstract description 12
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 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 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229950006238 nadide Drugs 0.000 description 7
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- WECBNRQPNXNRSJ-SSDOTTSWSA-N (2r)-2-hydroxy-2-[3-(trifluoromethyl)phenyl]acetic acid Chemical compound OC(=O)[C@H](O)C1=CC=CC(C(F)(F)F)=C1 WECBNRQPNXNRSJ-SSDOTTSWSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- FRYSEKUUHUUJPX-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=CC=2)=C1 FRYSEKUUHUUJPX-UHFFFAOYSA-N 0.000 description 1
- POYRLWQLOUUKAY-UHFFFAOYSA-N 6,7,8,9-tetrahydro-5h-carbazol-3-amine Chemical compound C1CCCC2=C1NC1=CC=C(N)C=C12 POYRLWQLOUUKAY-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000001419 dependent effect Effects 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
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical class [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B01J35/39—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a rhodium-based electronic mediator [ CpRh ](bpy)H 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 A surface method belongs to the technical field of photocatalyst preparation. The invention modifies carboxylic acid bipyridyl into MOF material UiO-66-NH through amidation reaction 2 The surface is reacted with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer to finally react with a rhodium-based electron mediator [ Cp & ltRh (bpy) H 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 The surface, the soluble rhodium electronic media is fixed on the surface of the solid catalyst, so that the homogeneous reaction catalyst is converted into a heterogeneous reaction catalyst, the recovery and the reutilization of the rhodium electronic media are realized, and the recovery and the reutilization of the rhodium electronic media are realized. In addition, the catalyst prepared by the invention shows excellent catalytic activity and stability in the photocatalysis NADH regeneration reaction.
Description
Technical Field
The invention relates to a rhodium-based electron mediator [ Cp & Rh (bpy) H 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 A surface method, belonging to the technical field of photocatalyst preparation.
Background
In recent years, enzyme-catalyzed reactions have been widely used in the chemical synthesis industry. Most of the redox enzyme catalytic reactions require Nicotinamide Adenine Dinucleotide (NADH) as a coenzyme to provide electrons and hydrogen, but the development of the enzyme catalytic reaction in the field of chemical synthesis is limited because NADH is expensive and cannot be recovered. Therefore, in the NADH-dependent enzyme-catalyzed reaction, it is necessary to design an efficient regeneration method to ensure the continuous supply of NADH to the enzyme.
The photocatalytic NADH regeneration process only utilizes solar energy to drive reaction, and the process is green and efficient. The enzyme catalysis uses NADH as a reducing agent, NADH changes to NAD after the reaction + When the enzyme catalysis reaction is combined with the photocatalysis, the photocatalyst absorbs photons to generate electron transition, so that NAD can be converted + Reducing the NADH into NADH, realizing the regeneration of the NADH, circularly participating in the reaction and reducing the cost of enzyme catalysis reaction. However, the energy of the electrons excited by the photocatalyst interacts with the NAD + The energy of the light source is not matched, and an electron mediator is needed to be used as a conveyor belt to transfer electrons excited by the photocatalyst to the NAD + Introduction of NAD into the host cell + Reducing to NADH. From dichloro (penta)The methyl cyclopentadienyl) rhodium (III) dimer reacts with bipyridine to prepare the rhodium-based electron mediator [ Cp & Rh (bpy) H 2 O] 2+ Is the most common electronic mediator, has high price, is dissolved in a reaction system in the reaction process and cannot be recycled. Therefore, it is necessary to provide a rhodium-based electron mediator which can be recovered and reused.
Disclosure of Invention
The invention provides a rhodium-based electronic medium [ Cp-Rh (bpy) H for solving the problem that the existing rhodium-based electronic medium cannot be recycled 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 A method of surfacing.
Rhodium-based electron mediator [ Cp-Rh (bpy) H 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 A method of surfacing, the method comprising the steps of:
step 1, carboxylic acid bipyridyl is immobilized in Uio-66-NH 2 Surface, obtaining bipyridine amide;
step 2, bipyramid is then reacted with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer to obtain [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Further, the operation process for preparing the bipyridine amide in the step 1 is as follows: carboxylic acid bipyridyl is refluxed and reacted for 1 to 4 hours in thionyl chloride solvent, dried by distillation to obtain bipyridyl acyl chloride, and then the bipyridyl acyl chloride and Uio-66-NH are 2 Stirring and reacting in a dichloromethane solvent for 2-12 h, filtering, and drying the obtained solid to obtain the bipyridyl amide.
Further, the carboxylic acid bipyridine is a bipyridine containing a carboxyl group.
Further, the carboxylic acid bipyridine is 2, 2-bipyridine-3-carboxylic acid, 2-bipyridine-4-carboxylic acid, 2-bipyridine-5-carboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid or 2,2 '-bipyridine-5, 5' -dicarboxylic acid.
Further, the mass volume ratio of the carboxylic acid bipyridyl to the thionyl chloride is 1mg: (1-5) mL.
Further, the mass-to-volume ratio of the carboxylic acid bipyridyl to the dichloromethane is 1mg: (1-5) mL.
Further, the reflux reaction temperature in the step 1 is 50-80 ℃.
Further, [ Cp. Multidot.Rh (bpy) H was prepared in step 2 2 O] 2+ @Uio-66-NH 2 The operation process of (1) is as follows: reacting the bipyridyl amide obtained in the step 1 with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer in a methanol solvent for 3-24H, filtering, washing and drying after reaction to obtain [ Cp & Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Further, carboxylic acid bipyridine, uio-66-NH 2 The mass ratio of the rhodium (III) chloride to the (pentamethylcyclopentadienyl) rhodium (III) dichloride is 1 (10-100) to 0.1-1.
Further, the mass-to-volume ratio of the carboxylic acid bipyridyl to methanol is 1mg: (1-5) mL.
The invention has the following beneficial effects: the invention modifies carboxylic acid bipyridyl into MOF material UiO-66-NH through amidation reaction 2 The surface is reacted with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer to finally react with a rhodium-based electron mediator [ Cp & ltRh (bpy) H 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 The surface is that the soluble rhodium-based electronic mediator is immobilized on the surface of the solid catalyst, so that the homogeneous reaction catalyst is converted into a heterogeneous reaction catalyst, the recovery and the reutilization of the rhodium-based electronic mediator are realized, and the recovery and the reutilization of the rhodium-based electronic mediator are realized. The catalyst prepared by the invention shows excellent catalytic activity and stability in the photocatalysis NADH regeneration reaction.
Drawings
FIG. 1 shows [ Cp. Multidot.Rh (bpy) H obtained in example 1 2 O] 2+ @Uio-66-NH 2 SEM picture of (a);
FIG. 2 shows [ Cp: rh (bpy) H obtained in example 1 2 O] 2+ @Uio-66-NH 2 The experimental yield of the photocatalysis NADH regeneration;
FIG. 3 shows [ Cp: rh (bpy) H obtained in example 1 2 O] 2+ @Uio-66-NH 2 NADH yield on repeated use.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
2mg of 2, 2-bipyridine-5-carboxylic acid is dissolved in 5mL of thionyl chloride, refluxed for 1h at 60 ℃ and evaporated to dryness, and 2mL of dichloromethane and 50mg of photocatalyst Uio-66-NH are added thereto 2 Stirring for 4h at normal temperature, filtering and drying; ultrasonically dispersing the obtained solid in 2mL of methanol, adding 2mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 12 hours, filtering and drying to obtain a material, namely Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Obtaining [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 The scanning electron microscope result of (a) is shown in fig. 1, and as can be seen from fig. 1, the obtained material is regular octahedron with regular appearance, uniform size and good dispersibility. The contents of the respective elements are shown in table 1 below.
TABLE 1[ 2 ], [ Cp ] Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 The content of each element in the
[ Cp ] Rh (bpy) H obtained by applying the example 2 O] 2+ @Uio-66-NH 2 Photocatalytic NADH regeneration:
the total volume of the reaction solution was 2mL, including 20mmol/L phosphate buffer and NAD + Concentration 1mmol/L, catalyst [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 2mg; and (3) irradiating for 20min under a 300W xenon lamp, and measuring the absorption wavelength at 340nm by using an ultraviolet-visible spectrophotometer every 5min so as to determine the yield of the NADH. The results of the photocatalytic NADH regeneration are shown in FIG. 2, and it can be seen from FIG. 2 that the NADH yield gradually increases with the time of illuminationIncreasing the light irradiation for 20min, and reaching the NADH yield of 98 percent. .
And (3) recycling the catalyst:
after the reaction, the catalyst [ Cp-Rh (bpy) H ] was collected by centrifugation 2 O] 2+ @Uio-66-NH 2 After drying, the catalytic experiment was repeated 4 times, the experimental results are shown in fig. 3, and it can be seen from fig. 3 that the catalyst [ Cp × Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 Has good stability, the catalytic effect is not obviously changed in the recycling process, and the NADH yield is over 95 percent. .
Example 2:
2, 2-bipyridine-5-carboxylic acid (2mg) is dissolved in 2mL thionyl chloride, refluxed for 4h at 50 ℃ and evaporated to dryness, and 2mL dichloromethane and 20mg photocatalyst Uio-66-NH are added 2 Stirring for 2h at normal temperature, filtering and drying; ultrasonically dispersing the obtained solid in 2mL of methanol, adding 0.2mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 24 hours, filtering and drying to obtain a material Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 3:
2mg of 2, 2-bipyridine-5-carboxylic acid was dissolved in 10mL of thionyl chloride, refluxed at 80 ℃ for 4 hours, evaporated to dryness, and then 10mL of dichloromethane and 200mg of photocatalyst Uio-66-NH were added thereto 2 Stirring at normal temperature for 6h, filtering and drying; ultrasonically dispersing the obtained solid in 6mL of methanol, adding 1mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring for 3 hours at normal temperature, filtering and drying to obtain a material, namely Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 4:
2, 2-bipyridine-3-carboxylic acid 2mg was dissolved in 4mL of thionyl chloride, refluxed at 70 ℃ for 1 hour, evaporated to dryness, and then 4mL of dichloromethane and 100mg of photocatalyst Uio-66-NH were added thereto 2 Stirring at normal temperature for 10h, filtering and drying; the obtained solid was ultrasonically dispersed in 8mL of methanol, to which was addedAdding 1mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 10h, filtering and drying to obtain a material Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 5:
2mg of 2, 2-bipyridine-4-carboxylic acid was dissolved in 6mL of thionyl chloride, refluxed at 60 ℃ for 2 hours, evaporated to dryness, and 10mL of dichloromethane and 200mg of photocatalyst Uio-66-NH were added thereto 2 Stirring at normal temperature for 8h, filtering and drying; ultrasonically dispersing the obtained solid in 10mL of methanol, adding 1.5mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 8 hours, filtering and drying to obtain a material, namely Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 6:
2,2 '-bipyridine-3, 3' -dicarboxylic acid (2mg) was dissolved in 3mL of thionyl chloride, refluxed at 70 ℃ for 3 hours, evaporated to dryness, and then 7mL of dichloromethane and 30mg of photocatalyst Uio-66-NH were added thereto 2 Stirring at normal temperature for 12h, filtering and drying; ultrasonically dispersing the obtained solid in 7mL of methanol, adding 0.5mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 16h, filtering and drying to obtain a material Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 7:
2mg of 2,2 '-bipyridine-4, 4' -dicarboxylic acid was dissolved in 8mL of thionyl chloride, refluxed at 60 ℃ for 1 hour and evaporated to dryness, and 3mL of dichloromethane and 160mg of photocatalyst Uio-66-NH were added thereto 2 Stirring for 7h at normal temperature, filtering and drying; ultrasonically dispersing the obtained solid in 4mL of methanol, adding 0.8mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 6 hours, filtering and drying to obtain a material, namely Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Example 8:
2,2 '-bipyridine-5, 5' -dicarboxylic acid 2mg was dissolved in 7mL of thionyl chloride, refluxed at 50 ℃ for 4 hours, evaporated to dryness, and then 8mL of dichloromethane and 80mg of photocatalyst Uio-66-NH were added thereto 2 Stirring at normal temperature for 5h, filtering, and drying; ultrasonically dispersing the obtained solid in 5mL of methanol, adding 1.2mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, stirring at normal temperature for 9 hours, filtering and drying to obtain a material Uio-66-NH 2 Immobilized [ Cp Rh (bpy) H 2 O] 2+ Metal mediator [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
Claims (8)
1. Rhodium-based electron mediator [ Cp & Rh (bpy) H 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 A method of surfacing, characterized in that the method comprises the steps of:
step 1, carboxylic acid bipyridyl is immobilized in Uio-66-NH 2 Surface, obtaining bipyridine amide;
the operation process for preparing the bipyridine amide in the step 1 is as follows: refluxing and reacting carboxylic acid bipyridyl in thionyl chloride solvent for 1-4 h, evaporating to dryness to obtain bipyridyl acyl chloride, and then reacting the bipyridyl acyl chloride with Uio-66-NH 2 Stirring and reacting in a dichloromethane solvent for 2-12 h, filtering, and drying the obtained solid to obtain bipyridyl amide;
step 2, the bipyridylamide is then reacted with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer to obtain [ Cp Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 ；
In the step 2, [ Cp ] Rh (bpy) H is prepared 2 O] 2+ @Uio-66-NH 2 The operation process comprises the following steps: reacting the bipyridyl amide obtained in the step 1 with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer in a methanol solvent for 3-24H, filtering, washing and drying after reaction to obtain [ Cp & Rh (bpy) H 2 O] 2+ @Uio-66-NH 2 。
2. The method of claim 1Rhodium-based electron mediator [ Cp-Rh (bpy) H 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 The surface method is characterized in that the carboxylic acid bipyridyl is bipyridyl containing carboxyl.
3. The rhodium-based electron mediator [ Cp x Rh (bpy) H according to claim 2 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 A method for treating surfaces, characterized in that the carboxylic acid bipyridine is 2, 2-bipyridine-3-carboxylic acid, 2-bipyridine-4-carboxylic acid, 2-bipyridine-5-carboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid or 2,2 '-bipyridine-5, 5' -dicarboxylic acid.
4. The rhodium-based electron mediator [ Cp x Rh (bpy) H according to claim 1 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 The surface method is characterized in that the mass-volume ratio of the carboxylic acid bipyridyl to the thionyl chloride is 1mg: (1-5) mL.
5. The rhodium-based electron mediator [ Cp x Rh (bpy) H according to claim 1 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 The surface method is characterized in that the mass-volume ratio of the carboxylic acid bipyridyl to the dichloromethane is 1mg: (1-5) mL.
6. The rhodium-based electron mediator [ Cp Rh (bpy) H as set forth in claim 1 2 O] 2+ Photocatalyst UOI-66-NH supported on 2 The surface method is characterized in that the reflux reaction temperature in the step 1 is 50-80 ℃.
7. The rhodium-based electron mediator [ Cp x Rh (bpy) H according to claim 1 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 The method for preparing the surface is characterized in that the carboxylic acid bipyridyl and Uio-66-NH are 2 The mass ratio of the (penta) methylcyclopentadienyl rhodium (III) dichloride to the (penta) methylcyclopentadienyl rhodium (III) dimer is 1 (10-100) to 0.1-1.
8. The rhodium-based electron mediator [ Cp ] Rh (bpy) H according to claim 7 2 O] 2+ Photocatalyst Uio-66-NH fixed on 2 The surface method is characterized in that the mass volume ratio of the carboxylic acid bipyridyl to the methanol is 1mg: (1-5) mL.
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