CN107051585B - Composite catalyst with high-efficiency photocatalytic oxidation and application thereof - Google Patents
Composite catalyst with high-efficiency photocatalytic oxidation and application thereof Download PDFInfo
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- CN107051585B CN107051585B CN201710359539.XA CN201710359539A CN107051585B CN 107051585 B CN107051585 B CN 107051585B CN 201710359539 A CN201710359539 A CN 201710359539A CN 107051585 B CN107051585 B CN 107051585B
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- hydroxymethylfurfural
- composite catalyst
- buffer solution
- photocatalytic
- oxidation
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 43
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 41
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 24
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007853 buffer solution Substances 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000005286 illumination Methods 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000008366 buffered solution Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 description 26
- 238000002474 experimental method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- FYSNRPHRLRVCSW-UHFFFAOYSA-N dodecasodium;tetraborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] FYSNRPHRLRVCSW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
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- B01J35/39—
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention belongs to the field of chemical industry, and particularly discloses a composite catalyst with high-efficiency photocatalytic oxidation and application thereof. The composite catalyst takes graphite-like phase carbon nitride as a carrier, and the octan-butylthio-tetraazacobalt porphyrin is supported on the graphite-like phase carbon nitride to form the composite catalyst, the composite catalyst has good photocatalytic activity, can utilize light energy and molecular oxygen to implement green selective oxidation of biomass-based micromolecule 5-hydroxymethylfurfural in a water system, can effectively carry out photocatalytic oxidation on the 5-hydroxymethylfurfural into 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid, and can be repeatedly used. Therefore, the method has very important significance for clean production of the oxidation product of the 5-hydroxymethylfurfural.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a composite catalyst with high-efficiency photocatalytic oxidation and application thereof.
Background
2, 5-furandicarboxaldehyde (DFF) and 2, 5-furandicarboxylic acid (FDCA) are important precursors of chemical industry products, and are furan derivatives generated by selective oxidation reaction of biomass-based small molecule 5-hydroxymethylfurfural. The development of a green and efficient selective catalytic oxidation system of 5-hydroxymethylfurfural is always one of the research hotspots in the field of biomass conversion and utilization.
The sulfur-containing aza metalloporphyrin and the graphite-like carbon nitride can be used as a photocatalyst to activate molecular oxygen in the air under the excitation of light, and the generated active oxygen species can effectively oxidize organic matters. The sulfur-containing aza metalloporphyrin and the graphite-like carbon nitride are subjected to binary composition, so that a photo-generated electron-hole pair can be effectively separated, the utilization rate of a photo-generated carrier is enhanced, the aim of improving the photocatalytic activity of the photocatalyst is fulfilled, and an effective way is provided for efficiently utilizing solar energy. The photocatalysis technology is applied to organic synthesis, high-selectivity synthesis of a target product can be realized by optimizing reaction conditions, and an energy-saving and green approach is provided for organic synthesis. The application of the photocatalytic technology in the field of organic synthesis is widely concerned by people today when green chemical industry is advocated.
Disclosure of Invention
In order to develop a green and efficient selective catalytic oxidation system of 5-hydroxymethylfurfural, aiming at the defects of the existing catalytic oxidation system of 5-hydroxymethylfurfural, the invention carries out binary composition on sulfur-containing aza-metalloporphyrin and graphite-like phase carbon nitride to form a composite photocatalyst, and develops application of the composite photocatalyst in photocatalytic activation of molecular oxygen to further selectively oxidize 5-hydroxymethylfurfural. The composite photocatalyst prepared by the invention can efficiently and selectively carry out photocatalytic oxidation on 5-hydroxymethylfurfural into 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid.
According to the application, graphite-like phase carbon nitride is used as a carrier, and sulfur-containing aza-metalloporphyrin is supported on the graphite-like phase carbon nitride to form the composite photocatalyst. Under mild conditions, oxygen is used as an oxidant, and the selective regulation of the oxidation product of the 5-hydroxymethylfurfural is realized by changing the pH value of a reaction system in a water system.
In order to achieve the above purpose of the present invention, the technical scheme adopted by the present invention is as follows:
a composite catalyst with high-efficiency photocatalytic oxidation performance is prepared by the following steps:
adding sulfur-containing aza metalloporphyrin and graphite-like carbon nitride into a solvent, uniformly mixing under the protection of nitrogen, and obtaining the composite catalyst after the solvent is completely volatilized.
Further, the sulfur-containing aza metalloporphyrin is any one of octan-butylthio-tetraazacobalt porphyrin, octan-butylthio-tetraazairon porphyrin and octan-butylthio-tetraazamanganese porphyrin;
further, the mass ratio of the sulfur-containing aza-metalloporphyrin to the graphite-like carbon nitride is 1:80-1: 120;
further, the condition of uniform mixing is that the mechanical stirring is carried out for 48 to 120 hours at the temperature of between 30 and 55 ℃;
further, the solvent is dichloromethane and methanol;
furthermore, the volume ratio of the dichloromethane to the methanol is 1: 1.
Mixing sulfur-containing aza metalloporphyrin and graphite-like carbon nitride, mechanically mixing the mixture uniformly by taking dichloromethane and methanol as solvents under the protection of nitrogen, and then realizing a self-assembly process at the temperature of 30-55 ℃ to prepare the catalyst.
The composite photocatalyst can be used in the field of photocatalysis. Therefore, the technical scheme of the invention also comprises an application experiment of the composite photocatalyst in the aspect of preparing 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid by photocatalytic oxidation of 5-hydroxymethylfurfural, and simultaneously the recycling efficiency of the composite photocatalyst is measured.
Adding a 5-hydroxymethylfurfural solution into a quartz jacket light reaction bottle, then adding a pH buffer solution, and then adding a composite catalyst; and then blowing air into the reaction system by using an air pump, and reacting under the condition of illumination of a xenon lamp to obtain the 2, 5-furan dicarbaldehyde or the 2, 5-furan dicarboxylic acid.
Further, the adding amount of the composite catalyst is 1 percent of the mass of the 5-hydroxymethylfurfural;
further, the pH buffer solution is a pH 6.86, pH 4.01, or pH 9.18 buffer solution;
further, the optical power density of the xenon lamp was 0.5W/cm2The illumination time is 2-14 h;
when the pH buffer solution is a buffer solution with a pH of 6.86 and the photocatalytic time is 14h, the product is 2, 5-furandicarboxylic acid; when the pH buffer solution is a buffer solution with a pH of 9.18 and the photocatalytic time is 14h, the product is 2, 5-furandicarboxaldehyde; when the pH buffer solution was a buffer solution with pH 4.01 and the photocatalytic time was 6h, the product was 2, 5-furandicarboxaldehyde.
The prepared composite catalyst can realize selective regulation and control of the oxidation product of the 5-hydroxymethylfurfural to be 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid by changing the pH value and the photocatalytic time of a reaction system in a water system by taking a xenon lamp as a light source and air as an oxygen source.
Compared with the similar compounds in the prior art, the composite photocatalyst has the advantages and beneficial effects that:
(1) the sulfur-containing aza-metalloporphyrin is supported on graphite-like carbon nitride to form a composite photocatalyst, and the 5-hydroxymethyl furfural is selectively catalyzed and oxidized to obtain 2, 5-furan dicarbaldehyde or 2, 5-furan dicarboxylic acid.
(2) Different from the existing catalyst for catalytic oxidation of 5-hydroxymethylfurfural, the composite photocatalyst can be used as a green bionic photocatalyst, and the catalytic oxidation of 5-hydroxymethylfurfural is carried out under the conditions that simulated sunlight of a xenon lamp is used as an energy source, air is used as an oxygen source and water is used as a solvent, so that an oxidation product of 5-hydroxymethylfurfural is cleanly produced.
Drawings
FIG. 1 shows g-C3N4(a) Composite photocatalyst CoPz (SBu) prepared in example 18@g-C3N4(b) SEM picture of (1);
FIG. 2 shows g-C3N4(a)、CoPz(SBu)8(b) And the composite photocatalyst CoPz (SBu)8@ g-C prepared in example 13N4(c) (ii) a uv-visible diffuse reflectance spectrum;
FIG. 3 shows g-C under 350nm excitation3N4(a)、CoPz(SBu)8(b) Composite photocatalyst CoPz (SBu) prepared in example 18@g-C3N4(c) A fluorescence spectrum of (a);
FIG. 4 is the conversion rate of 5-hydroxymethylfurfural and the selectivity of its oxidation products at pH 4.01 in example 3;
FIG. 5 is the results of the conversion of 5-hydroxymethylfurfural and the selectivity of its oxidation products at pH 9.18 in example 3;
figure 6 shows the yield of FDCA from the experiments of recycling of composite photocatalyst under neutral (pH 6.86).
Detailed Description
The preparation and use of the composite photocatalyst of the present invention are further described below by way of specific examples, but the following should not be construed as limiting the scope of the claimed invention in any way.
The main raw materials used in the following examples are as follows:
the molecular structure of the sulfur-containing aza metalloporphyrin is as follows:
m is Co, Ni or Mn.
pH 6.86 buffer solution: 0.025 mol. L-1Mixing phosphate; pH 4.01 buffer solution: 0.05 mol. L-1Potassium hydrogen phthalate; buffer solution at pH 9.18: 0.01 mol. L-1Sodium tetraborate.
Preparing graphite-like phase carbon nitride: 3.06g of urea was placed in a ceramic crucible and then calcined in a muffle furnace: at 5 ℃ min-1The temperature of the muffle furnace is raised to 550 ℃ at the temperature raising speed, and the temperature is kept at 550 ℃ for 3 hours, so that 2.56g of light yellow powder product, namely graphite-like phase carbon nitride, is prepared.
Example 1: octa-n-butylsulfanyl tetraazacobalt porphyrin is supported on graphite-like phase carbon nitride to form the composite photocatalyst
0.0029g of octan-butylthiotetraazacobalt porphyrin (abbreviated as CoPz (SBu))8) And 0.3102g of graphite-like phase carbon nitride (abbreviated as g-C)3N4) Was added to a mixed solvent of 30ml of methylene chloride and 30ml of methanol, followed by introducing nitrogen gas and mechanical stirring at 55 ℃ for 48 hours. Then transferring the solution into a 100ml beaker, and obtaining the composite photocatalyst after the solvent is completely volatilized, which is abbreviated as CoPz (SBu)8@g-C3N4。
g-C3N4Composite photocatalyst CoPz (SBu)8@g-C3N4Is shown in fig. 1. As can be seen from FIG. 1, g-C3N4Is smooth and supports CoPz (SBu)8Post-formed composite catalyst CoPz (SBu)8@g-C3N4The surface is obviously not smooth and granular substances are adhered. Further SEM-EDS analysis, g-C3N4The elements of the surface were mainly C, N, S, Co, indicating CoPz (SBu)8Carried on g-C3N4Of (2) is provided.
g-C3N4、CoPz(SBu)8And CoPz (SBu)8@g-C3N4The ultraviolet-visible diffuse reflectance spectrum of (a) is shown in fig. 2. As can be seen from FIG. 2(a), g-C3N4Can absorb visible light; FIG. 2(b) shows CoPz (SBu)8The characteristic absorption peak of (1) has a strong absorption peak between 500-700 nm; and composite catalyst CoPz (SBu)8@g-C3N4The optical properties of (A) are shown in FIG. 2(c), which shows CoPz (SBu)8Further indicating a characteristic absorption peak of CoPz (SBu)8Successfully loaded in g-C3N4On the surface of (a).
g-C under excitation at 350nm3N4、CoPz(SBu)8And CoPz (SBu)8@g-C3N4The fluorescence spectrum of (A) is shown in FIG. 3. As can be seen from FIG. 3, g-C3N4And CoPz (SBu)8The strong fluorescence emission occurred in the range of 400-650nm, while the composite catalyst CoPz (SBu) was under the same conditions8@g-C3N4The sample exhibited a fluorescence quenching phenomenon. Since CoPz (SBu)8And g-C3N4With matched band positions, the photogenerated carriers can be in CoPz (SBu)8And g-C3N4Are free to move, so CoPz (SBu)8And g-C3N4Fluorescence quenching occurs after complex formation. Indicating CoPz (SBu)8And g-C3N4The combination of the two materials can effectively prevent the combination of photon-generated carriers, enhance the utilization rate of the photon-generated carriers and further enhance the photocatalytic performance of the photon-generated carriers.
Example 2: determination of photocatalytic oxidation activity of 5-hydroxymethylfurfural by the composite photocatalyst prepared in example 1
The method comprises the following steps: 5ml of 0.01mol.L is added into a quartz jacket light reaction bottle-15-hydroxymethylfurfural solution, 40ml of buffer solution with pH 6.86 and 1% of the substrate mass (5-hydroxymethylfurfural) were added with a composite catalyst CoPz (SBu)8@g-C3N4. Then air is blown into the reaction system by an air pump, and the xenon lamp is used for illumination (0.5W/cm)2) The reaction is carried out for 14h, products of the reaction system are analyzed by HPLC, and the reaction system is an experiment under the illumination condition and is marked as CoPz (SBu)8@g-C3N4(Entry 1). The experiment under the condition of no illumination is carried out when the illumination of a xenon lamp is cancelled, and the group is marked as CoPz (SBu)8@g-C3N4(Entry 4)。
In addition, the other two groups were also set as controls: g-C3N4(Entry 2)、CoPz(SBu)8(Entry 3), the difference from Entry1 is: the catalyst of Entry 2 group is g-C3N4The mass of the catalyst is 1 percent of that of the substrate (5-hydroxymethylfurfural); the Entry 3 group catalyst is CoPz (SBu)8The mass of the catalyst is 1% of the mass of the substrate (5-hydroxymethylfurfural).
The results of the experiment are shown in table 1. The comparative experiment shows that the reaction is carried out for 14h under the condition of illumination, and the 5-hydroxymethylfurfural is reacted at g-C3N4The conversion rate reaches more than 99 percent under the condition of (1), but the selectivity and the yield of the oxidation product FDCA are both less than 0.01 percent (Entry 2); 5-hydroxymethylfurfural in CoPz (SBu)8The conversion rate reaches 40.16 percent under the condition of (1), and the oxidation product isThe selectivity of FDCA was 90% with a yield of 36.71% (Entry 3); and 5-hydroxymethylfurfural in CoPz (SBu)8@g-C3N4The conversion rate reached 99%, the selectivity of the oxidation product FDCA was 97%, and the yield was 97.24% (Entry 1). Indicating CoPz (SBu)8And g-C3N4The compound of the compound obviously improves the conversion rate of the 5-hydroxymethylfurfural, the selectivity and the yield of an oxidation product FDCA.
While the experiment under the condition of no illumination shows that the 5-hydroxymethylfurfural is applied to CoPz (SBu)8@g-C3N4The conversion was only 18.86% and the selectivity of the oxidation product FDCA was 90% with a yield of 16.97% (Entry4), indicating that light significantly promoted the oxidation of 5-hydroxymethylfurfural. In CoPz (SBu)8@g-C3N4In the photocatalysis system, the conversion rate of 5-hydroxymethylfurfural under the illumination condition is improved by 4.2 times compared with that under the non-illumination condition.
TABLE 1 catalytic oxidation of 5-hydroxymethylfurfural under neutral (pH 6.86) conditions
Example 3: effect of reaction System pH on Oxidation products of 5-hydroxymethylfurfural
The photocatalytic experiment was performed by changing the pH 6.86 buffer solution to a pH 4.01 buffer solution and a pH 9.18 buffer solution according to the procedure of Entry1 in example 2.
The results of the experiment at pH 4.01 are shown in fig. 4. The results show that: the conversion rate of 5-hydroxymethylfurfural after 6h of photocatalytic reaction is 55.72%, and the selectivity of an oxidation product DFF can reach more than 99%. The reaction time is prolonged, the photocatalytic reaction is carried out for 14 hours, the conversion rate of 5-hydroxymethylfurfural reaches 85.29%, the selectivity of an oxidation product DFF can reach 87.65%, and the selectivity of an oxidation product FDCA is only 10.29%.
The results of the experiment at pH 9.18 are shown in fig. 5. As a result: in the initial stage of the photocatalytic reaction, the oxidation products of 5-hydroxymethylfurfural are DFF and FDCA. The selectivity for FDCA increased and the selectivity for DFF decreased gradually with increasing reaction time. The conversion rate of 5-hydroxymethylfurfural reaches 98.01 percent after the photocatalytic reaction is carried out for 14h, the selectivity of an oxidation product DFF reaches 98.69 percent, and the selectivity of an oxidation product FDCA is only 1.05 percent. Experimental data indicate that acidic conditions favor the formation of the oxidation product DFF, while basic conditions favor the formation of the oxidation product FDCA.
Therefore, by using the composite catalyst prepared in example 1, the selective control of the oxidation product of 5-hydroxymethylfurfural to 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid can be realized by changing the pH value of the reaction system and the photocatalytic reaction time in a water system.
Example 4: determination of recycling efficiency of composite photocatalyst
5ml of 0.01mol.L is added into a quartz jacket light reaction bottle-15-hydroxymethylfurfural solution, 40ml of buffer solution with pH 6.86, 3mg of composite catalyst CoPz (SBu)8@g-C3N4. Then air is blown into the reaction system by an air pump, and the xenon lamp is used for illumination (0.5W/cm)2) Under the conditions of (1). After each reaction for 14h, 5ml of 0.01mol.L are removed again-1Adding the solution of the pentamethyl furfural into a reaction bottle for continuous reaction, and analyzing the product of the reaction system by using HPLC. Each 14h of reaction was a one-cycle experiment of the catalyst. The experimental result of the recycling efficiency of the composite photocatalyst is shown in fig. 6. As a result: composite photocatalyst CoPz (SBu)8@g-C3N4After 5 times of recycling, the yield of the oxidation product FDCA can reach 86 percent, which indicates that the composite photocatalyst has better stability.
Claims (6)
1. The application of the composite catalyst with high-efficiency photocatalytic oxidation property in preparing 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid by photocatalytic oxidation of 5-hydroxymethylfurfural is characterized by comprising the following specific steps:
adding a 5-hydroxymethylfurfural solution into a quartz jacket light reaction bottle, then adding a pH buffer solution, and then adding a composite catalyst; then blowing air into the reaction system by using an air pump, and reacting under the condition of xenon lamp illumination to obtain 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid;
the pH buffered solution is a pH =6.86, pH =4.01, or pH =9.18 buffered solution;
the optical power density of the xenon lamp is 0.5W/cm2The illumination time is 2-14 h;
the preparation method of the composite catalyst comprises the following steps:
adding sulfur-containing aza metalloporphyrin and graphite-like carbon nitride into a solvent, uniformly mixing under the protection of nitrogen, and obtaining a composite catalyst after the solvent is completely volatilized;
the sulfur-containing aza metalloporphyrin is any one of octan-butylthio-tetraazacobalt porphyrin, octan-butylthio-tetraazairon porphyrin and octan-butylthio-tetraazamanganese porphyrin.
2. Use according to claim 1, characterized in that: the mass ratio of the sulfur-containing aza metalloporphyrin to the graphite-like carbon nitride is 1:80-1: 120.
3. Use according to claim 1, characterized in that: the condition of uniform mixing is that the mechanical stirring is carried out for 48 to 120 hours at the temperature of 30 to 55 ℃.
4. Use according to claim 1, characterized in that: the solvent is dichloromethane and methanol.
5. Use according to claim 1, characterized in that: the adding amount of the composite catalyst is 1 percent of the mass of the 5-hydroxymethylfurfural.
6. Use according to claim 1, characterized in that: when the pH buffer solution is a pH =6.86 buffer solution and the photocatalytic time is 14h, the product is 2, 5-furandicarboxylic acid; when the pH buffer solution is a pH =9.18 buffer solution and the photocatalytic time is 14h, the product is 2, 5-furandicarboxaldehyde; when the pH buffer solution is a buffer solution of pH =4.01 and the photocatalytic time is 6h, the product is 2, 5-furandicarboxaldehyde.
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