CN116139925A - Hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide - Google Patents
Hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide Download PDFInfo
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- CN116139925A CN116139925A CN202111389669.0A CN202111389669A CN116139925A CN 116139925 A CN116139925 A CN 116139925A CN 202111389669 A CN202111389669 A CN 202111389669A CN 116139925 A CN116139925 A CN 116139925A
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- hydrogen peroxide
- titanium dioxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 74
- -1 bipyridine biphenyl modified titanium dioxide Chemical class 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000004305 biphenyl Substances 0.000 title claims abstract description 19
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 70
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- UXGIEYNFUOSRFI-UHFFFAOYSA-N 5-ethoxycarbonyl-2,6-dimethylpyridine-3-carboxylic acid Chemical compound CCOC(=O)C1=CC(C(O)=O)=C(C)N=C1C UXGIEYNFUOSRFI-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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Abstract
The invention discloses a hydrogen peroxide photocatalyst of bipyridine biphenyl modified titanium dioxide, which is prepared by modifying the surface interface structure of nano titanium dioxide through bis (2, 6-lutidine-3, 5-dicarboxylic ester) benzene, so as to accelerate the separation and transfer of photo-generated charges, expand the spectrum absorption range and improve the photocatalytic performance, and the prepared catalyst has high hydrogen peroxide production activity. The photocatalyst is easy to adjust the surface structure through the molecular structure of bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene, has low preparation cost, is easy to popularize and has good application prospect.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalyst for producing hydrogen peroxide.
Background
At present, a great amount of greenhouse gases generated by fossil energy sources are aggravating the deterioration of natural environment for human survival, causing more and more natural disasters, and searching for alternative energy sources and realizing sustainable development have come to an urgent degree. Hydrogen peroxide is a compound with wide application, can be used in a plurality of fields such as sterilization and disinfection, environmental management, decolorization and bleaching, hydrogen peroxide preparation and the like, is an energy substance with potential utilization value, has good development prospect especially in the field of fuel cells, and can provide an important direction for the development of new energy in the future. Hydrogen peroxide does not contain carbon atoms, and carbon dioxide is not generated in the later use, so that the hydrogen peroxide is a clean energy substance. The light-driven synthesis of hydrogen peroxide directly utilizes solar energy, does not consume fossil energy, is a green energy approach, and is increasingly receiving attention from people. Under the action of light, various photocatalysts with hydrogen peroxide generating activity, including metal oxides, graphenes, carbon nitrides, perovskite, high molecular polymers and the like, have been focused on the activity and application stability of the photocatalysts, and the search for photocatalysts with high activity is urgent. The nano titanium dioxide has the advantages of rich sources, high optical activity, light corrosion resistance and the like, but the spectrum absorption is concentrated in the ultraviolet region, the light utilization rate is low, and the surface structure is required to be further modified.
Disclosure of Invention
The invention aims to provide a hydrogen peroxide photocatalyst of bipyridine biphenyl modified titanium dioxide, which improves the surface interface structure of nano titanium dioxide through bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene, accelerates the separation and transfer of photo-generated charges, enlarges the spectral absorption range and improves the photocatalytic performance.
The invention relates to a hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide, which is a photocatalyst formed by loading a bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound on the surface of nano titanium dioxide. The structural general formula of the bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound is as follows:
wherein R is one of methyl, ethyl and propyl. The bis (2, 6-lutidine-3, 5-dicarboxylate) based benzene compounds may be prepared by literature methods [ Z.Gan, A.Okui, Y.Kawashita, M.Hayashi, convenient Synthesis of Linear-extended Bipyridines Involving a Central Phenyl Linking Group, chem. Lett.37 (2008) 1302-1303].
The photocatalyst of the bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound loaded on the surface of the nano titanium dioxide can be prepared by the following method:
the method comprises the following steps: dissolving a bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound in a solvent to prepare a solution, adding nano titanium dioxide, stirring uniformly, evaporating to remove the solvent, calcining the obtained solid at a certain temperature, naturally cooling, fully washing with the solvent, and drying to obtain the photocatalyst with the performance of preparing hydrogen peroxide by photocatalysis. The solvent is one of water, methanol, ethanol, propanol, butanol, amyl alcohol, acetic acid, propionic acid, ethyl acetate, butyl acetate, acetone, butanone, pentanone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. The certain temperature is 100-500 ℃, preferably 180-400 ℃; the calcination treatment (heat treatment) time is 0.5 to 48 hours.
The second method is as follows: the photocatalyst can also be prepared by a hydrothermal method or a solvothermal method, and the process comprises the steps of dissolving a bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound in a solvent to prepare a solution, adding nano titanium dioxide, uniformly stirring, completely transferring the solution into a high-pressure reaction kettle, reacting at the constant temperature of 120-300 ℃ for 0.5-48 h, cooling, filtering materials in the high-pressure reaction kettle, fully washing with the solvent, and drying to obtain the photocatalyst with the performance of preparing hydrogen peroxide by photocatalysis. The solvent is one of water, methanol, ethanol, propanol, butanol, amyl alcohol, acetic acid, propionic acid, ethyl acetate, butyl acetate, acetone, butanone, pentanone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The bipyridine biphenyl modified titanium dioxide photocatalyst is used for promoting the generation of hydrogen peroxide in water under the irradiation of light.
The invention has the beneficial effects that:
1) The bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound is loaded on the surface of the nano titanium dioxide, so that the conduction band position of the catalyst can be adjusted, the catalyst has excellent charge separation and transfer capacity, the photo-generated charge separation and transfer of the photocatalyst can be accelerated, and the activity of the catalyst is improved.
2) After heat treatment, the bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound forms a stable conjugated molecular structure on the surface of the nano titanium dioxide, which is beneficial to transfer and separation of photo-generated charges.
3) The bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound is directly utilized to change the surface structure of the titanium dioxide, and the method has the advantages of easiness in implementation, high efficiency, low cost and the like.
Drawings
The figure is a Mort-Schottky plot of the bipyridine biphenyl modified titanium dioxide hydrogen peroxide generating photocatalyst of example 1 and titanium dioxide.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the above formulas. It is pointed out that the following examples are only further illustrative of the invention and are not intended to limit the scope of the invention, since any insubstantial modifications and adaptations of the invention to those skilled in the art are within the scope of the invention as described above. The specific process parameters in the examples described below are also only one example of a range of preferred conditions and are not intended to limit the specific values in the examples.
Example 1
The hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titania is one comprising 1, 4-bis (2, 6-dimethyl pyridine-3, 5-methyl dicarboxylate) benzene supported on the surface of nanometer titania, and is prepared through adsorbing 1, 4-bis (2, 6-dimethyl pyridine-3, 5-methyl dicarboxylate) benzene onto the surface of nanometer titania and subsequent calcination, and includes the following steps:
weighing 0.2g of 1, 4-bis (2, 6-lutidine-3, 5-dicarboxylic acid methyl ester) benzene, adding into 30mL of tetrahydrofuran, dissolving under stirring, adding 3g of nano titanium dioxide, stirring uniformly, steaming in a rotary way, removing tetrahydrofuran to obtain a solid, putting the solid into a muffle furnace, heating to 150 ℃ at a heating rate of 5 ℃/min, standing for 30min, heating to 350 ℃, standing for 1h, naturally cooling, taking out a calcined catalyst, dispersing into 20mL of N, N-dimethylformamide, stirring for 5min, carrying out suction filtration, washing a filter cake with ethanol for 3 times (15 mL each time), drying the filter cake at 50 ℃ for 8h, and obtaining the hydrogen peroxide-producing photocatalyst containing 1, 4-dihydropyridine, wherein the conduction band position of the catalyst is negatively moved compared with that of titanium dioxide, and the surface structure of the catalyst is adjusted.
0.04g of the catalyst was added to 8mL of water, 0.1g of isopropyl alcohol was added as a sacrificial agent, and 47mM hydrogen peroxide was produced 12 hours under stirring with air and 350W xenon lamp irradiation.
Example 2
A bipyridine biphenyl modified titanium dioxide photocatalyst for producing hydrogen peroxide is a photocatalyst formed by loading 1, 4-bis (2, 6-dimethylpyridine-3, 5-dicarboxylic acid ethyl ester) benzene on the surface of nano titanium dioxide. The preparation method of the catalyst is that 1, 4-bis (2, 6-dimethylpyridine-3, 5-dicarboxylic acid ethyl ester) benzene is loaded on the surface of nano titanium dioxide by a solvothermal method, and the preparation method comprises the following steps:
adding 0.1g of 1, 4-bis (2, 6-lutidine-3, 5-dicarboxylic acid methyl ester) benzene into 20mL of N, N-dimethylacetamide, dissolving under stirring, adding 1.5g of nano titanium dioxide, uniformly stirring, transferring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to 200 ℃ for reaction for 6 hours, naturally cooling, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol for 5 times (10 mL each time), and drying the filter cake at 60 ℃ for 7 hours to obtain the hydrogen peroxide photocatalyst of bipyridine biphenyl modified titanium dioxide. As can be seen from the Mort-Schottky curve of the attached drawing, the flat-band potential of the bipyridine biphenyl modified titanium dioxide hydrogen peroxide-producing photocatalyst is-0.97V, and compared with the flat-band potential of the titanium dioxide, the flat-band potential of the titanium dioxide is obviously negatively shifted to 0.5V, so that the conduction band position is changed similarly, and the surface structure of the titanium dioxide is regulated.
The catalyst has better hydrogen peroxide production activity, 0.05g of the catalyst is added into 10mL of water, 0.04g of methanol is added as a sacrificial agent, and 36mM hydrogen peroxide is produced in 12h under the conditions of air stirring and 350W xenon lamp irradiation.
Example 3
The hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titania is one comprising 1, 3-bis (2, 6-dimethyl pyridine-3, 5-methyl dicarboxylate) benzene supported on the surface of nanometer titania, and is prepared through adsorbing 1, 3-bis (2, 6-dimethyl pyridine-3, 5-methyl dicarboxylate) benzene onto the surface of nanometer titania and subsequent calcination, and includes the following steps:
adding 0.15g of 1, 3-bis (2, 6-lutidine-3, 5-dicarboxylic acid methyl ester) benzene into 30mL of ethyl acetate, dissolving under stirring, adding 2g of nano titanium dioxide, stirring uniformly, steaming in a rotary way, removing n-butanol to obtain a solid, putting the solid into a muffle furnace, heating to 380 ℃ at a heating rate of 5 ℃/min, keeping the constant temperature for 3h, naturally cooling, taking out a calcined catalyst, dispersing into 20mL of N, N-dimethylformamide, stirring for 3min, carrying out suction filtration, washing a filter cake with ethanol for 3 times (15 mL for each time), and drying the filter cake at 50 ℃ for 10h to obtain the hydrogen peroxide photocatalyst containing 1, 4-dihydropyridine. The conduction band position of the catalyst is negatively moved compared with titanium dioxide, and the surface structure is adjusted.
0.04g of the catalyst was added to 10mL of water, 0.04g of benzyl alcohol was added as a sacrificial agent, and 51mM hydrogen peroxide was produced 12 hours under stirring with air and 350W xenon lamp irradiation.
Example 4
The preparation method of the catalyst is that 1, 3-bis (2, 6-dimethylpyridine-3, 5-dicarboxylic acid ethyl ester) yl benzene is loaded on the surface of nano titanium dioxide by a solvothermal method, and the catalyst comprises the following steps:
adding 0.2g of 1, 3-bis (2, 6-lutidine-3, 5-dicarboxylic acid methyl ester) benzene into 20mL of N-methylpyrrolidone, dissolving under stirring, adding 1.0g of nano titanium dioxide, uniformly stirring, transferring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to 220 ℃ for reacting for 5 hours, naturally cooling, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol for 4 times (20 mL of ethanol each time), and drying the filter cake at 60 ℃ for 7 hours to obtain the hydrogen peroxide photocatalyst of the bipyridine biphenyl modified titanium dioxide. The conduction band position of the catalyst is negatively moved compared with titanium dioxide, and the surface structure is adjusted.
The catalyst has better hydrogen peroxide production activity, 0.04g of the catalyst is added into 7mL of water, 0.04g of ethanol is added as a sacrificial agent, and 43mM hydrogen peroxide is produced in 12h under the conditions of air stirring and 350W xenon lamp irradiation.
Claims (6)
1. A bipyridine biphenyl modified titanium dioxide photocatalyst for producing hydrogen peroxide is a photocatalyst formed by loading bis (2, 6-dimethylpyridine-3, 5-dicarboxylic acid ester) benzene on the surface of nano titanium dioxide, and has the photocatalytic activity for producing hydrogen peroxide.
2. The hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide according to claim 1, wherein the bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound is 1, 4-or 1, 3-bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene, and the carboxylic acid ester is one of carboxylic acid methyl ester, carboxylic acid ethyl ester and carboxylic acid propyl ester.
3. The hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide according to claim 1, which can be prepared by the following method: dissolving a bis (2, 6-lutidine-3, 5-dicarboxylic acid ester) benzene compound in a solvent to prepare a solution, adding nano titanium dioxide, stirring uniformly, evaporating to remove the solvent, calcining the obtained solid at a certain temperature, naturally cooling, fully washing with the solvent, and drying to obtain the photocatalyst with the performance of preparing hydrogen peroxide by photocatalysis.
4. The process for preparing a hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide according to claim 3, wherein the solvent is one of water, methanol, ethanol, propanol, butanol, pentanol, acetic acid, propionic acid, ethyl acetate, butyl acetate, acetone, butanone, pentanone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the certain temperature is 100 ℃ to 500 ℃, preferably 150 ℃ to 400 ℃; the heat treatment time is 0.5 h-36 h.
5. The hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titania of claim 1 may be prepared through hydrothermal process or solvothermal process, and through dissolving bis (2, 6-dimethyl pyridine-3, 5-dicarboxylic acid ester) benzene compound in solvent to prepare solution, adding nanometer titania, stirring, transferring to high pressure reactor, reaction at 150-300 deg.c for 0.5-48 hr, cooling, filtering, washing with solvent and drying.
6. The method for preparing the hydrogen peroxide producing photocatalyst of bipyridine biphenyl modified titanium dioxide according to claim 5, wherein the solvent is one of water, methanol, ethanol, propanol, butanol, pentanol, acetic acid, propionic acid, ethyl acetate, butyl acetate, acetone, butanone, pentanone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
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| Title |
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| HENG LI ETAL.: "Dipyridylbenzene as a charming sensitizer to significantly enhance the photocatalytic activity of titanium dioxide", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 232, 27 March 2018 (2018-03-27), pages 472 - 480, XP085394352, DOI: 10.1016/j.apcatb.2018.03.096 * |
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