CN109331819B - Titanium dioxide supported Pt-Pd bimetallic photocatalyst and preparation method and application thereof - Google Patents
Titanium dioxide supported Pt-Pd bimetallic photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910018879 Pt—Pd Inorganic materials 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 26
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012696 Pd precursors Substances 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 42
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 14
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 240000003243 Thuja occidentalis Species 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 9
- 240000002924 Platycladus orientalis Species 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 241000218636 Thuja Species 0.000 description 4
- 235000008109 Thuja occidentalis Nutrition 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
Titanium dioxide negativeThe preparation method of the supported Pt-Pd bimetallic photocatalyst comprises the following steps: uniformly mixing nano titanium dioxide and a water solution of a platinum precursor, drying in vacuum, grinding into powder, heating to 550-850 ℃ in a sealed hydrogen atmosphere, and roasting for 2-6 hours to obtain titanium dioxide loaded with platinum; drying and crushing leaves of a Chinese arborvitae plant, adding the dried and crushed leaves into deionized water, stirring and filtering, collecting Chinese arborvitae filtrate, mixing the Chinese arborvitae filtrate with the deionized water and an aqueous solution of a palladium precursor, stirring for 1h at 90 ℃ to obtain a mixed solution, adding the obtained platinum-loaded titanium dioxide into the mixed solution, keeping the temperature and stirring for 1h, filtering, and drying a filter cake in vacuum to obtain the catalyst; the Pt-Pd/TiO prepared by the invention2The catalyst is used in the reaction of preparing benzaldehyde by photo-catalytic methanol solvent-free liquid phase oxidation, and has the characteristics of high activity, high selectivity and the like.
Description
(I) technical field
The invention relates to TiO for preparing benzaldehyde by photocatalytic benzyl alcohol oxidation2A load type Pt-Pd bimetallic catalyst and a preparation method thereof.
(II) background of the invention
Benzaldehyde of formula C6H5CHO, the simplest and most commonly used aromatic aldehyde in industry. The reagent has special almond smell, is widely applied to industries such as chemical engineering manufacture, environmental protection, medicine, organic synthesis and the like, has great demand, and benzaldehyde can be used for measuring a plurality of chemical substances such as ozone, phenol, alkaloid and the like and also can be used as an organic solvent for substances such as acetic acid, oil, nitrocellulose and the like (Chem Eng J2012, 187, 232-.
Semiconductor materialThe preparation of benzaldehyde by photocatalytic oxidation of benzyl alcohol is a novel technology, and CeO is a commonly used semiconductor catalytic material at present2CdS and TiO2(J Am Chem Soc 2008,130,1568-1570, Adv 2013,3,7215-7218.) and other semiconductor nano materials. The photocatalytic performance of a pure semiconductor material is poor, and metal modification is an effective means to improve the photocatalytic effect, such as Fe (J Catal 2014,311, 137-.
Disclosure of the invention
The invention aims to provide Pt-Pd/TiO2The invention relates to a bimetallic photocatalyst, a preparation method thereof and application thereof in preparing benzaldehyde by solvent-free photocatalytic benzyl alcohol oxidation.
The technical scheme of the invention is as follows:
a titanium dioxide supported Pt-Pd bimetallic photocatalyst is prepared by the following steps:
(1) uniformly mixing nano titanium dioxide (P25) and an aqueous solution of a 38.6mM platinum precursor, then carrying out vacuum drying (12h) at 60 ℃, then grinding into powder, heating to 550-850 ℃ (preferably 750-850 ℃) in a sealed hydrogen atmosphere, and roasting for 2-6 h to obtain platinum-loaded titanium dioxide;
the volume consumption of the aqueous solution of the platinum precursor is 1.33m L/g by mass of the nano titanium dioxide;
the platinum precursor is chloroplatinic acid or sodium chloroplatinite;
(2) drying and crushing leaves of a platycladus orientalis (C.Platylcladi) in the sun, and mixing the dried and crushed leaves according to the mass ratio of 1: adding 50-150 parts of the cacumen biotae into deionized water, stirring for 1-5 hours, filtering, collecting a cacumen biotae filtrate, mixing the cacumen biotae filtrate with the deionized water and a 74mM palladium precursor aqueous solution according to a volume ratio of 1: 1: 0.02, stirring for 1h at 90 ℃ (the solution changes from earthy yellow to black) to obtain a mixed solution, and then adding the mixed solution into the mixed solution according to the mass ratio of the feed liquid to the mixed solution of 1: 80-120, adding the platinum-loaded titanium dioxide obtained in the step (1), keeping the temperature, stirring for 1h, filtering, and drying a filter cake in vacuum at 60 ℃ for 12h to obtain the titanium dioxide-loaded Pt-Pd bimetallic photocatalyst;
the palladium precursor is a soluble palladium salt, such as palladium chloride or palladium nitrate.
The particle size of the prepared titanium dioxide supported Pt-Pd bimetallic photocatalyst is 3-7nm, the Pt loading amount is 0.5-2 wt%, and the Pd loading amount is 0.5-2 wt%.
The titanium dioxide supported Pt-Pd bimetallic photocatalyst prepared by the invention can be applied to the reaction of preparing benzaldehyde by the oxidation of the solvent-free photocatalytic benzyl alcohol. Specifically, the application method comprises the following steps:
adding the catalyst into benzyl alcohol, preheating for 5min at 90 ℃, refluxing (75-110 ℃), introducing oxygen at the speed of 90m L/min, simultaneously turning on a 150W metal halide lamp light source for photocatalytic reaction, and monitoring by HP L C until the reaction is complete;
the mass usage of the catalyst is 0.002-0.02 g/m L calculated by the volume of the benzyl alcohol.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares Pt-Pd/TiO for the first time2A bimetallic photocatalyst. Prepared Pt-Pd/TiO2The catalyst is used in the reaction of preparing benzaldehyde by photo-catalytic methanol solvent-free liquid phase oxidation, and has the characteristics of high activity, high selectivity and the like.
(IV) description of the drawings
FIG. 1 Pt-Pd/TiO prepared in example 32Transmission electron microscopy of bimetallic photocatalyst;
FIG. 2 Pt-Pd/TiO prepared in example 32An X-ray energy spectrum of the bimetallic photocatalyst.
(V) detailed description of the preferred embodiments
The invention is further illustrated by the following examples, without restricting its scope.
Example 1
1g of nano TiO is taken2(P25, purchased from Woodford Chuangsai EVONIK-DEGUSSA) into a 30m L crucible, adding thereto 1330. mu. L mM chloroplatinic acid using a pipette, stirring well with a small glass rod, drying in a vacuum drying oven at 60 ℃ for 12 hours, and grinding to a powder A. placing the powder A into a ceramic crucible, and further grinding to a powder APlacing the mixture in a tubular furnace, sealing, introducing hydrogen and roasting for 4 hours at the roasting temperature of 550 ℃ to obtain powder B.
Drying and crushing biota orientalis plant leaves, adding water according to the feed liquid mass ratio of 1: 100, stirring for 2h, filtering to obtain biota orientalis filtrate, taking 30m L deionized water, 30m L biota orientalis filtrate and a palladium nitrate solution with the concentration of 600 mu L of 74mM, putting the mixture into a 200m L conical flask, putting the conical flask into an oil bath kettle at 90 ℃, heating and stirring, fully stirring for 1h, putting the solution into 0.6g of powder B after the original yellow color of the solution is changed into black, fully stirring and heating for 1h, filtering, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain powdered Pt-Pd/TiO2A bimetallic photocatalyst a.
Benzyl alcohol oxidation reaction, adding Pt-Pd/TiO into a 50m L three-neck flask20.1g of catalyst and 10m L benzyl alcohol are added, then the three-neck flask is placed in a 90 ℃ oil bath pot to be preheated for 5min and refluxed, then oxygen of 90m L/min is introduced, a 150W metal halogen lamp light source is turned on to start the photocatalytic reaction, and the catalytic reaction result is shown in table 1.
Example 2
Preparing powder A according to the method of example 1, placing powder A into a ceramic crucible, placing into a tube furnace, sealing, introducing hydrogen gas for calcination for 4h, the calcination temperature is 650 ℃, obtaining powder C, placing 30m L deionized water, 30m L arborvitae filtrate, 600 mu L palladium nitrate solution with the concentration of 74mM into a 200m L conical flask, placing the conical flask into an oil bath kettle at 90 ℃, heating and stirring, after fully stirring for 1h, placing the solution into 0.6g of powder C after the solution turns from original yellow to black, fully stirring and heating for 1h, filtering, and placing into a vacuum drying oven at 60 ℃ for drying for 12h, thus obtaining powdered Pt-Pd/TiO2And (3) a bimetallic photocatalyst B. The catalyst evaluation conditions were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 3
Powder A was prepared according to the method of example 1, powder A was placed in a ceramic crucible, placed in a tube furnace again, sealed and calcined for 4h with introduction of hydrogen at 750 ℃ to give powder D, 30m L deionized water, 30m L arborvitae filtrate, 600 μ L palladium nitrate solution with a concentration of 74mM were taken and placed in a 200m L conical flask and placed in a ceramic crucible, and powder D was calcined for 4h with introduction of hydrogen gasHeating and stirring in oil bath at 90 deg.C. Stirring thoroughly for 1 hr until the color of the solution turns from yellow to black, adding 0.6g of powder D, stirring thoroughly, heating for 1 hr, filtering, and drying in a vacuum drying oven at 60 deg.C for 12 hr to obtain powdered Pt-Pd/TiO2The bimetallic photocatalyst C is shown in a TEM image 1 of the catalyst, and bimetallic nanoparticles are distributed at about 3-7 nm. EDX (FIG. 2) shows TiO2The surface has both Pt and Pd elements, which shows that the synthesized catalyst is a Pt-Pd bimetallic catalyst. The catalyst evaluation conditions were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 4
Preparing powder A according to the method of example 1, placing powder A into a ceramic crucible, placing into a tube furnace, sealing, introducing hydrogen gas for calcination for 4h, the calcination temperature is 850 ℃, obtaining powder E, placing 30m L deionized water, 30m L arborvitae filtrate, 600 mu L palladium nitrate solution with the concentration of 74mM into a 200m L conical flask, placing the conical flask into an oil bath kettle at 90 ℃, heating and stirring, after fully stirring for 1h, placing the solution into 0.6g of powder E after the original soil yellow color is changed into black, fully stirring and heating for 1h, filtering, and placing into a vacuum drying oven at 60 ℃ for drying for 12h, thus obtaining powdered Pt-Pd/TiO2A bimetallic photocatalyst D. The catalyst evaluation conditions were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 5 (non-photocatalytic reaction)
Catalyst C was prepared according to example 3 and used for the non-photocatalytic benzylalcohol oxidation reaction, i.e., benzylalcohol oxidation reaction in a 50m L three-necked flask with addition of Pt-Pd/TiO20.1g of catalyst, 10m of L m of benzyl alcohol was added, the three-necked flask was placed in a 90 ℃ oil bath to be preheated for 5min and refluxed, and then oxygen gas at 90m L/min was introduced to start the reaction, and the results of the catalytic reaction are shown in Table 1.
Example 6 (comparative)
Powder D was prepared according to example 3 and used for photocatalytic benzyl alcohol oxidation. The catalyst evaluation conditions were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 7 (comparative)
1g of nano TiO is taken2(P25) Placing the mixture into a 30m L crucible, adding 1330 mu L mM chloroplatinic acid and 600 mu L mM palladium nitrate solution with the concentration of 74mM by using a pipette, fully stirring the mixture by using a small glass rod, placing the mixture in a vacuum drying oven with the temperature of 60 ℃ for drying for 12 hours, grinding the mixture into powder F, placing the powder F into a ceramic crucible, placing the ceramic crucible into a tubular furnace again, sealing the ceramic crucible, introducing hydrogen for roasting for 4 hours, and roasting the powder at the roasting temperature of 750 ℃ to obtain a catalyst E, wherein the evaluation conditions of the catalyst are the same as those of example 1, and the catalytic reaction result is shown in Table 1.
Example 8 (comparative)
Adding TiO into the mixture2(P25) placing in a ceramic crucible, placing in a tube furnace, sealing, introducing hydrogen gas, roasting for 4h at 750 ℃ to obtain powder G, placing 30m L deionized water, 30m L arborvitae filtrate and 600 mu L palladium nitrate solution with the concentration of 74mM in a 200m L conical flask, placing in an oil bath kettle at 90 ℃ for heating and stirring, after fully stirring for 1h, placing the solution into 0.6G of powder G after the original yellow color of soil turns into black, fully stirring and heating for 1h, filtering, and placing in a vacuum drying oven at 60 ℃ for drying for 12h to obtain powdery Pd/TiO2A bimetallic photocatalyst F. The catalyst evaluation conditions were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
TABLE 1 Pt-Pd/TiO2Catalyst photocatalytic benzyl alcohol oxidation reaction performance
(a) The calcination temperature, benzaldehyde (BzH), benzoic acid (BzA), benzyl benzoate (BzB) and toluene (TO L).
Claims (6)
1. A titanium dioxide supported Pt-Pd bimetallic photocatalyst is characterized by being prepared by the following method:
(1) uniformly mixing nano titanium dioxide and an aqueous solution of a 38.6mM platinum precursor, drying in vacuum at 60 ℃, grinding into powder, heating to 550-850 ℃ in a sealed hydrogen atmosphere, and roasting for 2-6 hours to obtain platinum-loaded titanium dioxide;
the volume consumption of the aqueous solution of the platinum precursor is 1.33m L/g by mass of the nano titanium dioxide;
(2) drying and crushing leaves of the arborvitae plants, and mixing the dried and crushed leaves according to a feed liquid mass ratio of 1: adding 50-150 parts of the cacumen biotae into deionized water, stirring for 1-5 hours, filtering, collecting a cacumen biotae filtrate, mixing the cacumen biotae filtrate with the deionized water and a 74mM palladium precursor aqueous solution according to a volume ratio of 1: 1: 0.02, stirring for 1h at 90 ℃ to obtain a mixed solution, and then adding the mixed solution into the mixed solution according to the mass ratio of the feed liquid of 1: 80-120, adding the platinum-loaded titanium dioxide obtained in the step (1), keeping the temperature, stirring for 1h, filtering, and drying a filter cake in vacuum at 60 ℃ to obtain the titanium dioxide-loaded Pt-Pd bimetallic photocatalyst.
2. The titania-supported Pt-Pd bimetallic photocatalyst of claim 1, wherein the nano-titania is titania P25.
3. The titania-supported Pt-Pd bimetallic photocatalyst of claim 1, wherein the platinum precursor is chloroplatinic acid or sodium chloroplatinate.
4. The titania-supported Pt-Pd bimetallic photocatalyst of claim 1, wherein the palladium precursor is palladium chloride or palladium nitrate.
5. The use of the titania-supported Pt-Pd bimetallic photocatalyst as defined in claim 1 in the photocatalytic reaction of benzyl alcohol for preparing benzaldehyde.
6. The application of claim 5, wherein the method of applying is:
adding the catalyst into benzyl alcohol, preheating for 5min at 90 ℃, refluxing, introducing oxygen at the speed of 90m L/min, simultaneously turning on a 150W metal halide lamp light source for photocatalytic reaction, and monitoring by HP L C until the reaction is complete;
the mass usage of the catalyst is 0.002-0.02 g/m L calculated by the volume of the benzyl alcohol.
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