CN108579739B - Method for preparing aldehyde/ketone by selectively oxidizing alcohol under mild condition - Google Patents
Method for preparing aldehyde/ketone by selectively oxidizing alcohol under mild condition Download PDFInfo
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- CN108579739B CN108579739B CN201810311121.6A CN201810311121A CN108579739B CN 108579739 B CN108579739 B CN 108579739B CN 201810311121 A CN201810311121 A CN 201810311121A CN 108579739 B CN108579739 B CN 108579739B
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 150000002576 ketones Chemical class 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000001299 aldehydes Chemical class 0.000 title claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 title abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001298 alcohols Chemical class 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 3
- 238000002256 photodeposition Methods 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000003283 rhodium Chemical class 0.000 claims description 4
- 159000000008 strontium salts Chemical class 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- LMCBEWMQFKWHGU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O LMCBEWMQFKWHGU-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- -1 can be seen Chemical compound 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010626 work up procedure 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B01J35/39—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
Abstract
The present invention provides a process for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones. Mainly takes rhodium-doped strontium titanate as a semiconductor substrate, and obtains Pt/Rh-SrTiO through photo-deposition of platinum nano-particles3The heterojunction structure acts as a photocatalyst. The photocatalyst takes water as a reaction medium and an oxidant under the conditions of oxygen-free environment and visible light catalysis, can efficiently and selectively oxidize hydroxyl in alcohol molecules to obtain aldehyde/ketone, and simultaneously generates stoichiometric hydrogen. Compared with other traditional thermal catalytic alcohol oxidation methods, the method has the advantages of high efficiency, good selectivity, environmental friendliness, mild conditions and the like, and the method is a successful example of expanding the field of photocatalytic synthesis of solar fuels to heterogeneous catalytic organic molecule conversion by efficiently oxidizing the alcoholic hydroxyl group to the ketocarbonyl group in the aqueous medium at normal temperature and normal pressure.
Description
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to a method for preparing aldehyde/ketone by selectively oxidizing alcohol under mild conditions.
Background
The synthesis of aldehydes and ketones by selective oxidation of alcohols is a major reaction in organic synthesis and industrial chemistry.[1-3]However, not only do conventional thermal catalytic oxidation processes require harsh reaction conditions, but the use of corrosive reagents and toxic metal catalysts results in difficulties in by-product and product purification and work-up. Development of mild reaction conditions and environmental friendlinessGood reaction pathways for highly selective oxidation of alcohols, especially for oxidation of primary alcohols to aldehydes rather than over-conversion to acids, have been a great challenge in the field of heterogeneous catalysis.[4]To date, researchers have utilized inorganic semiconductors (e.g., TiO)2,[5-7]CdS,[8-10]WO3,[11,12]CeO2,[13-15]Metal Organic Framework (MOFs)[16]) And organic semiconductors[3,17-19]Carrying out organic catalytic conversion such as alcohol oxidation. These aerobic oxidation reactions mostly use organic solvents such as acetonitrile, trifluorotoluene, etc. to increase O2Or to reduce side reactions.[12,14,20,21]
In the absence of oxygen, Pattenden et al indicate that platinum-loaded titanium dioxide in benzene solvent is capable of catalyzing the oxidation of alcohols to aldehydes and ketones by exposure to light and simultaneously producing hydrogen, which provides a clean route to alcohol oxidation.[22]Recently, Xu and co-workers reported the cleavage of alcohols into hydrogen and the corresponding carbonyl compounds on nickel-modified cadmium sulfide nanoparticles in acetonitrile.[23]However, cadmium sulfide semiconductors generally suffer from severe performance degradation due to the effects of self-corrosion.
Considering that in the research of preparing hydrogen by photocatalytic water splitting half reaction, alcohol is generally used as a sacrificial agent and is over-oxidized into acid, even carbon dioxide and the like, most of the research shows that a photocatalytic hydrogen production system under visible light of solar fuel which can selectively oxidize alcohol to obtain aldehyde/ketone and the like with stable performance and simultaneously generate hydrogen is not reported. Porous doped strontium titanate is prepared by a method of using a precursor of a polymeric metal organic complex, and the valence state of doped rhodium element is controlled by adjusting the calcination temperature of the precursor to control the concentration of surface oxygen defects, so that the chemical adsorption behavior of alcohol molecules on the surface of a catalyst is influenced, and the photocatalyst with high catalytic efficiency and good selectivity is obtained. Meanwhile, a photocatalytic reaction system is adjusted, and alcohol hydroxyl is oxidized into carbonyl by taking water as an oxidant under an inert atmosphere, and stoichiometric hydrogen is formed at the same time.
Reference documents:
[1]R.A.Sheldon,I.Arends,A.Dijksman,New developments in catalyticalcohol oxidations for fine chemicals synthesis,Catalysis Today,57(2000)157-166.
[2]J.M.Thomas,R.Raja,G.Sankar,R.G.Bell,Molecular-sieve catalysts forthe selective oxidation of linear alkanes by molecular oxygen,Nature,398(1999)227.
[3]W.Huang,B.C.Ma,H.Lu,R.Li,L.Wang,K.Landfester,K.A.I.Zhang,Visible-Light-Promoted Selective Oxidation of Alcohols Using a Covalent TriazineFramework,ACS Catalysis,7(2017)5438-5442.
[4]P.Zhang,Y.Gong,H.Li,Z.Chen,Y.Wang,Solvent-free aerobic oxidationof hydrocarbons and alcohols with Pd@N-doped carbon from glucose,Naturecommunications,4(2013)1593.
[5]X.Lang,W.Ma,C.Chen,H.Ji,J.Zhao,Selective Aerobic OxidationMediated by TiO2 Photocatalysis,Accounts of Chemical Research,47(2014)355-363.
[6]D.Tsukamoto,Y.Shiraishi,Y.Sugano,S.Ichikawa,S.Tanaka,T.Hirai,GoldNanoparticles Located at the Interface of Anatase/Rutile TiO2Particles asActive Plasmonic Photocatalysts for Aerobic Oxidation,Journal of the AmericanChemical Society,134(2012)6309-6315.
[7]V.Augugliaro,T.Caronna,V.Loddo,G.Marcì,G.Palmisano,L.Palmisano,S.Yurdakal,Oxidation of aromatic alcohols in irradiated aqueous suspensionsof commercial and home‐prepared rutile TiO2:a selectivity study,Chemistry-AEuropean Journal,14(2008)4640-4646.
[8]S.Liu,N.Zhang,Z.-R.Tang,Y.-J.Xu,Synthesis of One-Dimensional CdS@TiO2 Core–Shell Nanocomposites Photocatalyst for Selective Redox:The DualRole of TiO2 Shell,ACS Applied Materials&Interfaces,4(2012)6378-6385.
[9]N.Zhang,S.Liu,X.Fu,Y.-J.Xu,Fabrication of coenocytic Pd@CdSnanocomposite as a visible light photocatalyst for selective transformationunder mild conditions,Journal of Materials Chemistry,22(2012)5042-5052.
[10]N.Zhang,Y.Zhang,X.Pan,X.Fu,S.Liu,Y.-J.Xu,Assembly of CdSnanoparticles on the two-dimensional graphene scaffold as visible-light-driven photocatalyst for selective organic transformation under ambientconditions,The Journal of Physical Chemistry C,115(2011)23501-23511.
[11]N.Zhang,X.Li,H.Ye,S.Chen,H.Ju,D.Liu,Y.Lin,W.Ye,C.Wang,Q.Xu,J.Zhu,L.Song,J.Jiang,Y.Xiong,Oxide Defect Engineering Enables to Couple SolarEnergy into Oxygen Activation,Journal of the American Chemical Society,138(2016)8928-8935.
[12]D.Tsukamoto,M.Ikeda,Y.Shiraishi,T.Hara,N.Ichikuni,S.Tanaka,T.Hirai,Selective photocatalytic oxidation of alcohols to aldehydes in waterby TiO2 partially coated with WO3,Chemistry-A European Journal,17(2011)9816-9824.
[13]A.Tanaka,K.Hashimoto,H.Kominami,Preparation of Au/CeO2exhibitingstrong surface plasmon resonance effective for selective or chemoselectiveoxidation of alcohols to aldehydes or ketones in aqueous suspensions underirradiation by green light,Journal of the American Chemical Society,134(2012)14526-14533.
[14]Y.Zhang,N.Zhang,Z.-R.Tang,Y.-J.Xu,A unique silk mat-likestructured Pd/CeO2 as an efficient visible light photocatalyst for greenorganic transformation in water,ACS Sustainable Chemistry&Engineering,1(2013)1258-1266.
[15]A.Tanaka,K.Hashimoto,H.Kominami,Selective photocatalyticoxidation of aromatic alcohols to aldehydes in an aqueous suspension of goldnanoparticles supported on cerium(IV)oxide under irradiation of green light,Chemical Communications,47(2011)10446-10448.
[16]Y.-Z.Chen,Z.U.Wang,H.Wang,J.Lu,S.-H.Yu,H.-L.Jiang,Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF:TheRoles of Photothermal Effect and Pt Electronic State,Journal of the AmericanChemical Society,139(2017)2035-2044.
[17]F.Su,S.C.Mathew,G.Lipner,X.Fu,M.Antonietti,S.Blechert,X.Wang,mpg-C3N4-Catalyzed Selective Oxidation of Alcohols Using O2 and Visible Light,Journal of the American Chemical Society,132(2010)16299-16301.
[18]F.Su,S.C.Mathew,L.
M.Antonietti,X.Wang,S.Blechert,Aerobic oxidative coupling of amines by carbon nitride photocatalysis withvisible light,Angewandte Chemie International Edition,50(2011)657-660.
[19]Y.Wang,J.Zhang,X.Wang,M.Antonietti,H.Li,Boron‐and Fluorine‐Containing Mesoporous Carbon Nitride Polymers:Metal‐Free Catalysts forCyclohexane Oxidation,Angewandte Chemie International Edition,49(2010)3356-3359.
[20]Y.Zhang,Y.-J.Xu,Bi 2 WO 6:a highly chemoselective visible lightphotocatalyst toward aerobic oxidation of benzylic alcohols in water,RscAdvances,4(2014)2904-2910.
[21]Y.Zhang,N.Zhang,Z.-R.Tang,Y.-J.Xu,Identification of Bi 2WO 6as ahighly selective visible-light photocatalyst toward oxidation of glycerol todihydroxyacetone in water,Chemical Science,4(2013)1820-1824.
[22]F.H.Hussein,G.Pattenden,R.Rudham,J.J.Russell,Photo-oxidation ofalcohols catalysed by platinised titanium dioxide,Tetrahedron letters,25(1984)3363-3364.
[23]Z.Chai,T.-T.Zeng,Q.Li,L.-Q.Lu,W.-J.Xiao,D.Xu,Efficient VisibleLight-Driven Splitting of Alcohols into Hydrogen and Corresponding CarbonylCompounds over a Ni-Modified CdS Photocatalyst,Journal of the AmericanChemical Society,138(2016)10128-10131.
disclosure of Invention
In one aspect of the present invention, a method for preparing a photocatalyst is provided, comprising the steps of:
the method comprises the following steps: ethylene glycol and citric acid are used as complexing molecules and are subjected to complex reaction with titanium isopropoxide, strontium nitrate and rhodium nitrate to obtain a metal polymer precursor;
step two: calcining the metal polymer precursor obtained in the step one at a high temperature to form rhodium-doped strontium titanate with a mesoporous structure;
step three: mixing sacrificial agent, rhodium-doped strontium titanate and chloroplatinic acid (H) with the mesoporous structure2PtCl6) And carrying out light deposition on the platinum nanoparticles by using the mixed solution of the solution under illumination to obtain the photocatalyst.
Further, in the first step, titanium isopropoxide is dissolved in ethylene glycol and stirred, citric acid, strontium nitrate and rhodium nitrate are sequentially added, the obtained mixture is stirred for half an hour at the temperature of 60 ℃, then full polymerization is carried out at the temperature of 150 ℃ until reddish brown viscous gel appears, and the gel is carbonized for 2 hours at the temperature of 350 ℃ in an inert atmosphere to obtain the black fluffy metal polymer precursor.
Further, in the second step, the metal polymer precursor is uniformly ground and then calcined at the temperature of 500-900 ℃ for 10 hours to obtain the rhodium-doped strontium titanate with the mesoporous structure.
Further, in the third step, rhodium is doped with strontium titanate and chloroplatinic acid (H)2PtCl6) Mixing the solution with sacrificial agent, stirring, irradiating for 5 hr, washing and drying to obtain Pt/Rh-SrTiO3A photocatalyst of a heterojunction structure.
Alternatively, the calcination in step two may be performed in an air, argon, nitrogen or helium atmosphere.
Optionally, the sacrificial agent in step three may be selected from one or more of alcohols. The alcohols include methanol, isopropanol, ethanol, and propanol.
Further, the light irradiation in the third step is ultraviolet light irradiation.
Alternatively, titanium isopropoxide salts, strontium nitrate, rhodium nitrate may be replaced with other hydrolysable titanium salts, strontium salts, rhodium salts.
Alternatively, the inert atmosphere used in the carbonization process includes an argon, nitrogen or helium atmosphere.
In another aspect, the present invention provides a method for preparing aldehydes/ketones by selective oxidation of alcohols under mild conditions, comprising: dispersing the photocatalyst sample obtained by the method in the degassed aqueous solution, adding benzyl alcohol, and sampling/ketone after illuminating for several hours.
Further, in this method, irradiation with visible light is performed at a temperature of 14 ℃ in an inert atmosphere.
Alternatively, the inert atmosphere may be argon, helium, neon or nitrogen.
As described above, the present invention has advantages in that: rhodium-doped strontium titanate is used as a semiconductor substrate, and Pt/Rh-SrTiO3 heterojunction is obtained as a photocatalyst through photo-deposition of platinum nanoparticles. The photocatalyst can efficiently and selectively oxidize hydroxyl in alcohol molecules to obtain aldehyde/ketone and simultaneously generate stoichiometric hydrogen under the visible light catalysis condition in an oxygen-free environment. Compared with the traditional method for oxidizing alcohol by utilizing an oxidant under high temperature and high pressure through thermal catalysis, the method has the advantages of mild catalytic reaction conditions, simplicity in operation, lower requirements on equipment, good stability, good efficiency and high selectivity, and is suitable for mass production.
Drawings
FIG. 1 is an XRD pattern of a sample of rhodium-doped strontium titanate calcined at different temperatures according to the present invention;
FIG. 2 is a graph showing UV-VIS absorption spectra of samples of rhodium-doped strontium titanate and pure strontium titanate obtained by calcination at different temperatures in accordance with the present invention;
FIG. 3 is a TEM image of a platinum-loaded RhSTO-600 sample according to the present invention;
FIG. 4a shows the oxidation performance of rhodium-doped strontium titanate (loaded with 3% Pt) obtained by calcination at different temperatures in the present invention on p-benzyl alcohol under visible light illumination, and FIG. 4b shows the oxidation performance of RhSTO-600 samples loaded with different platinum masses in the present invention on p-benzyl alcohol under visible light illumination (catalytic conditions: 25mg of catalyst, 0.2mmol of benzyl alcohol, 5mL of water, argon atmosphere, 300W xenon lamp, visible light wavelength greater than 400nm,14 ℃,6 h);
FIG. 5 is a graph showing the long-term catalytic oxidation performance of Pt-loaded Rh-STO-600 catalyst on benzyl alcohol under visible light, i.e., the time relationship between the production of benzaldehyde and hydrogen (catalytic conditions: 50mg of catalyst, 6mmol of benzyl alcohol, 20mL of water, argon atmosphere, 300W xenon lamp, visible light wavelength of more than 400nm,14 ℃,6 h).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a method for preparing a photocatalyst, which comprises the following steps:
the method comprises the following steps: ethylene glycol and citric acid are used as complexing molecules and are subjected to complex reaction with titanium isopropoxide, strontium nitrate and rhodium nitrate to obtain a metal polymer precursor;
step two: calcining the metal polymer precursor obtained in the step one at a high temperature to form rhodium-doped strontium titanate with a mesoporous structure;
step three: doping strontium titanate and chloroplatinic acid (H) with sacrificial agent and rhodium with mesoporous structure2PtCl6) And carrying out light deposition on the platinum nanoparticles by using the mixed solution of the solution under illumination to obtain the photocatalyst.
In the first step, titanium isopropoxide can be dissolved in ethylene glycol and stirred, citric acid, strontium nitrate and rhodium nitrate are sequentially added, the obtained mixture is stirred at 60 ℃ for half an hour and then fully polymerized at 150 ℃ until a reddish brown viscous gel appears, and the gel is carbonized at 350 ℃ for 2 hours in argon gas to obtain the black fluffy metal polymer precursor.
The isopropanol titanium salt, strontium nitrate and rhodium nitrate can be replaced by other hydrolysable titanium salt, strontium salt and rhodium salt. Hydrolysable titanium salts such as TiCl4 or tetrabutyl titanate; hydrolyzable strontium salts such as strontium chloride; hydrolyzable rhodium salts such as rhodium chloride.
And then, in the second step, the metal polymer precursor is uniformly ground and then calcined for 10 hours at the temperature of 500-900 ℃ to obtain the rhodium-doped strontium titanate with the mesoporous structure. The calcination may be performed in an air atmosphere, an argon atmosphere, a nitrogen atmosphere, or a helium atmosphere.
FIG. 1 is an XRD pattern of a rhodium-doped strontium titanate sample calcined at different temperatures in the present invention, from which it can be seen that, except for a small amount of carbon-induced miscellaneous peaks at 500 ℃, other samples are perovskite pure phases, which indicates that the method can successfully prepare strontium titanate materials.
FIG. 2 shows UV-VIS absorption spectra of samples of rhodium-doped strontium titanate and pure strontium titanate obtained by calcination at different temperatures in the present invention,wherein rhodium doping is capable of red-shifting the absorption edge of strontium titanate to the visible region, and calcination at different temperatures has a significant effect on the resulting doped strontium titanate structure, the material exhibits an absorption peak at 580nm when the calcination temperature is above 800 ℃, and the peak intensity is greater at higher temperatures, which is believed to be due to electrons from the strontium titanate valence band to Rh4+Transitions without occupying the d-track.
Then, in the third step, doping rhodium with strontium titanate and chloroplatinic acid (H)2PtCl6) Mixing the solution with sacrificial agent, stirring, irradiating for 5 hr, washing and drying to obtain Pt/Rh-SrTiO3A photocatalyst of a heterojunction structure. The sacrificial agent may be selected from one or more of alcohols. Alcohols such as methanol, isopropanol, ethanol. The light irradiation is ultraviolet light irradiation.
FIG. 3 is a TEM image of a platinum loaded RhSTO-600 sample of the present invention in which the strontium titanate particles are about 20-30nm in size and the platinum particles are about 2-3nm in size, showing that the lattice spacing (0.277) is that of the strontium titanate (110) interplanar spacing.
The present invention also provides a method for preparing aldehyde/ketone by selective oxidation of alcohol under mild conditions, comprising: the photocatalyst sample prepared by the method is dispersed in the aqueous solution after degassing treatment, benzyl alcohol is added, and the sample is taken and centrifuged after illumination for a plurality of hours to obtain alcohol/ketone.
In this method, irradiation with visible light is carried out at a temperature of 14 ℃ in an inert atmosphere. The inert atmosphere can be argon, helium, neon or nitrogen.
In one embodiment, Pt/Rh-SrTiO can be taken3Dispersing 25mg of a photocatalyst sample with a heterojunction structure in 5ml of degassed water solution, adding 0.2mmol of benzyl alcohol, keeping the temperature of a reaction system at 14 ℃, illuminating for several hours in an inert atmosphere under visible light, sampling, centrifuging, analyzing supernate by gas chromatography, and collecting and measuring the volume of generated hydrogen in a catalytic device by an exhaust method.
FIG. 4a shows the oxidation performance of rhodium-doped strontium titanate (loaded with 3 wt% Pt) obtained by calcination at different temperatures under visible light irradiation on benzyl alcohol, and the performance of Rh-STO-600 obtained at 600 ℃ is the best. FIG. 4b shows that different platinum loadings have a significant effect on the performance of Rh-STO-600 samples on the oxidation of benzyl alcohol under visible light, with the initial 3 wt% Pt being the optimum loading. The catalytic conditions for the reactions in FIGS. 4a and 4b are: 25mg of catalyst, 0.2mmol of benzyl alcohol and 5mL of water, wherein the inert atmosphere is argon atmosphere, a 300W xenon lamp is used, the wavelength of visible light is more than 400nm, the temperature of a reaction system is 14 ℃, and the illumination time is 6 h.
As can be seen in Table 1, the photocatalytic oxidation of different alcohol molecules on Pt-loaded Rh-STO-600 catalyst all showed high selectivity, aldehyde/ketone formation, and the oxidation rates appeared to be significantly different due to the different strength of the C-H bond on the alpha carbon in different alcohol molecules, and the position of the hydroxyl group in the substrate alcohol molecule also affected the oxidation rate due to steric effects. The catalytic conditions for the reactions in Table 1 are the same as for FIGS. 4a and 4 b.
TABLE 1
In the second embodiment, as shown in FIG. 5, the catalytic oxidation performance of the catalyst Rh-STO-600 on p-benzyl alcohol for a long time under visible light, i.e. the time relationship between the generated benzaldehyde and hydrogen, can be seen, and benzaldehyde can be stably generated (36.1. mu. mol/h) and hydrogen with stoichiometric amount can be generated. The catalytic conditions for the reaction in FIG. 5 are: 50mg of catalyst, 6mmol of benzyl alcohol and 20mL of water, wherein the inert atmosphere is argon atmosphere, a 300W xenon lamp is used, the wavelength of visible light is more than 400nm, the temperature of a reaction system is 14 ℃, and the illumination time is 6 h.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.
Claims (12)
1. A process for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones comprising the steps of:
the method comprises the following steps: ethylene glycol and citric acid are used as complexing molecules and are subjected to complex reaction with titanium isopropoxide, strontium nitrate and rhodium nitrate to obtain a metal polymer precursor;
step two: calcining the metal polymer precursor obtained in the step one at a high temperature to form rhodium-doped strontium titanate with a mesoporous structure;
step three: carrying out photo-deposition on platinum nanoparticles by using a sacrificial agent and a mixed solution of rhodium-doped strontium titanate and chloroplatinic acid solution with the mesoporous structure under illumination to obtain a photocatalyst;
step four: dispersing the photocatalyst obtained in the third step into the degassed aqueous solution, adding benzyl alcohol, and sampling aldehyde/ketone after illuminating for several hours.
2. The process according to claim 1 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: in the first step, titanium isopropoxide is dissolved in ethylene glycol and stirred, citric acid, strontium nitrate and rhodium nitrate are sequentially added, the obtained mixture is stirred at 60 ℃ for half an hour and then fully polymerized at 150 ℃ until reddish brown viscous gel appears, and the gel is carbonized at 350 ℃ for 2 hours in an inert atmosphere to obtain the black fluffy metal polymer precursor.
3. The process according to claim 2 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: in the second step, the metal polymer precursor is uniformly ground and then calcined at the temperature of 500-900 ℃ for 10 hours to obtain the rhodium-doped strontium titanate with the mesoporous structure.
4. The process according to claim 3 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: in the third step, the rhodium-doped strontium titanate, the chloroplatinic acid solution and the sacrificial agent are mixed and are stirred to be irradiated for 5 hours, and the Pt/Rh-SrTiO is obtained after washing and drying3A photocatalyst of a heterojunction structure.
5. The process according to claim 1 or 3 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the calcination in the second step can be performed in an atmosphere of air, argon, nitrogen or helium.
6. The process according to claim 1 or 4 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the sacrificial agent in the third step can be one or more selected from alcohols.
7. The process according to claim 6 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the alcohols include methanol, isopropanol, ethanol, propanol.
8. The process according to claim 1 or 4 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: and the illumination in the third step is ultraviolet illumination.
9. The process according to claim 1 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the isopropanol titanium salt, strontium nitrate and rhodium nitrate can be replaced by other hydrolysable titanium salt, strontium salt and rhodium salt.
10. The process according to claim 2 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the inert atmosphere used in the carbonization process includes an argon or helium atmosphere.
11. The process according to claim 1 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: in the fourth step, irradiation with visible light is carried out at a temperature of 14 ℃ in an inert atmosphere.
12. The process according to claim 11 for the selective oxidation of alcohols under mild conditions to produce aldehydes/ketones, characterized in that: the inert atmosphere can be argon, helium or neon.
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