CN110449154A - A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application - Google Patents
A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application Download PDFInfo
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- CN110449154A CN110449154A CN201910658398.0A CN201910658398A CN110449154A CN 110449154 A CN110449154 A CN 110449154A CN 201910658398 A CN201910658398 A CN 201910658398A CN 110449154 A CN110449154 A CN 110449154A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 40
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 79
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 229960004643 cupric oxide Drugs 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JIQILHWIXUIMIO-UHFFFAOYSA-N OC.COC=O Chemical compound OC.COC=O JIQILHWIXUIMIO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- LBPGGVGNNLPHBO-UHFFFAOYSA-N [N].OC Chemical compound [N].OC LBPGGVGNNLPHBO-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
Abstract
The invention discloses a kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application.The present invention is by nitric acid copper salt solution and anatase TiO2Spindle mixing, sodium borohydride reduction agent is then added, regulate and control CuO nanoparticle and { 101 } and { 001 } interplanar coordination mode and active force, so that CuO nanoparticle is selectively deposited in { 101 } crystal face, construct copper oxide and titanium dioxide heterogeneous knot complex catalyst system.The catalyst is in the reaction of photochemical catalytic oxidation preparation of methyl formate from methanol, and at 25 DEG C, for the conversion ratio of methanol up to 95%, the selectivity of methyl formate is up to 85%.The present invention has rationally constructed copper oxide and titanium dioxide heterogeneous knot composite catalyst, it realizes that light induced electron and hole separate to the greatest extent using the synergistic effect of heterogeneous interface, further promotes the reactivity and selectivity of 15-45 DEG C of photochemical catalytic oxidation preparation of methyl formate from methanol of low temperature.
Description
Technical field
The invention belongs to composite material and photocatalysis technology field, in particular to a kind of copper oxide and titanium dioxide heterogeneous knot
Composite catalyst and its preparation method and application, specifically, the present invention is selective by CuO nanoparticle using deposition-precipitation method
Ground is deposited on anatase TiO2{ 101 } crystal face of spindle, rationally constructs copper oxide and titanium dioxide heterogeneous knot composite catalyst,
It promotes light induced electron and hole separates to the greatest extent, realizing low temperature, (photocatalysis methanol prepares formic acid first under (15-45 DEG C)
The Efficient Conversion of ester.
Background technique
With the variation of global energy structure, the trans-utilization and C of coal, natural gas and biomass1The development of chemistry is increasingly
It is taken seriously, and becomes the important channel with the following solution energy problem at this stage.Important derivative of the methyl formate as methanol
Object is widely used in producing formic acid, formamide and other tens kinds of chemical products, can also be directly used as pharmacy, pesticide, gasoline
Additive is C1Important organic synthesis body in chemistry.Moreover, continually developing, using neck with methyl formate downstream product
The gradually expansion in domain, quicklys increase the demand of methyl formate.On the other hand, current domestic methanol excess capacity, with methanol
Methyl formate is prepared for raw material, can both produce multi-chemical, the situation of methanol excess capacity can also be alleviated, chemical industry is produced
The sustainable development of industry is of great significance.
With it, the characteristics such as green, energy saving, pollution-free show pole in preparation of methyl formate from methanol reaction for photochemical catalytic oxidation
Big advantage and considerable prospect.This method can realize the conversion of methanol to methyl formate at (< 45 DEG C) of low temperature, due to reaction
Temperature is low, and by-product is few, therefore has very important theory significance and practical value.TiO2As a kind of important semiconductor
Material has excellent catalytic activity in the reaction of photochemical catalytic oxidation preparation of methyl formate from methanol.Traditional anatase TiO2
Nano material photocatalysis efficiency is low.Recently research have indicated that co-catalyst (metal or metal oxide) is in TiO2Surface deposition can
Heterogeneous interface knot is formed, in time by TiO2Surface light induced electron and hole are transferred to co-catalyst surface, are conducive to light induced electron
With the further separation in hole, reactivity worth is promoted.However, existing hetero-junctions composite catalyst is that co-catalyst exists mostly
TiO2The non-selectively deposition of nanoparticle surface causes the co-catalyst of part to become light induced electron and hole instead
Complex centre limits the raising of reactivity, therefore how to realize co-catalyst in anatase TiO2The selectivity on surface is heavy
Product is the key that realize photocatalysis preparation of methyl formate from methanol Efficient Conversion.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of copper oxide and titanium dioxide heterogeneous knot are provided
Composite catalyst and preparation method thereof, and photocatalysis preparation of methyl formate from methanol under low temperature (15-45 DEG C) will be used for.
Technical solution is as follows:
A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst are with anatase TiO2Spindle is carrier, using heavy
CuO nanoparticle is selectively deposited in anatase TiO by the product precipitation method2{ 101 } crystal face of spindle forms copper oxide and two
Titanium oxide heterojunction composite catalyst.The mass fraction of the CuO nanoparticle is 3-10%.
Preferably, anatase TiO2Spindle exposes 82% { 101 } crystal face.
A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst the preparation method comprises the following steps:
(1) at room temperature, 2-8mL butyl titanate is added in 20mL acetic acid, is obtained after being vigorously stirred colorless and transparent molten
Liquid is simultaneously transferred into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene；It is naturally cooled to after 150-250 DEG C of constant temperature 12-36h
Room temperature；Anatase TiO is made after dry in the product centrifugal filtration that will be obtained, washing precipitating2Spindle；
(2) by the 0.01-0.1molL of 20-150mL-1Cu(NO3)2Solution is added in round bottom beaker, is then added and is gone
Ionized water；The anatase TiO of 0.5-2g step (1) synthesis is added in stirring2Spindle is put into supersonic cleaning machine after stirring
Middle ultrasound；Sodium borohydride is then added under stiring, 12-36h is stirred at room temperature；The product centrifugal filtration that will be obtained, washing
Copper oxide and titanium dioxide heterogeneous knot composite catalyst is made after dry in precipitating.
Preferably, the amount of copper nitrate is added according to the amount that theoretical CuO mass fraction is 3%-10%, respectively corresponds addition
0.01mol·L-1Cu(NO3)2Amount is 37.71-125.71mL.
Preferably, heating rate is 5-7 DEG C/min in step (1).
Above-mentioned copper oxide and titanium dioxide heterogeneous knot composite catalyst are used for photocatalysis preparation of methyl formate from methanol.Light is urged
The reaction temperature of change is 15-45 DEG C.
The present invention by nitric acid copper salt solution and exposure 82% { 101 } and 18% { 001 } crystal face anatase TiO2Spindle
Sodium borohydride reduction agent is then added in mixing, utilizes { 101 } and { 001 } interplanar atom composition, coordination mode and electronic structure
Difference, regulation CuO nanoparticle and { 101 } and { 001 } interplanar coordination mode and active force makes the selection of CuO nanoparticle
It is deposited on to property { 101 } crystal face, constructs copper oxide and titanium dioxide heterogeneous knot complex catalyst system.Copper oxide and titanium dioxide
Hetero-junctions composite catalyst has showed the photocatalytic activity of enhancing in the reaction of photochemical catalytic oxidation preparation of methyl formate from methanol, at 25 DEG C,
For the conversion ratio of its methanol up to 95%, the selectivity of methyl formate is up to 85%.This is the result shows that CuO nanoparticle and rutile titania
Mine TiO2{ 101 } interplanar heterogeneous interface constructs the separation that can effectively facilitate light induced electron and hole, realizes photocatalysis methanol
Prepare the efficient conversion of methyl formate.
Detailed description of the invention
Fig. 1 is TiO2With the XRD characterization of copper oxide and titanium dioxide composite catalyst.
Fig. 2 is TiO2It is characterized with the Electronic Speculum of 7% copper oxide and titanium dioxide composite catalyst.
Fig. 3 is TiO2It is reacted with the photocatalysis preparation of methyl formate from methanol of 7% copper oxide and titanium dioxide composite catalyst
Performance.
Specific embodiment
To make those skilled in the art more fully understand technical solution of the present invention, below with reference to embodiment to the present invention
A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst for there is provided and its preparation method and application are described in detail.Below
Embodiment is merely to illustrate the range of the present invention and is not intended to limit the present invention.
The preparation of 1 copper oxide of embodiment and titanium dioxide heterogeneous knot composite catalyst:
At room temperature, 5mL butyl titanate is added in 20mL acetic acid, is vigorously stirred 10min, mixed solution becomes colorless
It is transparent, then mixed solution is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and is placed in baking oven, with 5 DEG C/min liter
Warm rate is warming up to 200 DEG C, is kept for 200 DEG C of constant temperature, reaction for 24 hours, is then naturally cooled to room temperature.Obtained product was centrifuged
Filter, be washed with deionized precipitating three times, dehydrated alcohol washing precipitating it is primary, then at 80 DEG C, rutile titania is made in dry 12h
Mine TiO2Spindle is labeled as TiO2-P；Respectively by 37.71mL, 62.86mL, 88.00mL, the 0.01molL of 125.71mL- 1Cu(NO3)2Solution is added in 500mL round bottom beaker, and 100mL deionized water is then added, and 1g anatase is added in stirring
TiO2Spindle is put into ultrasound 30min in supersonic cleaning machine, sodium borohydride, In is then added under stiring after stirring 5min
Stir the product centrifugal filtration that will be obtained for 24 hours at room temperature, be washed with deionized precipitating three times, dehydrated alcohol washing precipitating one
Secondary, then at 60 DEG C, 3%, 5%, 7%, 10% copper oxide and titanium dioxide heterogeneous knot composite catalyst is made in dry 12h.
Butyl titanate used in the present invention is to analyze pure, purity >=99.0%, and acetic acid is to analyze pure, concentration >=99.5%, nitre
Sour copper is to analyze pure, purity >=99.0%, and sodium borohydride is to analyze pure, purity >=98.0%.Anatase prepared by the present invention
TiO2Spindle is marked as TiO2-P；Gained catalyst according to copper nitrate additive amount 37.71mL, 62.86mL, 88.00mL,
125.71mL is respectively labeled as 3% copper oxide and titanium dioxide-P, 5% copper oxide and titanium dioxide-P, 7% copper oxide and two
Titanium oxide-P, 10% copper oxide and titanium dioxide-P.
Fig. 1 gives the XRD spectra of copper oxide and titanium dioxide heterogeneous knot composite catalyst, and rutile titania is presented in gained sample
Mine TiO2Diffraction maximum, there is no Cu, CuO, Cu2The appearance of the diffraction maximum of O shows that CuO nanoparticle is evenly dispersed in TiO2It spins
On the surface of hammer body.
Fig. 2 gives TiO2With the morphology characterization of copper oxide and titanium dioxide composite catalyst, Fig. 2 a-c is TiO2Spindle
Electron microscopic picture.Anatase TiO2It can clearly be seen that interplanar distance is 0.35nm and 0.47nm, angle is for the side of spindle
70 ° of lattice fringe, top surface is it can be seen that spacing is 0.19nm, and the lattice fringe that angle is 90 °, this shows anatase TiO2Side
Face mainly exposes { 101 } crystal face, and its ratio be 82%, top surface mainly exposes { 001 } crystal face, and its ratio be 18%.Fig. 2 d-f gives
The morphology characterization for having gone out copper oxide and titanium dioxide composite catalyst shows that copper oxide and titanium dioxide composite catalyst are still just in
Existing regular spindle structure.It can see from Fig. 2 e, f, { 001 } crystal face smoother, and be able to observe that in { 101 } crystal face
Partial size is the nanoparticle of 3.5nm, while in nanoparticle surface it can clearly be seen that interplanar distance is the lattice of 0.23nm
Striped, corresponding is CuO { 111 } crystal face, based on the above analysis, shows that CuO nanoparticle has been selectively deposited in rutile titania
Mine TiO2{ 101 } crystal face of spindle.
2 copper oxide of embodiment and the reaction of titanium dioxide composite catalyst photocatalysis preparation of methyl formate from methanol:
Photochemical catalytic oxidation methanol prepares formic acid reaction and carries out in the aluminium alloy reactor continuously flowed.Catalyst is uniform
Ground is coated on the suitable rectangle-shaped slides of three chip sizes, then glass slide is put into reactive tank, then puts one on reactive tank again
Block quartz glass seals reactive tank.Above quartz glass install a 500W high-pressure sodium lamp so that be coated with catalyst that
Glass slide on one side is fully exposed under mercury lamp, and entire reaction is controlled the temperature of reaction at 25-45 DEG C using cooling water circulation.
Methanol/oxygen/nitrogen gaseous mixture is passed through above catalyst to be reacted.Gaseous mixture is to pass through low temperature in a manner of being bubbled by nitrogen
Methanol bubbler, and with the another two-way nitrogen after metering, oxygen mix, the percentage by volume of methanol is no more than 3%, methanol and oxygen
Gas is than control between 0.1-3.Reaction product detection is using the gas-chromatography (Agilent that FID and TCD dual detector is housed
GC7820A) on-line checking.The influence of temperature, luminous intensity and methanol/oxygen blending ratio to reactivity worth is investigated in test process.
The dosage of catalyst is 20mg, and before reaction, catalyst is in 3vol.%O2/N2Locate in advance at 45 DEG C under (flow 30mL/min) atmosphere
Manage 30min, then this atmosphere purging drop to room temperature, after switch to unstripped gas 1.5vol.%CH3OH, 0.5vol.%O2/
N2.Gas flow rate is controlled by mass flowmenter, and reactor feed gas is kept the temperature at 150 DEG C.It can be seen from figure 3 that copper oxide and titanium dioxide
Titanium hetero-junctions composite catalyst shows the reactivity of enhancing, and 7% copper oxide and titanium dioxide-P give best catalysis
Performance, at 25 DEG C, the conversion ratio of methanol is up to 95%, and the selectivity of methyl formate is up to 85%, and by-product is only titanium dioxide
Carbon.
The morphology controllable synthesis of nano-structured calalyst not only contributes to prepare advanced catalysis agent, Er Qieneng for goal response
The deep enough structure-activity relationship understood between catalyst structure and reactivity worth.The present invention is using sodium borohydride as reducing agent, using heavy
The product precipitation method are successfully realized CuO nanoparticle in anatase TiO2{ 101 } selective deposition of crystal face has rationally constructed oxidation
Copper and titanium dioxide heterogeneous knot composite catalyst realize light induced electron and hole utmostly using the synergistic effect of heterogeneous interface
Separation, further promoted low temperature (15-45 DEG C) photochemical catalytic oxidation preparation of methyl formate from methanol reactivity and selectivity.
Example of the invention is explained in detail above in conjunction with embodiment, but the present invention is not limited to examples detailed above,
Within the knowledge of a person skilled in the art, it can also make without departing from the purpose of the present invention
Various change also should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst, which is characterized in that with anatase TiO2Spindle is to carry
CuO nanoparticle is selectively deposited in anatase TiO using deposition-precipitation method by body2{ 101 } crystal face of spindle forms oxygen
Change copper and titanium dioxide heterogeneous knot composite catalyst.
2. copper oxide according to claim 1 and titanium dioxide heterogeneous knot composite catalyst, which is characterized in that described
The mass fraction of CuO nanoparticle is 3-10%.
3. the preparation method of a kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst, which comprises the steps of:
(1) at room temperature, 2-8mL butyl titanate is added in 20mL acetic acid, colourless transparent solution is obtained after being vigorously stirred simultaneously
It is transferred into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene；Room temperature is naturally cooled to after 150-250 DEG C of constant temperature 12-36h；
Anatase TiO is made after dry in the product centrifugal filtration that will be obtained, washing precipitating2Spindle；
(2) by the 0.01-0.1molL of 20-150mL-1 Cu(NO3)2Solution is added in round bottom beaker, and deionization is then added
Water；The anatase TiO of 0.5-2g step (1) synthesis is added in stirring2Spindle is put into supersonic cleaning machine after stirring and is surpassed
Sound；Sodium borohydride is then added under stiring, 12-36h is stirred at room temperature；The product centrifugal filtration that will be obtained, washing precipitating,
Copper oxide and titanium dioxide heterogeneous knot composite catalyst are made after drying.
4. the preparation method of copper oxide and titanium dioxide heterogeneous knot composite catalyst according to claim 3, which is characterized in that
Heating rate is 5-7 DEG C/min in step (1).
5. copper oxide and titanium dioxide heterogeneous knot composite catalyst light that the method according to claim 3 or 4 is prepared
Catalysis methanol prepares the application of methyl formate.
6. application according to claim 5, which is characterized in that the light-catalysed reaction temperature is 15-45 DEG C.
Priority Applications (1)
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| CN114602467A (en) * | 2022-04-02 | 2022-06-10 | 新疆油苗环保科技有限公司 | Copper oxide doped mixed crystal titanium dioxide nanotube photocatalytic composite material and preparation method and application thereof |
| CN114984965A (en) * | 2022-05-30 | 2022-09-02 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
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