CN112569919A - Based on TiO2-xHindered Lewis acid-base photocatalyst and preparation method and application thereof - Google Patents
Based on TiO2-xHindered Lewis acid-base photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112569919A CN112569919A CN202011445324.8A CN202011445324A CN112569919A CN 112569919 A CN112569919 A CN 112569919A CN 202011445324 A CN202011445324 A CN 202011445324A CN 112569919 A CN112569919 A CN 112569919A
- Authority
- CN
- China
- Prior art keywords
- lewis acid
- photocatalyst
- tio
- reaction
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000006722 reduction reaction Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000002841 Lewis acid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000007517 lewis acids Chemical class 0.000 claims description 9
- 239000002879 Lewis base Substances 0.000 claims description 8
- 150000007527 lewis bases Chemical class 0.000 claims description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- 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 7
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001089 mineralizing effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910013722 M(NO3)2 Inorganic materials 0.000 claims description 3
- 230000033558 biomineral tissue development Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 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 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910018965 MCl2 Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of material synthesis and catalytic reaction, and particularly relates to a catalyst based on TiO2‑xThe hindered Lewis acid-base photocatalyst and its preparation process and application includes the first synthesis of perovskite MTiO with certain structure3Then MTiO is added3In situ topology transformation chelation removal of M2+Thereby obtaining the photocatalyst of the hindered Lewis acid-base pair containing the oxygen vacancy and the surface adjacent hydroxyl. The TiO being2‑xThe base photocatalyst has higher CO2The adsorption capacity can realize the adsorption and activation of gas molecules, thereby improving the CO content2And (4) reducing efficiency. The preparation method of the catalyst is simple and easy to implement, and the reaction conditions areMild, in reducing CO in the atmosphere2Has wide application prospect in the aspect of realizing chemical energy conversion by efficiently utilizing solar energy and content, is a developable novel method for constructing a hindered Lewis acid-base pair and can be used for efficiently catalyzing CO2And (4) carrying out reduction reaction.
Description
Technical Field
The invention belongs to the field of material synthesis and catalytic reaction, and particularly relates to a catalyst based on TiO2-xThe hindered Lewis acid-base photocatalyst and the preparation method and the application thereof.
Background
Energy shortage and environmental problems are serious problems facing the human society today. CO is generated due to the over-exploitation and use of fossil fuels such as coal, oil, natural gas and the like2Excessive emission seriously influences the balance of carbon cycle in the nature, brings serious environmental problems, especially the greenhouse effect is increasingly serious, so that the development of clean energy for replacing the traditional non-renewable energy has great research significance. CO conversion by photocatalytic technology2Conversion into valuable hydrocarbon fuels, e.g. CO, CH4，CH3OH，CH3COOH, provides a way to address carbon emissions and alleviate energy crisis. The photocatalysis technology has the advantages of low cost, mild reaction condition, environmental protection and the like, and CO is used at present2The reduction field has potential advantages.
Recent research results indicate that the hindered lewis acid-base pair contributes to CO2Adsorption and activation of gas molecules and effective CO increase2Photocatalytic activity of (1). Dong et al reported that Bi was converted into Bi3+For In3+Optimized In-adjustment by isomorphous substitution2O3-x(OH)ySurface hindered Lewis acid-base pairs of (A) for adsorbing and activating CO2Molecule, enhanced photocatalytic CO2Efficiency of reduction reaction (adv. sci.2018,5,1700732). Wang et al reported CoGeO2-x(OH)yUsing photo-induced surface oxygen vacancies (O)Vs) And a hindered Lewis acid-base pair of adjacent surface hydroxyls for CO2Capture and activation of molecules, increasing CO2Efficiency of the reduction reaction (adv. funct. mater.2018,28,1804191).
At present, CO2The adsorption and activation of molecules on the surface of the photocatalyst material restrict the photocatalysis of CO2One of the decisive factors for the reduction efficiency. Photocatalytic reduction of CO by hindered Lewis acid-base pair2The molecular adsorption and activation have important functions, the construction of the hindered Lewis acid-base on the surface of the existing catalyst has important practical challenges for the fine operation process in the technology, and the atomic-level hindered Lewis acid-base pair regulation and control on the surfaces of different materials are difficult to realize. Thus in the photocatalysis of CO2In the reduction field, the hindered Lewis acid-base pair on the surface of the high-efficiency photocatalyst is designed and constructed to be CO2The improvement of the reduction performance has great challenges and important research significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a TiO-based material2-xThe hindered Lewis acid-base photocatalyst and its preparation method and application use topology in-situ conversion method to convert the constructed perovskite into TiO containing hindered Lewis acid-base pair constructed by taking oxygen vacancy as Lewis acid site and surface hydroxyl as Lewis base site2-xAnd (3) a hollow structure. The invention uses a simple and special preparation method to prepare the perovskite MTiO by a top-down method3Taking the material as a precursor, and adding M in the crystal2+Chelating and removing to obtain hindered Lewis acid-base pair containing oxygen vacancy and surface adjacent hydroxyl, and benefiting CO2The adsorption and activation of gas molecules are helpful for high-efficiency CO2The reduction reaction is carried out.
The technical scheme of the invention is as follows:
based on TiO2-xThe preparation method of the hindered Lewis acid-base photocatalyst comprises the following steps:
(1) weighing a certain mass of salt (MCl)2、MCO3、M(NO3)2And its hydrous compound) is dissolved in the mixed solution of ethanol and polyethylene glycol, and the solution is stirred uniformly; wherein the added salt has a solubility of less than or equal to that of the mixed solvent;
(2) adding a certain amount of titanium source into the uniformly mixed solution, uniformly stirring, adding a certain mass of alkaline mineralized reagent, putting the alkaline mineralized reagent into a reaction kettle, and putting the reaction kettle into an oven for heating reaction;
(3) will be provided withThe reactant is centrifugally separated and washed to obtain a perovskite product MTiO with a certain structure3；
(4) Adding a mixed reagent of water and ethylene glycol into the perovskite prepared in the step (3), then adding a chelating reagent, wherein the molar ratio of the added chelating agent to the perovskite is more than or equal to 1, uniformly stirring the mixed solution, putting the mixed solution into a reaction kettle, and putting the reaction kettle into an oven for heating reaction;
(5) centrifugally separating the obtained product to obtain the TiO with the hindered Lewis acid-base pair2-xA photocatalyst.
The volume ratio of the polyethylene glycol to the ethanol solution added in the step (1) is 1: 1 to 39.
The titanium source added in the step (2) is one or two of isopropyl titanate and tetrabutyl titanate; the alkaline mineralizing agent added is any one of NaOH or KOH.
The perovskite product MTiO obtained in the step (3)3Wherein M is Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn; the perovskite MTiO3Is a micro-cubic structure.
The volume ratio of the ethylene glycol to the aqueous solution added in the step (4) is 1: 1-19; the chelating agent is disodium ethylene diamine tetraacetate or a hydrous compound thereof.
Mol of added(titanium source)：mol(salt)＝1：0.8～1.2，mol(titanium source)：mol(alkaline mineralizing agent)＝1：0.4～10。
The reaction temperature is 150-220 ℃, and the reaction time is 10-30 h.
TiO-based material prepared by the preparation method of any one of the above2-xThe hindered lewis acid-base photocatalyst of (1). The preparation method of the catalyst is to synthesize perovskite (MTiO) with a certain structure3M ═ Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn), followed by M ═ Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn), and then M θ3In situ topology transformation chelation removal of M2+Thereby obtaining a mixture containing oxygen vacancies (O)VsLewis acid) and surface OH (Lewis base) modified TiO containing a hindered Lewis acid-base pair2-x。
The TiO-based2-xThe hindered Lewis acid and base can be used for photocatalyst to catalyze CO2Application in reduction reaction. The application method is to apply the TiO2-xAdding the photocatalyst into a quartz tube containing a certain volume of water solution, irradiating with one of LED lamp or xenon lamp with ultraviolet or visible light wave band, and performing CO treatment with the irradiation wave band determined according to the light range absorbed by the prepared photocatalyst2And (4) carrying out reduction reaction. The volume of the water solution in the quartz tube can be selected to be 10-20 mL.
The invention has the beneficial effects that:
(1) the invention provides a TiO containing hindered Lewis acid-base pair2-xBased on photocatalysts with high CO content2The adsorption capacity can realize the adsorption and activation of gas molecules, thereby improving the CO content2And (4) reducing efficiency. The preparation method of the catalyst is simple and easy to implement, the reaction condition is mild, and CO in the atmosphere is reduced2Has wide application prospect in the aspect of realizing chemical energy conversion by efficiently utilizing solar energy and content, is a developable novel method for constructing a hindered Lewis acid-base pair and can be used for efficiently catalyzing CO2And (4) carrying out reduction reaction.
(2) The preparation method provided by the invention is simple and convenient, innovative and strong in practicability, and is beneficial to CO2Adsorption and activation of gas molecules in photocatalytic CO2The field of reduction preparation of the high-efficiency photocatalyst has potential application value.
Drawings
FIG. 1 shows CaTiO synthesized in accordance with the present invention3Scanning Electron Microscope (SEM) photograph of (a);
FIG. 2 shows TiO synthesized in accordance with an embodiment of the present invention2-xSEM photograph of (a);
FIG. 3 shows TiO synthesized in accordance with an embodiment of the present invention2-xA sample ultraviolet-visible diffuse reflection absorption spectrum;
FIG. 4 shows TiO synthesized in accordance with an embodiment of the present invention2-xA sample electron spin resonance spectrogram;
FIG. 5 shows TiO synthesized in accordance with an embodiment of the present invention2-xSample for CO2Temperature programmed desorption Curve (CO) of gas2-TPD)；
FIG. 6 shows TiO synthesized in accordance with an embodiment of the present invention2-xSample for NH3Temperature programmed desorption curve (NH) of gas3-TPD)；
FIG. 7 shows TiO synthesized in accordance with an embodiment of the present invention2-xSample photocatalytic CO2Reduction testing the CO yield versus time curve;
FIG. 8 shows TiO synthesized in accordance with an embodiment of the present invention2Photocatalytic CO of sample A2Reduction test CO production was plotted against time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
For a further understanding of the invention, reference will now be made to the following description taken in conjunction with the accompanying drawings and examples.
It should be noted that the total volume of the mixed solution added in the synthesis step of the present invention does not exceed 4/5 of the total volume of the reaction vessel used, i.e., the total volume of the reactants added in the reaction system does not exceed 4/5 of the total volume of the reaction system.
Containing hindered Lewis acid-base pair TiO2-xThe preparation method and the application of the material photocatalyst comprise the following steps:
(1) 1mmol of salt (MCl)2、MCO3、M(NO3)2Dissolving M ═ Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu and Zn) in 10-40 mL of mixed solution of ethanol and polyethylene glycol, uniformly stirring the solution, then adding 1mmol of titanium source (n-butyl titanate and isopropyl titanate) into the solution, uniformly stirring, adding 6mmol of alkaline mineralized reagent (NaOH and KOH), uniformly stirring, transferring into a reaction kettle, putting into an oven at 150-200 ℃ for reaction for 12-25 h, and centrifugally washing to obtain the perovskite material MTiO3。
(2) 0.5mmol of the above-prepared MTiO was weighed3Adding the mixture into a mixed solution of 20-60 mL of water and polyethylene glycol, adding 1mmol of chelating reagent (EDTA-2Na or hydrate thereof), stirring the solution uniformly, putting the solution into a reaction kettle, reacting for 10-20 h in a drying oven at 150-200 ℃, and centrifugally washing to obtain the TiO containing the hindered Lewis acid-base pair2-xA photocatalyst material.
(3) Weighing 5-100mg TiO2-xPhotocatalyst, carrying out photocatalysis on CO in a pure water reaction system of 10-25mL2Reduction reaction, sealing the reaction system, vacuumizing the system by using a vacuum pump, and introducing CO2Gas, finally CO2The gas fills the entire reaction apparatus. Magnetically stirring at room temperature, irradiating with ultraviolet or visible light-emitting diode (LED) or xenon lamp, sampling at intervals, and detecting generated CO and CH by gas chromatography (FID II)4And TCD detection of Generation H2Gas content.
Example 1CaTiO3Preparation of the catalyst
(1) Adding 1mmol of CaCl2·H2Dissolving O in 20mL of mixed solution of ethanol and polyethylene glycol, stirring the solution uniformly, adding 1mmol of titanium source (n-butyl titanate and isopropyl titanate) into the solution, stirring uniformly, adding 6mmol of alkaline mineralization reagent (NaOH and KOH), stirring uniformly, transferring into a reaction kettle, and putting into an oven at 180 ℃ for reaction for 15 hours. Obtaining perovskite material MTiO after centrifugal washing3(as shown in fig. 1).
(2) 0.5mmol of CaTiO prepared as described above was weighed3Adding into 40mL of mixed solution of water and polyethylene glycol, adding 1mmol of chelating reagent (EDTA-2Na or hydrate thereof), stirring the solution uniformly, putting into a reaction kettle, reacting in an oven at 180 ℃ for 12h, and centrifuging and washing to obtain the TiO containing the hindered Lewis acid-base pair2Photocatalyst (morphology is shown in figure 2).
The hindered Lewis acid-base pair is formed by a Lewis acid site with an oxygen vacancy defect and a Lewis base site adjacent to a surface hydroxyl group, and is correspondingly characterized in that the absorption peak position of an ultraviolet-visible diffuse reflection spectrum (shown in figure 3) is red shifted, an electron spin resonance spectrum (shown in figure 4) reveals the oxygen vacancy, and the hindered Lewis acid-base pair is used for treating CO2(acid gas) and NH3Temperature programmed desorption curves (shown in fig. 5 and 6) for TiO containing hindered lewis acid-base pairs (basic gas)2Has higher adsorption capacity.
Example 2MgCl2Preparation of the catalyst
(1) 1.2mmol of MgCl2Dissolving the mixture in 30mL of mixed solution of ethanol and polyethylene glycol, uniformly stirring the solution, then adding 1mmol of titanium source (n-butyl titanate and isopropyl titanate) into the solution, uniformly stirring, adding 4mmol of NaOH reagent, uniformly stirring, transferring the solution into a reaction kettle, and putting the reaction kettle into an oven at 180 ℃ for reaction for 15 hours. Obtaining perovskite material MgTiO after centrifugal washing3。
(2) Weigh 0.5mmol of MgTiO prepared above3Adding into 30mL of mixed solution of water and polyethylene glycol, adding 1mmol of chelating reagent (EDTA-2Na or hydrate thereof), stirring the solution uniformly, putting into a reaction kettle, reacting in an oven at 180 ℃ for 12h, and centrifuging and washing to obtain the TiO containing the hindered Lewis acid-base pair2A photocatalyst.
Example 3FeCl2Preparation of the catalyst
(1) Adding 1mmol of CaCl2·H2Dissolving O in 40mL of mixed solution of ethanol and polyethylene glycol, uniformly stirring the solution, then adding 1mmol of titanium source (n-butyl titanate and isopropyl titanate) into the solution, uniformly stirring, adding 8mmol of KOH reagent, uniformly stirring, transferring into a reaction kettle, and putting into an oven at 180 ℃ for reaction for 15 hours. Obtaining perovskite material FeTiO after centrifugal washing3。
(2) Weigh 0.5mmol of FeTiO prepared as described above3Adding into 50mL of mixed solution of water and polyethylene glycol, adding 1mmol of chelating reagent (EDTA-2Na or hydrate thereof), stirring the solution uniformly, putting into a reaction kettle, reacting in an oven at 180 ℃ for 12h, and centrifuging and washing to obtain the TiO containing the hindered Lewis acid-base pair2A photocatalyst.
Example 4Ba (NO)3)2Preparation of the catalyst
(1) 0.8mmol of Ba (NO)3)2Dissolving in 20mL of mixed solution of ethanol and polyethylene glycol, and stirringAnd (2) uniformly adding 1mmol of titanium source (n-butyl titanate and isopropyl titanate) into the solution, uniformly stirring, adding 5mmol of alkaline mineralization reagent (NaOH and KOH), uniformly stirring, transferring into a reaction kettle, and putting into an oven at 180 ℃ for reaction for 15 hours. Obtaining perovskite material BaTiO after centrifugal washing3。
(2) Weigh 0.5mmol of BaTiO prepared above3Adding into 40mL of mixed solution of water and polyethylene glycol, adding 1mmol of chelating reagent (EDTA-2Na or hydrate thereof), stirring the solution uniformly, putting into a reaction kettle, reacting in an oven at 180 ℃ for 12h, and centrifuging and washing to obtain the TiO containing the hindered Lewis acid-base pair2A photocatalyst.
Example 5
Photocatalytic CO2Reduction test
Weigh 20mg TiO2-xPhotocatalyst, photocatalytic CO in a reaction System of 15mL pure Water2Reduction reaction, sealing the reaction system, vacuumizing the system by using a vacuum pump, and introducing CO2Gas, finally CO2The gas fills the entire reaction apparatus. The samples were taken every 1h under magnetic stirring at room temperature and light irradiation, and the amount of CO gas generated was determined by gas chromatography (the results of the data are shown in FIG. 7).
Comparative example
Preparation of TiO for eliminating hindered Lewis acid-base pair2Photocatalyst and process for producing the same
The hindered Lewis acid-base pair-containing TiO prepared in example 1 above2The photocatalyst is annealed for 2 hours at 400 ℃ to eliminate TiO2-xOxygen vacancy defects and surface hydroxyls of the material destroy the hindered lewis acid-base pair (the material is named as TiO)2-A)。
Test examples
Test example 1
Photocatalytic CO2Reduction test
Use of the hindered Lewis acid-base Pair eliminating TiO prepared in comparative example2The photocatalyst, other reaction conditions as in example 2, and the amount of gas produced were determined by gas chromatography (results of test data are shown in FIG. 8).
Test example 2
Photocatalytic CO2Reduction test (plus Lewis acid)
Adding a certain amount of AlCl into a reaction system of 15mL of pure water3Reagents (lewis acids), other reaction conditions as in example 2, gas chromatography was used to measure the amount of gas generated (results of test data are shown in fig. 7, 8).
Test example 3
Photocatalytic CO2Reduction test (addition of Lewis base)
A certain amount of triethylamine reagent (Lewis base) was added to a reaction system containing 15mL of pure water under other reaction conditions as in example 2, and the amount of generated gas was measured by gas chromatography (the results of the data are shown in FIGS. 7 and 8).
Photocatalytic CO by comparative example 22Amount of CO gas generated in reduction test, and photocatalytic CO in test examples 1, 2, and 32Reduction tests (elimination of hindered Lewis acid base pairs or addition of Lewis acid/base) gave CO yields, which were evident from TiO containing hindered Lewis acid base pairs2Has high photocatalytic CO2And (4) reducing activity.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or modification made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Based on TiO2-xThe preparation method of the hindered Lewis acid-base photocatalyst is characterized by comprising the following steps:
(1) weighing a certain mass of salt, dissolving the salt in a mixed solution of ethanol and polyethylene glycol, and uniformly stirring the solution;
(2) adding a certain amount of titanium source into the uniformly mixed solution in the step (1), uniformly stirring, adding a certain mass of alkaline mineralization reagent, and carrying out heating reaction;
(3) centrifugally separating and washing the reactant obtained in the step (2) to obtain a perovskite product MTiO with a certain structure3；
(4) Adding a mixed reagent of water and ethylene glycol into the perovskite prepared in the step (3), then adding a chelating reagent, and heating for reaction after the mixed solution is uniformly stirred;
(5) centrifugally separating the product obtained in the step (4) to obtain the TiO with the hindered Lewis acid-base pair2-xA photocatalyst.
2. The method according to claim 1, wherein the salt added in step (1) is MCl2、MCO3、M(NO3)2And aqueous compounds thereof; the volume ratio of the added polyethylene glycol to the ethanol solution is 1: 1 to 39.
3. The method of claim 1, wherein: the titanium source added in the step (2) is isopropyl titanate and tetrabutyl titanate; the alkaline mineralizing agent added is any one of NaOH or KOH.
4. The method of claim 1, wherein: the perovskite product MTiO obtained in the step (3)3Wherein M is Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn; the perovskite MTiO3Is a micro-cubic structure.
5. The method of claim 1, wherein: the volume ratio of the ethylene glycol to the aqueous solution added in the step (4) is 1: 1-19; the chelating agent is disodium ethylene diamine tetraacetate or a hydrous compound thereof; the molar ratio of the chelating agent added in the step (4) to the perovskite is more than or equal to 1.
6. The method of claim 1, wherein: mol of added(titanium source)：mol(salt)＝1：0.8～1.2，mol(titanium source)：mol(alkaline mineralizing agent)＝1：0.4～10。
7. The method of claim 1, wherein: the reaction temperature of the preparation method is 150-220 ℃, and the reaction time is 10-30 h.
8. TiO-based material obtained by the preparation method of any one of claims 1 to 72-xThe hindered lewis acid-base photocatalyst of (1).
9. The TiO-based composition according to claim 82-xThe hindered Lewis acid and base can be used for photocatalyst to catalyze CO2Application in reduction reaction.
10. Use according to claim 9, characterized in that it comprises the following steps: subjecting the TiO to a reaction2-xAdding the photocatalyst into a quartz tube containing a certain volume of water solution, irradiating with LED lamp or xenon lamp with certain wavelength, wherein the irradiation waveband is determined according to the light range absorbed by the prepared photocatalyst, and performing CO2And (4) carrying out reduction reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011445324.8A CN112569919B (en) | 2020-12-11 | 2020-12-11 | Based on TiO 2-x Hindered Lewis acid-base photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011445324.8A CN112569919B (en) | 2020-12-11 | 2020-12-11 | Based on TiO 2-x Hindered Lewis acid-base photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112569919A true CN112569919A (en) | 2021-03-30 |
| CN112569919B CN112569919B (en) | 2022-08-02 |
Family
ID=75130948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011445324.8A Active CN112569919B (en) | 2020-12-11 | 2020-12-11 | Based on TiO 2-x Hindered Lewis acid-base photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112569919B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114984982A (en) * | 2022-03-23 | 2022-09-02 | 安阳师范学院 | High-activity, high-selectivity, low-price and nontoxic photo-thermal catalytic reduction carbon dioxide catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2392401A1 (en) * | 2009-02-02 | 2011-12-07 | Pioneer Corporation | TiO2 NANOPARTICLES |
| CN109759069A (en) * | 2019-03-18 | 2019-05-17 | 福州大学 | A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide |
-
2020
- 2020-12-11 CN CN202011445324.8A patent/CN112569919B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2392401A1 (en) * | 2009-02-02 | 2011-12-07 | Pioneer Corporation | TiO2 NANOPARTICLES |
| CN109759069A (en) * | 2019-03-18 | 2019-05-17 | 福州大学 | A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide |
Non-Patent Citations (1)
| Title |
|---|
| KULBIR KAUR GHUMAN ET AL.: "Photoexcited Surface Frustrated Lewis Pairs for Heterogeneous Photocatalytic CO2 Reduction", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114984982A (en) * | 2022-03-23 | 2022-09-02 | 安阳师范学院 | High-activity, high-selectivity, low-price and nontoxic photo-thermal catalytic reduction carbon dioxide catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112569919B (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112642482B (en) | Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof | |
| CN107649159B (en) | Organic dye modified carbon nitride graphene composite material and application thereof | |
| CN111905817B (en) | Reduction of CO 2 Preparation method and application of efficient photocatalytic material PCN-222-Zn serving as formic acid | |
| CN109201115B (en) | Photocatalytic hydrogen production catalyst and preparation method and application thereof | |
| CN111450814B (en) | Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof | |
| CN113101964B (en) | Mesoporous cerium oxide photocatalyst and preparation method and application thereof | |
| CN110327988A (en) | A kind of preparation and application of PCN-222 (Cu)/titanic oxide nano compound material | |
| CN115591582B (en) | MOF-303/g-C 3 N 4 Heterojunction material and preparation method and application thereof | |
| CN112569919B (en) | Based on TiO 2-x Hindered Lewis acid-base photocatalyst and preparation method and application thereof | |
| CN109317176A (en) | A kind of azotized carbon nano piece that Fe (III) is modified and its application in photocatalysis fixed nitrogen | |
| CN111470482A (en) | Multistage tubular carbon nitride and preparation method and application thereof | |
| Liu et al. | Defective NH2-UiO-66 (Zr) effectively converting CO2 into cyclic carbonate under ambient pressure, solvent-free and co-catalyst-free conditions | |
| CN112295604B (en) | Metal organic framework nanosheet, preparation method thereof and application of nanosheet in efficient photocatalytic reduction of carbon dioxide | |
| Zhang et al. | Enhanced photocatalytic reduction of CO2 into CH4 over N, Eu co-doped TiO2: Insight into the synergistic effect of N and Eu | |
| CN114289036A (en) | Sulfide photocatalyst containing rare earth elements and preparation method and application thereof | |
| CN115505135B (en) | Fe-Zr MOFs and preparation method and application thereof | |
| CN105521766A (en) | Gold-palladium-modified MIL-101 and preparation method thereof | |
| CN111774051A (en) | Catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration and preparation method thereof | |
| CN114931949B (en) | Photocatalyst for carbon dioxide reduction and preparation method and application thereof | |
| CN116020535A (en) | Preparation method and application of efficient Fe/ZSM-5 catalyst | |
| CN115463667A (en) | Preparation method of composite photocatalytic nitrogen fixation material with different crystal faces of cuprous oxide loaded with iridium | |
| CN111659429B (en) | Preparation method of cadmium sulfide-cesium phosphotungstate composite material and application of composite material as visible-light-driven photocatalyst to hydrogen preparation | |
| CN114425392A (en) | Carbon-nitrogen-based composite material, preparation method and application thereof | |
| CN116099535B (en) | Preparation method of crystal-face-dependent cerium oxide photocatalytic nitrogen fixation material | |
| CN109759087B (en) | NiS/MgAl-LDH photocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |