CN114534764A - Non-metal element doped strontium titanate catalyst and preparation method thereof - Google Patents
Non-metal element doped strontium titanate catalyst and preparation method thereof Download PDFInfo
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000002843 nonmetals Chemical class 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001879 gelation Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 4
- 229910033181 TiB2 Inorganic materials 0.000 claims description 4
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 3
- 229910010348 TiF3 Inorganic materials 0.000 claims description 3
- 229910003092 TiS2 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical group O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000003438 strontium compounds Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 239000011941 photocatalyst Substances 0.000 description 10
- 229910002367 SrTiO Inorganic materials 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910002370 SrTiO3 Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
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- 238000002791 soaking Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-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
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The application provides a non-metal element doped strontium titanate catalyst and a preparation method thereof. The preparation method of the non-metal element doped strontium titanate catalyst comprises the following steps: performing first pre-oxidation on a titanium-containing compound containing a target doped non-metal element by using a pre-oxidant to obtain a first reaction precursor; mixing a first reaction precursor, a strontium-containing compound and a first solvent to carry out a first reaction, then adjusting the system to be alkaline, and continuing the reaction to obtain a second reaction precursor; heating the second reaction precursor for second pre-oxidation and gelation to obtain a precursor xerogel; and carrying out heat treatment on the xerogel to obtain the non-metal element doped strontium titanate catalyst. The preparation method of the non-metal element doped strontium titanate catalyst can effectively avoid the use of exogenous volatile raw materials rich in target non-metal elements and the use of an organic titanium source with strong hydrolysis effect, thereby effectively simplifying synthesis conditions and improving preparation efficiency.
Description
Technical Field
The application relates to the field of catalysts, in particular to a nonmetallic element doped strontium titanate catalyst and a preparation method thereof.
Background
With the continuous development of human society, the global energy crisis and environmental pollution problems become more severe, and the photocatalytic technology has the characteristics of low cost, environmental friendliness and the like in solving the problems, but the new high-efficiency catalyst is deficient, so that the development of the photocatalyst with excellent performance is urgently needed.
Perovskite type SrTiO3The photocatalyst is a semiconductor photocatalyst with high activity, high stability, no toxicity and low cost. SrTiO3The photocatalyst has good response to ultraviolet light, but the ultraviolet light only accounts for 3 percent of the sunlight, and more than 40 percent of visible light is not effectively utilized, so that SrTiO is greatly reduced3The catalytic efficiency of the photocatalyst; in addition, the photocatalyst has serious photo-induced electron-hole recombination phenomenon and low quantum efficiency, and the problems also restrict SrTiO3Development of photocatalysts. By analysis, SrTiO3The band gap of the photocatalyst is wide, only a small amount of sunlight can be absorbed, and the photocatalyst needs to be modified to widen the light absorption range, so that the wavelength range of exciting light is enlarged, the separation efficiency of photo-generated electrons and holes is improved, the recombination of photo-generated carriers is inhibited, and the efficiency and the stability of the photocatalyst are improved. At present, for SrTiO3The research on the photocatalytic material mainly focuses on SrTiO3The doping modification of (2). The following methods are mainly used for doping modification: non-metal doping method, non-metal and metal co-doping, noble metal deposition method, dye sensitization method and the like. Among them, non-metal doping is a very effective means, and the current non-metal doping method is more or lessAll have some problems, such as over high price of raw materials and difficult control of reaction, especially, the doping concentration of non-metal elements is low, and the non-metal elements are difficult to enter SrTiO3The stability of the system is poor after the crystal lattice and the doping, and the problems of high reaction temperature, harsh conditions and the like exist.
Disclosure of Invention
The present application aims to provide a non-metal element doped strontium titanate catalyst and a preparation method thereof, so as to solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a preparation method of a nonmetallic element doped strontium titanate catalyst comprises the following steps:
carrying out first pre-oxidation on a titanium-containing compound containing a target doped non-metallic element by using a pre-oxidant to obtain a first reaction precursor;
mixing the first reaction precursor, the strontium-containing compound and the first solvent to carry out a first reaction, then adjusting the system to be alkaline, and continuing the reaction to obtain a second reaction precursor;
heating the second reaction precursor for second pre-oxidation and gelation to obtain a precursor xerogel;
and carrying out heat treatment on the xerogel to obtain the nonmetallic element doped strontium titanate catalyst.
Preferably, the titanium-containing compound containing the target doping non-metallic element comprises TiB2、TiC、Ti3C2、TiN、Ti2N2、Ti3N4、TiF3、TiP、TiS2One or more of (a).
Preferably, the titanium-containing compound containing the target doping non-metallic element is dispersed in a second solvent to obtain a dispersion liquid before use;
preferably, the second solvent is water or an aqueous ethanol solution.
Preferably, the pre-oxidant comprises one or more of concentrated nitric acid, concentrated sulphuric acid, concentrated hydrochloric acid and hydrogen peroxide;
preferably, the mass concentration of the pre-oxidant is 0.05 mol/L-maximum saturation concentration;
preferably, the mass-to-volume ratio of the titanium-containing compound containing the target doping non-metallic element to the pre-oxidizer is 1 g: (10-200) ml.
Preferably, the strontium containing compound comprises SrO, SrCO3、Sr(OH)2、Sr(NO3)2、SrCl2、O8P2Sr3And C4H6O4Sr;
preferably, the molar ratio of the titanium-containing compound containing the target doping non-metallic element to the strontium-containing compound is 1: (1-1.5);
preferably, the first solvent comprises one or more of water, nitric acid, sulfuric acid, hydrochloric acid.
Preferably, the substance used for adjusting the system to alkaline comprises one or more of NaOH, KOH and ammonia water;
preferably, the alkalinity corresponds to a pH of 10 to 14.
Preferably, the temperature of the heat treatment is 50-500 ℃ and the time is 1-24 h.
Preferably, the precursor xerogel is crushed before the heat treatment;
preferably, the heat treatment further comprises: repeatedly washing the heat-treated product by using a third solvent and a fourth solvent, and then drying in vacuum;
preferably, the third solvent is water or ethanol water solution, and the fourth solvent comprises one or more of water, nitric acid, sulfuric acid and hydrochloric acid;
preferably, the temperature of the vacuum drying is 50-200 ℃, and the time is 6-24 h.
The application also provides a non-metal element doped strontium titanate catalyst, and the preparation method of the non-metal element doped strontium titanate catalyst is used for preparing the catalyst.
Preferably, the general structural formula of the non-metal element doped strontium titanate catalyst is SrTiO3-iXiWherein X represents a target doped non-metal element,x is any one selected from B, C, N, F, P, S; i represents the doping content.
Compared with the prior art, the beneficial effect of this application includes:
according to the preparation method of the non-metal element doped strontium titanate catalyst, the titanium-containing compound containing the target non-metal doped element is selected as a typical raw material doped with non-metal atoms and titanium in a rich and targeted manner, and the raw material containing strontium is combined and treated under the reaction condition of controllable gradient oxidizing atmosphere (chemical oxidation + thermal oxidation) such as first pre-oxidation and second pre-oxidation, so that the preparation of the in-situ non-metal element doped strontium titanate catalyst is realized. The method has the advantages that the target non-metal doping atoms and titanium atoms are uniformly mixed in the crystal lattice at the atomic level in the raw material compound and exist in a high-concentration occurrence form, and the structure regulation of the target compound and the controllable preparation of the doping amount and the type of the related non-metal elements are realized by subsequently constructing the reaction condition with controllable gradient oxidizing atmosphere; the method can effectively avoid relevant problems and difficulties caused by using exogenous volatile raw materials rich in target non-metallic elements and using an organic titanium source with strong hydrolysis effect, thereby effectively simplifying synthesis conditions and improving preparation efficiency.
The application provides a non-metallic element doping strontium titanate catalyst has controllable target non-metallic element doping rate, and visible light absorptivity is strong, and ultraviolet visible light arouses catalytic effect good.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a flow chart illustrating the preparation of an embodiment of the present application;
FIG. 2 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd the X-ray diffraction patterns of the control samples synthesized in comparative example 1 and comparative example 2;
FIG. 3 is a drawing showingExample 1 synthetic nitrogen-doped strontium titanate SrTiO3-iNi and X-ray photoelectron spectra of the control synthesized in comparative example 1;
FIG. 4 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd solid ultraviolet-visible diffuse reflectance (UV-vis DRS) plots for the control synthesized in comparative example 1 and comparative example 2;
FIG. 5 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd the visible light degradation methylene blue pattern of the control synthesized in comparative example 1 and comparative example 2.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A preparation method of a nonmetallic element doped strontium titanate catalyst comprises the following steps:
carrying out first pre-oxidation on a titanium-containing compound containing a target doped non-metallic element by using a pre-oxidant to obtain a first reaction precursor;
mixing the first reaction precursor, the strontium-containing compound and the first solvent to carry out a first reaction, then adjusting the system to be alkaline, and continuing the reaction to obtain a second reaction precursor;
heating the second reaction precursor for second pre-oxidation and gelation to obtain a precursor xerogel;
and carrying out heat treatment on the xerogel to obtain the nonmetallic element doped strontium titanate catalyst.
In an alternative embodiment, the titanium-containing compound containing the target doping non-metallic element comprises TiB2、TiC、Ti3C2、TiN、Ti2N2、Ti3N4、TiF3、TiP、TiS2One or more of (a).
In an alternative embodiment, the titanium-containing compound containing the target doping non-metallic element is dispersed in a second solvent to obtain a dispersion solution before use;
in an alternative embodiment, the second solvent is water or an aqueous ethanol solution.
In an alternative embodiment, the pre-oxidant comprises one or more of concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid, and hydrogen peroxide;
in an alternative embodiment, the mass concentration of the pre-oxidant is between 0.05mol/L and the maximum saturation concentration;
in an alternative embodiment, the mass to volume ratio of the target doped non-metallic element-containing titanium-containing compound to the pre-oxidizer is 1 g: (10-200) ml.
Optionally, the mass-to-volume ratio of the titanium-containing compound containing the target doping non-metallic element to the pre-oxidizer may be 1 g: 10ml, 1 g: 50ml, 1 g: 100ml, 1 g: 150ml, 1 g: 200ml or 1 g: (10-200) ml.
In an alternative embodiment, the strontium containing compound comprises SrO, SrCO3、Sr(OH)2、Sr(NO3)2、SrCl2、O8P2Sr3And C4H6O4Sr;
in an alternative embodiment, the molar ratio of the target doped non-metallic element-containing titanium compound to the strontium-containing compound is 1: (1-1.5);
in an alternative embodiment, the first solvent comprises one or more of water, nitric acid, sulfuric acid, hydrochloric acid.
In an alternative embodiment, the substances used to adjust the system to alkaline include one or more of NaOH, KOH, ammonia;
in an alternative embodiment, the alkalinity corresponds to a pH of 10 to 14.
In an alternative embodiment, the temperature of the heat treatment is 50 ℃ to 500 ℃ for 1h to 24 h.
Optionally, the temperature of the heat treatment may be any value between 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 50 ℃ to 500 ℃, and the time may be any value between 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or 1h to 24 h.
The temperature and time used for the first pre-oxidation, the first reaction, the continuing reaction, the second pre-oxidation, and the gelation vary with each other, and need to be set according to the degree of pre-oxidation.
In an alternative embodiment, the precursor xerogel is comminuted prior to the thermal treatment;
in an alternative embodiment, the heat treatment further comprises, after the heat treatment: repeatedly washing the heat-treated product by using a third solvent and a fourth solvent, and then drying in vacuum;
in an alternative embodiment, the third solvent is water or an aqueous ethanol solution, and the fourth solvent comprises one or more of water, nitric acid, sulfuric acid, hydrochloric acid;
in an alternative embodiment, the temperature of the vacuum drying is 50 ℃ to 200 ℃ and the time is 6h to 24 h.
Optionally, the temperature of the vacuum drying may be any value between 50 ℃, 100 ℃, 150 ℃, 200 ℃ or 50 ℃ to 200 ℃, and the time may be any value between 6h, 12h, 18h, 24h or 6h to 24 h.
The application also provides a non-metal element doped strontium titanate catalyst, and the preparation method of the non-metal element doped strontium titanate catalyst is used for preparing the catalyst.
In an alternative embodiment, the nonmetallic element-doped strontium titanate catalyst has the general structural formula of SrTiO3-iXiWherein X represents a target doped non-metal element, and is selected from B, C, N, F, P, S; i represents the doping content.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
As shown in fig. 1, this embodiment provides a preparation method of a non-metal element doped strontium titanate catalyst, which includes the following specific steps:
(1) weighing 0.62g (0.01mol) of titanium nitride (TiN), dispersing in 10ml of deionized water, placing in a 300ml beaker, stirring at room temperature for 10min (or ultrasonically dispersing for 5min), and obtaining a corresponding dispersion liquid containing TiN;
(2) the TiN dispersion obtained in step (1) was placed on a heating stirrer, and 20ml (30% H) was added2O2) Heating the initial solution reaction mixed system to 40 ℃, stopping heating, allowing the reaction system to continue to react for 60min, and performing pre-oxidation reaction to obtain nitrogen-titanium-polyhydroxy intermediate state sol;
(3) adding 1.59g of SrCl weighed into the reaction precursor obtained in the step (2)2(0.01mol) and 20ml of deionized water, continuously reacting for 60min, adjusting the pH value of the reaction mixed solution to about 13 (in an alkaline environment) by using 1mol/L NaOH solution, and continuously stirring and reacting at room temperature for 120min to obtain intermediate sol after the preoxidation of the nitrogen-titanium-strontium-polyhydroxy compound;
(4) putting the reaction precursor obtained in the step (3) into a vacuum oven, controlling the temperature to be 80 ℃, continuously reacting for 12 hours, and further pre-oxidizing and gelatinizing to obtain nitrogen-titanium-strontium-polyhydroxy intermediate gel;
(5) taking out the dry gel of the precursor obtained in the step (4), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(6) placing the powdery precursor obtained in the step (5) in a muffle furnace in an air atmosphere, controlling the temperature at 130 ℃ and the reaction time for 240min for heat treatment, and reacting;
(7) after the reaction is finished, taking out the material, soaking the material for 120min by using 30ml of 0.02mol/L diluted hydrochloric acid solution, and then washing the material for multiple times by using deionized water until the supernatant is neutral;
(8) vacuum drying the solid sample collected in the step (7), controlling the temperature at 80 ℃ for 24 hours to obtain the nitrogen-doped strontium titanate catalyst SrTiO3-iNi。
Example 2
The embodiment provides a preparation method of a nonmetallic element-doped strontium titanate catalyst, which comprises the following specific steps:
(1) weighing 0.60g (0.01mol) of titanium carbide (TiC) to be dispersed in 10ml of deionized water, placing the mixture in a 250ml flask, and stirring the mixture for 10min at room temperature (or ultrasonically dispersing the mixture for 5min) to obtain corresponding TiC-containing dispersion liquid;
(2) placing the TiC dispersion liquid obtained in the step (1) on a heating stirrer, and adding 40ml of HNO3(6mol/L), heating the initial solution reaction mixed system to 70 ℃, reacting for 6 hours, and carrying out pre-oxidation reaction to obtain carbon-titanium-polyhydroxy intermediate sol;
(3) adding weighed 1.22g of Sr (OH) into the reaction precursor obtained in the step (2)2(0.01mol) and 20ml deionized water, continuously reacting for 60min, adjusting the pH value of the reaction mixed solution to about 13 (in an alkaline environment) by using 10mol/LKOH solution, and continuously stirring and reacting at room temperature for 180min to obtain intermediate sol after the carbon-titanium-strontium-polyhydroxy compound is preoxidized;
(4) putting the reaction precursor obtained in the step (3) into a vacuum oven, controlling the temperature to be 90 ℃, continuously reacting for 16 hours, and further pre-oxidizing and gelatinizing to obtain carbon-titanium-strontium-polyhydroxy intermediate gel;
(5) taking out the dry gel of the precursor obtained in the step (4), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(6) placing the powdery precursor obtained in the step (5) in a muffle furnace in an air atmosphere, controlling the temperature at 200 ℃ and the reaction time at 240min for heat treatment, and reacting;
(7) after the reaction is finished, taking out the material, soaking the material for 120min by 40ml of 0.005mol/L dilute sulfuric acid solution, and then washing the material for multiple times by deionized water until the supernatant is neutral;
(8) vacuum drying the solid sample collected in the step (7), controlling the temperature at 80 ℃ for 24 hours to obtain the carbon-doped strontium titanate catalyst SrTiO3-iCi。
Example 3
The embodiment provides a preparation method of a nonmetallic element-doped strontium titanate catalyst, which comprises the following specific steps:
(1) weighing titanium diboride (TiB)2)0.69g (0.01mol) of the TiB is dispersed in 10ml of deionized water and placed in a 250ml flask, and stirred for 10min at room temperature (or ultrasonically dispersed for 5min) to obtain the corresponding TiB-containing solution2The dispersion of (1);
(2) the TiB obtained in the step (1) is treated2The dispersion was placed on a heated stirrer and 30ml of H was added2SO4(9mol/L), heating the initial solution reaction mixed system to 90 ℃, reacting for 8 hours, and carrying out pre-oxidation reaction to obtain boron-titanium-polyhydroxy intermediate sol;
(3) adding a solution prepared by weighing 1.04g of SrO (0.01mol) and 20ml of 0.5mol/L dilute sulfuric acid into the reaction precursor obtained in the step (2), continuously reacting for 60min, adjusting the pH value of the reaction mixed solution to be about 13 (in an alkaline environment) by using 10mol/L NaOH solution, and continuously stirring at room temperature for reacting for 180min to obtain intermediate sol after preoxidation of the boron-titanium-strontium-polyhydroxy compound;
(4) putting the reaction precursor obtained in the step (3) into a vacuum oven, controlling the temperature to be 90 ℃, continuously reacting for 20 hours, and further pre-oxidizing and gelling to obtain boron-titanium-strontium-polyhydroxy intermediate gel;
(5) taking out the dry gel of the precursor obtained in the step (4), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(6) placing the powdery precursor obtained in the step (5) in a muffle furnace in an air atmosphere, controlling the temperature at 250 ℃ and the reaction time at 240min for heat treatment, and reacting;
(7) after the reaction is finished, taking out the material, soaking the material for 120min by 40ml of 0.005mol/L dilute sulfuric acid solution, and then washing the material for multiple times by deionized water until the supernatant is neutral;
(8) vacuum drying the solid sample collected in the step (7), controlling the temperature at 80 ℃ for 24 hours to obtain the boron-doped strontium titanate catalyst SrTiO3-iBi。
Example 4
The embodiment provides a preparation method of a nonmetallic element-doped strontium titanate catalyst, which comprises the following specific steps:
(1) weighing titanium disulfide (TiS)2) Dispersing 1.12g (0.01mol) in 10ml deionized water, placing in a 250ml flask, stirring at room temperature for 10min (or ultrasonic dispersing for 5min), to obtain corresponding TiS-containing2The dispersion of (1);
(2) the TiS obtained in the step (1) is treated2Placing the dispersion on a heating stirrer, adding 50ml of HCl (12mol/L), heating an initial solution reaction mixed system to 80 ℃, and reacting for 24 hours; cooling to room temperature, adding 5ml hydrogen peroxide (30% H)2O2) Continuously reacting at room temperature for 60min, and carrying out pre-oxidation reaction to obtain sulfur-titanium-polyhydroxy intermediate state sol;
(3) adding 1.48g of weighted SrCO into the reaction precursor obtained in the step (2)3(0.01mol) and 20ml of 1mol/L dilute hydrochloric acid, continuously reacting for 60min, adjusting the pH value of the reaction mixed solution to about 13 (in an alkaline environment) by using 10mol/L KOH solution, and continuously stirring and reacting for 180min at room temperature to obtain intermediate sol after the sulfur-titanium-strontium-polyhydroxy compound is pre-oxidized;
(4) putting the reaction precursor obtained in the step (3) into a vacuum oven, controlling the temperature to be 90 ℃, continuously reacting for 24 hours, and further pre-oxidizing and gelling to obtain sulfur-titanium-strontium-polyhydroxy intermediate gel;
(5) taking out the dry gel of the precursor obtained in the step (4), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(6) placing the powdery precursor obtained in the step (5) in a muffle furnace in an air atmosphere, controlling the temperature at 300 ℃ and the reaction time at 240min for heat treatment, and reacting;
(7) after the reaction is finished, taking out the material, soaking the material for 120min by 40ml of 0.01mol/L diluted hydrochloric acid solution, and then washing the material for multiple times by deionized water until the supernatant is neutral;
(8) vacuum drying the solid sample collected in the step (7), controlling the temperature at 80 ℃ for 24 hours to obtain the sulfur-doped strontium titanate catalyst SrTiO3-iSi。
Comparative example 1
(1) Measuring titanium tetrachloride (TiCl)4) Slowly dropping 1.1ml (0.01mol) into 20ml deionized water (pH is controlled to be about 1.0), placing the mixture into a 300ml beaker, and stirring the mixture for 60min at room temperature to obtain a corresponding titanium-containing precursor dispersion liquid;
(2) placing the titanium-containing precursor dispersion obtained in the step (1) on a heating stirrer, and adding 20ml (30% H)2O2) Heating the initial solution reaction mixed system to 40 ℃, stopping heating, allowing the reaction system to continue to react for 60min, and performing pre-oxidation reaction to obtain titanium-polyhydroxy intermediate sol;
(3) adding 1.59g of SrCl weighed into the reaction precursor obtained in the step (2)2(0.01mol) and 20ml deionized water, continuing the reaction for 60min, and adding ammonia water (25%, NH)3·H2O) adjusting the pH value of the reaction mixed solution to about 13 (in an alkaline environment), and continuously stirring and reacting at room temperature for 120min to obtain intermediate sol after the pre-oxidation of the nitrogen-titanium-strontium-polyhydroxy compound;
(4) putting the reaction precursor obtained in the step (3) into a vacuum oven, controlling the temperature to be 80 ℃, continuously reacting for 12 hours, and further pre-oxidizing and gelatinizing to obtain nitrogen-titanium-strontium-polyhydroxy intermediate gel;
(5) taking out the dry gel of the precursor obtained in the step (4), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(6) placing the powdery precursor obtained in the step (5) in a muffle furnace in an air atmosphere, controlling the temperature at 130 ℃ and the reaction time for 240min for heat treatment, and reacting;
(7) after the reaction is finished, taking out the material, soaking the material for 120min by using 30ml of 0.02mol/L diluted hydrochloric acid solution, and then washing the material for multiple times by using deionized water until the supernatant is neutral;
(8) and (4) drying the solid sample collected in the step (7) in vacuum, controlling the temperature at 80 ℃ for 24 hours, and obtaining the nitrogen-doped comparative example 1 sample.
Comparative example 2
(1) Weighing 1.24g (0.02mol) of titanium nitride (TiN) and dispersing in 20ml of deionized water, placing in a 300ml beaker, and stirring at room temperature for 20min (or ultrasonically dispersing for 10min) to obtain a corresponding dispersion liquid containing TiN;
(2) putting the TiN dispersion liquid obtained in the step (1) on a heating stirrer as a comparison sample, adding no pre-oxidation reagent, only adding the strontium-containing raw material, adding the weighed 3.18g SrCl2(0.02mol) and 60ml of deionized water, continuously reacting for 60min, adjusting the pH value of the reaction mixed solution to about 13 (in an alkaline environment) by using 1mol/L NaOH solution, and continuously stirring and reacting for 120min at room temperature to obtain a precursor mixture;
(3) putting the reaction precursor obtained in the step (2) into a vacuum oven, and controlling the temperature to be 80 ℃ for drying;
(4) taking out the dry gel of the precursor obtained in the step (3), and putting the dry gel into an agate mortar for grinding and crushing to obtain a powdery precursor;
(5) placing the powdery precursor obtained in the step (4) in a muffle furnace in an air atmosphere, controlling the temperature at 130 ℃ and the reaction time for 240min for heat treatment, and reacting;
(6) after the reaction is finished, taking out the material, soaking the material for 120min by using 30ml of 0.02mol/L diluted hydrochloric acid solution, and then washing the material for multiple times by using deionized water until the supernatant is neutral;
(7) and (4) drying the solid sample collected in the step (6) in vacuum, controlling the temperature at 80 ℃ for 24 hours, and obtaining the nitrogen-doped comparative example 2 sample.
The catalysts obtained in the examples and comparative examples were subjected to the following performance tests:
the used photocatalytic degradation system consists of a dark box, a condensing system, a quartz kettle (250ml), a xenon lamp (300W) and a lifting platform. Visible light is generated by adding a CUT400 filter. The distance between the xenon lamp head and the liquid level is controlled to be 10 cm. In the experiment for evaluating the specific catalytic performance, 100mL of Methylene Blue (MB) solution with the concentration of 20ppm is added100mg of the nitrogen-doped strontium titanate SrTiO prepared in example 13-iNiStirring in dark for 30min, irradiating under visible light for reaction, sampling at interval of 10min, testing absorbance with ultraviolet-visible spectrophotometer, and making into C/C0(C is the corresponding concentration at the sampling point, C0Initial concentration after 30min of adsorption protected from light) as a function of time. In addition, the experiment for degrading methylene blue by visible light for the blank control sample prepared in comparative example 1 is a control group, and the same procedure as above is used for C/C0(C is the corresponding concentration at the sampling point, C0Initial concentration after 30min of adsorption protected from light) as a function of time.
FIG. 2 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd the X-ray diffraction patterns of the control samples synthesized in comparative example 1 and comparative example 2; FIG. 3 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNi and X-ray photoelectron spectra of the control synthesized in comparative example 1; FIG. 4 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd solid ultraviolet-visible diffuse reflectance (UV-vis DRS) plots for the control synthesized in comparative example 1 and comparative example 2; FIG. 5 shows the nitrogen-doped strontium titanate SrTiO synthesized in example 13-iNiAnd the visible light degradation methylene blue pattern of the control synthesized in comparative example 1 and comparative example 2.
By comparison, the nonmetallic element-doped strontium titanate prepared by the method has good visible light catalytic performance.
It should be noted that, if the pre-oxidation is not performed twice, the titanium-containing compound and the strontium-containing compound containing the target doped non-metal element are directly used as raw materials, and the heat treatment is performed at the lower temperature used in the examples, because the raw materials are still in a stable state under the condition, the chemical reaction is difficult to occur, and therefore, the comparative catalyst obtained by the treatment contains many raw material impurity peaks and has poor crystallinity.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A preparation method of a non-metal element doped strontium titanate catalyst is characterized by comprising the following steps:
carrying out first pre-oxidation on a titanium-containing compound containing a target doped non-metallic element by using a pre-oxidant to obtain a first reaction precursor;
mixing the first reaction precursor, the strontium-containing compound and the first solvent to carry out a first reaction, then adjusting the system to be alkaline, and continuing the reaction to obtain a second reaction precursor;
heating the second reaction precursor for second pre-oxidation and gelation to obtain a precursor xerogel;
and carrying out heat treatment on the xerogel to obtain the nonmetallic element doped strontium titanate catalyst.
2. The method of claim 1, wherein the titanium-containing compound containing the target doped non-metallic element comprises TiB2、TiC、Ti3C2、TiN、Ti2N2、Ti3N4、TiF3、TiP、TiS2One or more of (a).
3. The method for preparing a non-metallic element-doped strontium titanate catalyst according to claim 1, wherein the titanium-containing compound containing the target doped non-metallic element is dispersed in a second solvent to obtain a dispersion solution before use;
preferably, the second solvent is water or an aqueous ethanol solution.
4. The method of claim 1, wherein the pre-oxidizer comprises one or more of concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid, and hydrogen peroxide;
preferably, the mass concentration of the pre-oxidant is 0.05 mol/L-maximum saturation concentration;
preferably, the mass-to-volume ratio of the titanium-containing compound containing the target doping non-metallic element to the pre-oxidizer is 1 g: (10-200) ml.
5. The method of claim 1, wherein the strontium compound comprises SrO or SrCO3、Sr(OH)2、Sr(NO3)2、SrCl2、O8P2Sr3And C4H6O4Sr;
preferably, the molar ratio of the titanium-containing compound containing the target doping non-metallic element to the strontium-containing compound is 1: (1-1.5);
preferably, the first solvent comprises one or more of water, nitric acid, sulfuric acid, hydrochloric acid.
6. The method for preparing the non-metal element doped strontium titanate catalyst according to claim 1, wherein the substance used for adjusting the system to be alkaline comprises one or more of NaOH, KOH and ammonia water;
preferably, the alkalinity corresponds to a pH of 10 to 14.
7. The method for preparing the non-metal element-doped strontium titanate catalyst according to claim 1, wherein the temperature of the heat treatment is 50-500 ℃ and the time is 1-24 h.
8. The method for preparing a strontium titanate catalyst doped with a nonmetallic element according to any one of claims 1 to 7, wherein the precursor xerogel is pulverized before the heat treatment;
preferably, the heat treatment further comprises: repeatedly washing the heat-treated product by using a third solvent and a fourth solvent, and then drying in vacuum;
preferably, the third solvent is water or ethanol water solution, and the fourth solvent comprises one or more of water, nitric acid, sulfuric acid and hydrochloric acid;
preferably, the temperature of the vacuum drying is 50-200 ℃, and the time is 6-24 h.
9. A non-metal element doped strontium titanate catalyst, characterized in that it is prepared by the method of any one of claims 1 to 8.
10. The non-metal element doped strontium titanate catalyst of claim 9, wherein the general structural formula of the non-metal element doped strontium titanate catalyst is SrTiO3-iXiWherein X represents a target doped non-metal element, and is selected from B, C, N, F, P, S; i represents the doping content.
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| CN115582111A (en) * | 2022-10-27 | 2023-01-10 | 安徽大学 | SrTiO derived from MXene 3 Base photocatalyst and application thereof |
| CN115582111B (en) * | 2022-10-27 | 2024-04-09 | 安徽大学 | SrTiO derived from MXene 3 Base photocatalyst and application thereof |
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