CN110937628A - TiO with oxygen vacancy2Method for producing a material - Google Patents

TiO with oxygen vacancy2Method for producing a material Download PDF

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CN110937628A
CN110937628A CN201911251015.4A CN201911251015A CN110937628A CN 110937628 A CN110937628 A CN 110937628A CN 201911251015 A CN201911251015 A CN 201911251015A CN 110937628 A CN110937628 A CN 110937628A
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tio
titanium dioxide
biomass
cellulose
oxygen
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王建国
周强
魏中哲
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/043—Titanium sub-oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide

Abstract

The invention discloses TiO with oxygen vacancy2Method for preparing material, said TiO having oxygen vacancies2The material is prepared by in-situ reduction of a titanium dioxide raw material by biomass, wherein the titanium dioxide raw material is TiO reduced by the biomass in-situ reduction2In the material, the proportion of the number of formed oxygen vacancies is 3-60%. The method mainly adopts a biomass in-situ reduction method, N atoms or C atoms in the biomass and O in titanium dioxide react at high temperature to be converted into nitrogen oxides or carbon oxides, the nitrogen oxides or the carbon oxides formed by conversion drift out along with inert gas, and therefore oxygen atoms in the titanium dioxide are pulled out to form TiO with oxygen vacancies2A material. TiO having oxygen vacancy of the invention2The preparation method of the material has the advantages of simple method, safe reaction, good stability of the generated oxygen vacancy and the like.

Description

TiO with oxygen vacancy2Method for producing a material
Technical Field
The invention relates to the field of materials, in particular to TiO with oxygen vacancy2A method for preparing the material.
Background
TiO2Is a semiconductor with great development prospect, has been widely concerned in the past decades due to the great application potential in the fields of photoelectricity, biomedicine, photocatalysis and the like, and has the defect of influencing TiO2Important factors for the properties, in TiO2Among the defects found in (c), oxygen vacancy is one of the most important defects. Now, no matter byBoth theoretical calculations and experiments have conducted extensive studies on oxygen vacancies in metal oxides. The results show that oxygen vacancies can be used as important adsorption and active sites of heterogeneous catalysis, and have strong influence on the reactivity of the metal oxide. In addition, studies have shown that the photocatalytic properties of titanium oxide metal oxides, including electronic structure, charge transport, and surface properties, are closely related to oxygen vacancies. In principle, the formation of oxygen vacancies of titanium dioxide leads to the creation of unpaired electrons or Ti3 +Central, thereby forming a donation level of TiO of electronic structure2. Furthermore, oxygen vacancies are believed to affect the electron-hole recombination process of the catalyst, resulting in a chemical change rate depending on the electron or hole of the charge transfer. Theoretical and experimental results show that the redundant electrons in the oxygen vacancy state affect TiO2Surface adsorption and key adsorbates (e.g. O)2Or H2O) reactivity.
At present, the method for obtaining oxygen vacancies is mainly H2Heat treatment (ACS appl. mater. Interfaces 2013,5, 11129-. However, these methods still have some problems, such as H2The method is flammable and explosive, the reaction conditions for reducing the metal simple substance are too harsh, oxygen vacancies obtained by reducing the sodium borohydride liquid phase are unstable, and the like.
Disclosure of Invention
In view of the above technical problems in the prior art, the present invention aims to provide a TiO with oxygen vacancy2The invention relates to a preparation method of a material, which can form TiO with different proportions of oxygen vacancies by regulating the amount of biomass2。
The TiO with oxygen vacancy2Process for the preparation of a material, characterized in that the TiO with oxygen vacancies2The material is prepared by in-situ reduction of a titanium dioxide raw material by biomass, wherein the titanium dioxide raw material is TiO reduced by the biomass in-situ reduction2In the material, the proportion of the number of formed oxygen vacancies is 3-60%.
Said oneTiO with oxygen vacancy2The preparation method of the material is characterized in that the specific steps of in-situ reduction of the titanium dioxide raw material by biomass are as follows:
1) adding biomass and titanium dioxide into a solvent, stirring until uniform dispersion liquid is formed, heating and stirring to completely volatilize the solvent, and obtaining a solid mixture;
2) calcining the solid mixture obtained in the step 1) in an inert gas atmosphere at the temperature of 600-1200 ℃ for 0.5-6 h to ensure that N atoms or C atoms in the biomass react with O in titanium dioxide at high temperature to be converted into nitrogen oxides or carbon oxides, and drifting the nitrogen oxides or the carbon oxides formed by conversion out along with the inert gas to form TiO with oxygen vacancies2A material.
The TiO with oxygen vacancy2The preparation method of the material is characterized in that the biomass is one or a mixture of more than two of sucrose, fructose, glucose, galactose, chitosan, cellulose and glucosamine hydrochloride.
The TiO with oxygen vacancy2The preparation method of the material is characterized in that in the step 1), the titanium dioxide is TiO2（B）。
The TiO with oxygen vacancy2The preparation method of the material is characterized in that in the step 1), the mass of the biomass and the titanium dioxide is 0.1-15: 1, preferably 0.6-10: 1.
The TiO with oxygen vacancy2The preparation method of the material is characterized in that in the step 2), the inert gas is one of nitrogen and argon.
The TiO with oxygen vacancy2The preparation method of the material is characterized in that in the step 1), the solvent is ethanol or water.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention takes biomass and titanium oxide as raw materials, and TiO with different proportions of oxygen vacancies is generated in situ by one-step calcination2A material. And conventionally by H2IsoreducibilityGas and TiO2Calcination of the TiO with oxygen vacancies of the present invention2The preparation method of the material has the advantages of simple method, safe reaction, good stability of the generated oxygen vacancy and the like.
2. Because the amount of the biomass can be simply and effectively controlled, the number of oxygen vacancies generated in the calcining process can be effectively and simply controlled. TiO prepared by the invention2The oxygen vacancy distribution is uniform and the proportion of the oxygen vacancy can be effectively controlled.
3. TiO having oxygen vacancy of the invention2In the preparation process of the material, after the biomass and the titanium dioxide are uniformly mixed in the solvent, the mixture is heated and stirred until the solvent is completely volatilized, so that the titanium dioxide and the biomass can be closely and uniformly combined in the later calcining process under the inert gas atmosphere, although in the high-temperature calcining process, N atoms or C atoms in the biomass and O in the titanium dioxide react at high temperature to be converted into nitrogen oxides or carbon oxides, the converted nitrogen oxides or carbon oxides float out along with the inert gas, and therefore oxygen atoms in the titanium dioxide are pulled out to form TiO with oxygen vacancies2A material.
Drawings
FIG. 1 shows the in-situ reduced TiO form of cellulose obtained in example 12An EPR map of the material;
FIG. 2 shows the in-situ reduced TiO form of cellulose obtained in example 12XPS plot of material;
FIG. 3 is an EPR plot of the TiO2 material obtained in example 10 after treatment with both cellulose and hydrogen;
FIG. 4 is an XPS plot of the TiO2 material obtained in example 10 after treatment with both cellulose and hydrogen;
FIG. 5a is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.1, and the obtained TiO is subjected to in-situ reduction by the cellulose2An EPR map of the material;
FIG. 5b is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.2, and the obtained TiO is subjected to in-situ reduction by the cellulose2An EPR map of the material;
FIG. 5c is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.4, and the obtained TiO is subjected to in-situ reduction by the cellulose2An EPR map of the material;
FIG. 5d is TiO2(B) When the mass ratio of the TiO to the cellulose is 2, the obtained TiO reduced in situ by the cellulose2An EPR map of the material;
FIG. 6a is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.1, and the obtained TiO is subjected to in-situ reduction by the cellulose2XPS plot of material;
FIG. 6b is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.2, and the obtained TiO is subjected to in-situ reduction by the cellulose2XPS plot of material;
FIG. 6c is TiO2(B) The mass ratio of the obtained TiO to the cellulose is 0.4, and the obtained TiO is subjected to in-situ reduction by the cellulose2XPS plot of material;
FIG. 6d is TiO2(B) When the mass ratio of the TiO to the cellulose is 2, the obtained TiO reduced in situ by the cellulose2XPS plot of material;
FIG. 7 shows the in-situ reduced TiO of cellulose obtained in comparative example 12EPR map of material.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 based on TiO2(B) TiO with oxygen vacancy synthesized by taking cellulose as raw material2
0.5g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent Co., Ltd.) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then added TiO2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the cellulose are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then the TiO reduced in situ by the cellulose is obtained2A material.
Example 1 cellulose in situ reduced TiO2The EPR characterization results of the materials are shown in FIG. 1, and the XPS characterization results are shown in FIG. 2. As can be seen from fig. 1 and 2: TiO reduced in situ by cellulose2In the material, oxygen vacancies do occur, and
formed TiO with oxygen vacancies2Accounting for 36 percent.
Example 2 based on TiO2(B) And D-glucose as raw material2
0.5g D-glucose (available from Sigma reagent Co.) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then TiO was added2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the D-glucose are closely and uniformly combined after the later calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then TiO reduced by D-glucose glycogen potential is obtained2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 34 percent.
Example 3 TiO-based2(B) TiO synthesized by taking sucrose as raw material and having oxygen vacancy2
0.5g sucrose (from Sigma reagent) and 50mL deionized water were added to a 100 mL beaker, stirred to dissolve and TiO was added2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the cane sugar are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, thus obtaining the TiO reduced in situ by the sucrose2A material. TiO reduced in situ by sucrose2In the material, TiO with oxygen vacancies is formed2Accounting for 25 percent.
Example 4 based on TiO2(B) TiO synthesized by taking fructose as raw material and having oxygen vacancy2
0.5g fructose (from Sigma reagent Co.) and 50mL deionized water were added to a 100 mL beaker, stirred to dissolve and TiO was added2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the fructose are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, thus obtaining TiO reduced by fructose in situ2A material. TiO reduced by fructose in situ2In the material, TiO with oxygen vacancies is formed2Accounting for 32 percent.
Example 5 based on TiO2(B) TiO synthesized by taking glucosamine hydrochloride as raw material and having oxygen vacancy2
0.5g glucosamine hydrochloride (purchased from Sigma reagent Co.) and 50mL deionized water were added to a 100 mL beaker, dissolved with stirring and then TiO was added2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the glucosamine hydrochloride are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then the TiO reduced by glucosamine hydrochloride in situ is obtained2A material. TiO in-situ reduced by glucosamine hydrochloride2In the material, TiO with oxygen vacancies is formed2Accounting for 27 percent.
Example 6 based on TiO2(B) TiO with oxygen vacancy synthesized by taking chitosan as raw material2
0.5g of chitosan (low viscosity,<200 mpa.s, purchased from Sigma) and 50mL of deionized water, dissolved with stirring and then added with TiO2(B) 0.4g, stirred to a uniform mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the chitosan are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 h in a nitrogen furnace after the temperature is programmed to 650 DEG CTo obtain TiO reduced by chitosan in situ2A material. TiO reduced by chitosan in situ2In the material, TiO with oxygen vacancies is formed2Accounting for 30 percent.
From the experimental results of examples 1-6, it can be seen that different types of biomass were used for in situ reduction, and TiO was obtained from a titanium dioxide feedstock by in situ reduction of the biomass2The proportion of the number of oxygen vacancies formed is different in the material.
Example 7 preparation of cellulose with varying proportions of oxygen vacancies
1.0 g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then TiO was added2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced in situ by the cellulose2A material. TiO22(B) The mass ratio of the obtained TiO to the cellulose is 0.1, and the obtained TiO is subjected to in-situ reduction by the cellulose2The EPR diagram of the material is shown in FIG. 5a, the XPS diagram is shown in FIG. 6a, and the formed TiO with oxygen vacancy is measured by the XPS characterization2Accounting for 25 percent.
0.5g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent) and 25mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then added TiO2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced in situ by the cellulose2A material. TiO22(B) The mass ratio of the obtained TiO to the cellulose is 0.2, and the obtained TiO is subjected to in-situ reduction by the cellulose2The EPR chart of the material is shown in FIG. 5b, the XPS chart is shown in FIG. 6b, and the formed TiO with oxygen vacancy is measured by the XPS characterization2Accounting for 28 percent.
Adding 0.25 cellulose (artificial) into 100 ml beakerSynthetic cellulose, 65 μm particle size, available from Meclin reagent Co.) and 25mL of deionized water were dissolved with stirring and then TiO was added2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced in situ by the cellulose2A material. TiO22(B) The mass ratio of the obtained TiO to the cellulose is 0.4, and the obtained TiO is subjected to in-situ reduction by the cellulose2The EPR chart of the material is shown in FIG. 5c, the XPS chart is shown in FIG. 6c, and the formed TiO with oxygen vacancy is measured by the XPS characterization2Accounting for 32 percent.
1g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent Co., Ltd.) and 100 mL of deionized water were added to a 100 mL beaker, respectively, and dissolved with stirring and then TiO was added2(B) 2g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced in situ by the cellulose2A material. TiO22(B) When the mass ratio of the TiO to the cellulose is 2, the obtained TiO reduced in situ by the cellulose2The EPR chart of the material is shown in FIG. 5d, the XPS chart is shown in FIG. 6d, and the formed TiO with oxygen vacancy is measured by the XPS characterization2Accounting for 39 percent.
1g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent) and 200 mL of deionized water were added to a 250 mL beaker, dissolved with stirring and then added TiO2(B) 4g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced in situ by the cellulose2A material. TiO reduced in situ by cellulose2In the material, TiO with oxygen vacancies is formed2Accounting for 30 percent.
1g of cellulose (synthetic cellulose, particle size 65 μm, from Michelin) was added to 500 ml beakersReagent company) and 300mL of deionized water, dissolved with stirring and then TiO was added2(B) 10 g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium oxide and the cellulose are closely and uniformly combined after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then the TiO reduced in situ by the cellulose is obtained2A material. TiO reduced in situ by cellulose2In the material, TiO with oxygen vacancies is formed2Accounting for 25 percent.
From the experimental results of examples 1 and 7, it can be seen that when different amounts of biomass are used for in-situ reduction, TiO formed by in-situ reduction of titanium dioxide raw material with biomass is obtained2The proportion of the number of oxygen vacancies formed is different in the material. Therefore, TiO with different proportions of oxygen vacancies can be formed by regulating and controlling the addition amount of biomass2。
Example 8 preparation of D-glucose with different oxygen vacancy numbers
1g of D-glucose (available from Sigma reagent Co.) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then TiO was added2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the TiO is calcined at the later stage2(B) And D-glucose are closely and uniformly combined. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then TiO reduced by D-glucose glycogen potential is obtained2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 18 percent.
0.5g D-glucose (available from Sigma reagent Co.) and 25mL of deionized water were added to a 100 mL beaker, dissolved with stirring and TiO was added2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, heating the solid mixture in a nitrogen furnace to 650 ℃ by a program, calcining for 1 h to obtain the product reduced by the D-glucose sugar levelAfter TiO22A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 25 percent.
0.25g D-glucose (available from Sigma reagent Co.) and 25mL of deionized water were added to a 100 mL beaker, dissolved with stirring and TiO was added2(B) 0.1g, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced by the D-glucose sugar level2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 32 percent.
1g D-glucose (available from Sigma reagent Co.) and 100 mL of deionized water were added to a 250 mL beaker, dissolved with stirring and TiO was added2(B) 2g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced by the D-glucose sugar level2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 40 percent.
1g D-glucose (available from Sigma reagent Co.) and 200 mL of deionized water were added to a 250 mL beaker, dissolved with stirring and TiO was added2(B) 4g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, and calcining the solid mixture for 1 h in a nitrogen furnace at the temperature of 650 ℃ by programming to obtain the TiO reduced by the D-glucose sugar level2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 25 percent.
1g D-glucose (available from Sigma reagent Co.) and 300mL of deionized water were added to a 500 mL beaker, dissolved with stirring and TiO was added2(B) 10 g, stirring to obtain a uniform mixed solution. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid mixture isThe solid mixture is calcined for 1 hour after the temperature is programmed to 650 ℃ in a nitrogen furnace, and the TiO reduced by the D-glucose glycogen potential is obtained2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 20 percent.
The experimental results of examples 7-8 show that instead of a greater amount of biomass addition resulting in a greater number of oxygen vacancies, there is an optimum ratio of titania to biomass content.
Example 9 oxygen vacancies generated at different ratios based on different temperatures
Experimental procedure example 1 was repeated except that the calcination temperature was different and the remaining conditions were the same as in example 1. The results of the reaction at different calcination temperatures are shown in Table 1.
TABLE 1
Figure DEST_PATH_IMAGE002
As is clear from example 9, the effect of the firing temperature on the oxygen vacancies is large, and the higher the temperature is, the larger the number of vacancies is produced.
Example 10 TiO obtained in example 12Reduction and reprocessing with hydrogen
0.2g of the cellulose in-situ reduced TiO prepared in example 1 was taken2The material is put into a tube furnace and H is introduced2Roasting, namely heating the temperature to 400 ℃ by a program and roasting for 1 h to obtain the TiO treated by the cellulose and the hydrogen2A material. Example 10 TiO treated with both cellulose and Hydrogen2The EPR characterization results of the materials are shown in FIG. 3, the XPS characterization results are shown in FIG. 4, and TiO with oxygen vacancy is shown in the specification2Accounting for 42 percent.
Comparative example 1 TiO with oxygen vacancies synthesized on the basis of titanium dioxide P25 and cellulose2
1g of cellulose (synthetic cellulose, particle size 65 μm, available from Meclin reagent Co., Ltd.) and 50mL of deionized water were added to a 100 mL beaker, and after stirring to dissolve, 250.1 g of titanium dioxide P was added and stirred to obtain a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide P25 after later calcination and the cellulose are closely and uniformly combined. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then the TiO reduced in situ by the cellulose is obtained2A material. TiO reduced in situ with cellulose obtained in comparative example 12EPR map of the Material As shown in FIG. 7, TiO with oxygen vacancies formed2Accounting for 0 percent.
Comparative example 2 TiO with oxygen vacancies synthesized on the basis of titanium dioxide P25 and D-glucose2
1g D-glucose (available from Sigma reagent Co.) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then 250.1 g of titanium dioxide P was added and stirred to a homogeneous mixture. The solid obtained by the method can ensure that the titanium dioxide P25 and the D-glucose are combined closely and uniformly after the post-calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, and then TiO reduced by D-glucose glycogen potential is obtained2A material. Reduced TiO by D-glucose sugar locus2In the material, TiO with oxygen vacancies is formed2Accounting for 0.6 percent.
Comparative example 3 TiO with oxygen vacancies synthesized based on titanium dioxide P25 and sucrose2
1g of sucrose (purchased from Sigma reagent Co.) and 50mL of deionized water were added to a 100 mL beaker, dissolved with stirring and then 250.1 g of titanium dioxide P was added, stirred to a homogeneous mixture. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can uniformly combine the titanium oxide and the cane sugar after the later-stage calcination. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, thus obtaining the TiO reduced in situ by the sucrose2A material. TiO reduced in situ by sucrose2In the material, TiO with oxygen vacancies is formed2Accounting for 0.5 percent.
Comparative example 4 device synthesized based on titanium dioxide P25 and fructoseTiO with oxygen vacancies2
To a 100 mL beaker was added 1g of fructose (available from Sigma reagent Co.) and 50mL of deionized water, and then 250.1 g of titanium dioxide P was added and stirred to dissolve it and stir the mixture until it was homogeneous. Heating and stirring until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide P25 after post-calcination and the fructose are closely and uniformly combined. The solid mixture is calcined for 1 hour in a nitrogen furnace after the temperature is programmed to 650 ℃, thus obtaining TiO reduced by fructose in situ2A material. TiO reduced by fructose in situ2In the material, TiO with oxygen vacancies is formed2Accounting for 0.2 percent.
As can be seen from comparative examples 1 to 4, the reaction of titanium dioxide p25 with biomass did not produce a large number of oxygen vacancies.

Claims (7)

1. TiO with oxygen vacancy2Process for the preparation of a material, characterized in that the TiO with oxygen vacancies2The material is prepared by in-situ reduction of a titanium dioxide raw material by biomass, wherein the titanium dioxide raw material is TiO reduced by the biomass in-situ reduction2In the material, the proportion of the number of formed oxygen vacancies is 3-60%.
2. TiO with oxygen vacancy according to claim 12The preparation method of the material is characterized in that the specific steps of in-situ reduction of the titanium dioxide raw material by biomass are as follows:
1) adding biomass and titanium dioxide into a solvent, stirring until uniform dispersion liquid is formed, heating and stirring to completely volatilize the solvent, and obtaining a solid mixture;
2) calcining the solid mixture obtained in the step 1) in an inert gas atmosphere at the temperature of 600-1200 ℃ for 0.5-6 h to ensure that N atoms or C atoms in the biomass react with O in titanium dioxide at high temperature to be converted into nitrogen oxides or carbon oxides, and drifting the nitrogen oxides or the carbon oxides formed by conversion out along with the inert gas to form TiO with oxygen vacancies2A material.
3. TiO with oxygen vacancy according to claim 22The preparation method of the material is characterized in that the biomass is one or a mixture of more than two of sucrose, fructose, glucose, galactose, chitosan, cellulose and glucosamine hydrochloride.
4. TiO with oxygen vacancy according to claim 22The preparation method of the material is characterized in that in the step 1), the titanium dioxide is TiO2（B）。
5. TiO with oxygen vacancy according to claim 22The preparation method of the material is characterized in that in the step 1), the mass of the biomass and the titanium dioxide is 0.1-15: 1, preferably 0.6-10: 1.
6. TiO with oxygen vacancy according to claim 22The preparation method of the material is characterized in that in the step 2), the inert gas is one of nitrogen and argon.
7. TiO with oxygen vacancy according to claim 22The preparation method of the material is characterized in that in the step 1), the solvent is ethanol or water.
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CN114314649A (en) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of Pd modified oxygen vacancy titanium oxide composite material, product and application thereof
CN114702065A (en) * 2022-03-25 2022-07-05 扬州大学 Oxygen-enriched defective TiO2Carbon composite material, preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111992206A (en) * 2020-08-30 2020-11-27 浙江工业大学 Ultra-dispersed noble metal heterogeneous catalyst and application thereof
CN113336265A (en) * 2021-03-10 2021-09-03 北京航空航天大学 Preparation method of black titanium dioxide B nanosheet with high-content oxygen vacancy defects
CN114314649A (en) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of Pd modified oxygen vacancy titanium oxide composite material, product and application thereof
CN114314649B (en) * 2021-12-29 2024-02-13 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of Pd modified oxygen vacancy titanium oxide composite material, product and application thereof
CN114702065A (en) * 2022-03-25 2022-07-05 扬州大学 Oxygen-enriched defective TiO2Carbon composite material, preparation method and application thereof

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