CN114984937A - Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof - Google Patents

Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114984937A
CN114984937A CN202210423640.8A CN202210423640A CN114984937A CN 114984937 A CN114984937 A CN 114984937A CN 202210423640 A CN202210423640 A CN 202210423640A CN 114984937 A CN114984937 A CN 114984937A
Authority
CN
China
Prior art keywords
vacancy
catalyst
titanium
homojunction
titanium dioxide
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
Application number
CN202210423640.8A
Other languages
Chinese (zh)
Other versions
CN114984937B (en
Inventor
沈意
刘莎莎
朱超
许俊杰
张海忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202210423640.8A priority Critical patent/CN114984937B/en
Publication of CN114984937A publication Critical patent/CN114984937A/en
Application granted granted Critical
Publication of CN114984937B publication Critical patent/CN114984937B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • 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)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a spatially separated double-vacancy titanium dioxide homojunction catalyst, a preparation method and application thereof, wherein the catalyst comprises titanium vacancy-containing TiO 2 Inner core and TiO with oxygen-containing vacancy coated on outer side of inner core 2 The double-vacancy of the catalyst is a titanium vacancy and an oxygen vacancy. The invention creatively synthesizes the double-vacancy (titanium vacancy and oxygen vacancy) titanium dioxide homojunction catalyst with separated space by a one-step hydrothermal method, integrates the advantages of vacancy, pn junction and homojunction, and can provide continuous energy band bonding to effectively addCharge transfer across the interface. The catalyst has high catalytic efficiency, and is particularly suitable for photocatalytic hydrolysis hydrogen production.

Description

Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a spatially separated double-vacancy titanium dioxide homojunction catalyst, and a preparation method and application thereof.
Background
The solar cracking hydrogen production technology provides an important carbon neutralization idea for the development of renewable energy sources, but the utilization of solar energy and the charge separation capacity of the photocatalyst are the limiting factors of the development, so that the design of a high-efficiency and durable photolysis water catalyst is key. Because of the characteristics of good photocatalytic performance, light corrosion resistance and the like, metal semiconductors are always the focus of research on water photolysis catalysts. Wherein the TiO is 2 The method has the advantages of environmental friendliness, low price, easy obtainment, stable property, high oxidizability and the like, and is most widely researched. However, TiO 2 The forbidden band width of the solar cell is wide, only ultraviolet light which only accounts for 5% of the total energy of sunlight can be absorbed, and photo-generated electrons and holes are easy to combine in the migration process, so that the solar energy utilization rate and the energy conversion efficiency are low, and the application of the solar cell is severely limited. To improve TiO 2 The energy conversion efficiency of (2) is required to be modified, the electron/hole recombination is inhibited, the utilization rate of sunlight is improved, and the catalytic performance of the solar cell is improved.
In recent years, a great deal of research has been conducted on defect engineering, which has been found to have a significant effect on the regulation of both the interface electronic structure and the active center. It is known that defects in a photocatalyst can be used as traps for photo-generated electrons to promote the separation of photo-generated carriers and can also be used as recombination centers of the photo-generated carriers to reduce the photocatalytic activity, and a junction formed by two semiconductors can effectively separate photo-excited electron-hole pairs and then transfer through an interface to improve the problems caused by the defects. In this structure, the energy levels of the two semiconductors are matched to each other, and a built-in electric field is formed due to band bending at the interface, which facilitates the photo-excited electrons and holes to move in opposite directions. In addition, a homojunction made of materials of the same composition and/or crystal structure can provide continuous band bonding and effectively accelerate charge transfer across the interface, as compared to a heterojunction composed of two different materials. The present invention recognizes that vacancy dominated p-n homojunctions are more promising for photocatalytic hydrogen production because they combine the advantages of defect engineering, p-n junctions, and homojunctions.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a spatially separated double-vacancy titanium dioxide homojunction catalyst, and a preparation method and application thereof. The invention innovatively synthesizes the titanium dioxide homojunction with double vacancy (titanium vacancy and oxygen vacancy) separated in space by a one-step hydrothermal method, the catalyst has higher catalytic efficiency, and is particularly suitable for photocatalytic hydrolysis hydrogen production.
In order to fully utilize the structural characteristics and photocatalytic characteristics of titanium dioxide, the invention adopts a brand new thought: the titanium dioxide containing titanium vacancies can form a hole type semiconductor (p-type semiconductor), and the titanium dioxide containing oxygen vacancies can form the structural characteristics of an electron type semiconductor (n-type semiconductor); and the same semiconductor containing the pn junction can form a homojunction that can provide continuous band bonding and efficiently accelerate charge transfer across the interface.
The invention also aims to provide a preparation method of the spatially separated double-vacancy titanium dioxide homojunction synthesized by the one-step hydrothermal method, which is realized by the following technical scheme:
a spatially separated double-vacancy titanium dioxide homojunction catalyst is prepared from the titanium-containing vacancy inner core TiO 2 Outer shell TiO coated with oxygen-containing vacancy 2 And obtaining the spatially separated double-vacancy titanium dioxide homojunction catalyst, wherein the double vacancies of the catalyst are titanium vacancies and oxygen vacancies.
The preparation method of the spatially separated double-vacancy titanium dioxide homojunction catalyst adopts a one-step hydrothermal preparation method and comprises the steps of firstly synthesizing a titanium vacancy-containing precursor and then synthesizing oxygen vacancy-containing TiO 2 The one-step hydrothermal process of (1).
A preparation method of a spatially separated double-vacancy titanium dioxide homojunction catalyst comprises the following specific steps of a one-step hydrothermal method:
1) mixing glycerol and lower alcohols, stirring uniformly, adding titanium salt into the mixed solution, and stirring fully to obtain a first mixture;
2) dropwise adding deionized water into the first mixture, and stirring uniformly to obtain a second mixture; and transferring the second mixture into a hydrothermal reaction kettle, stirring, putting the hydrothermal reaction kettle into an oven, heating for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing and drying the product, and calcining at high temperature to obtain the spatially separated double-vacancy titanium dioxide homogeneous catalyst.
Further, the titanium salt includes at least one of titanium acetate, titanium oxalate, tetrabutyl titanate, and titanium sulfate, and the lower alcohol includes at least one of methanol, ethanol, propanol, and isopropanol.
Preferably, the volume ratio of glycerol to lower alcohols is 5-40 mL: 40-75 mL, preferably 10-15 mL: 65-70 mL; the volume of glycerol and the amount of titanium salt are (5-20) mL: (5-10) mmol, preferably (10-15) mL: (6-7) mmol.
Preferably, in the step 2), the heating temperature of the oven is 100-300 ℃, preferably 180-200 ℃, and the heating time is 1-48 hours, preferably 20-30 hours; in the step 2), the high-temperature calcination is carried out in an air atmosphere, the calcination temperature is 350-500 ℃, and the calcination time is 1-5 h.
Preferably, the volume ratio of the deionized water to the first mixture in the step 2) is 0.1-1: 80-82, preferably 0.2-0.5: 80-82.
The spatially separated double-vacancy titanium dioxide homojunction catalyst is applied to photocatalytic hydrogen production.
Further, the application method comprises the following steps: under the illumination condition, hydrogen is produced by photocatalysis of an aqueous solution containing a sacrificial agent by using a spatially separated double-vacancy titanium dioxide homojunction catalyst, wherein the aqueous solution of the sacrificial agent comprises at least one of methanol, isopropanol, triethanolamine, formic acid and ascorbic acid.
Preferably, the specific application method is as follows: adding the catalyst material into a sacrificial agent aqueous solution, adding a chloroplatinic acid solution after bubbling argon, irradiating the obtained mixed solution under a high-pressure mercury lamp for 0.5-1h to carry platinum, then discharging argon to carry out a hydrogen production experiment, magnetically stirring in the dark for 0.5-1h to achieve adsorption-desorption balance, and turning on a metal halide lamp to carry out photocatalytic hydrogen production.
Preferably, the aqueous solution of the sacrificial agent is an aqueous methanol solution, and the volume concentration of the aqueous methanol solution is 10-70%, preferably 30%; the ratio of the mass of the catalyst to the volume of the aqueous solution of the sacrificial agent is (10-30) mg: 100mL, preferably 20 mg: 100 mL; the mass ratio of the platinum element to the catalyst in the chloroplatinic acid solution is 0.5-2: 20, preferably 1: 20.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
the inner core containing the titanium vacancy and the outer shell containing the oxygen vacancy are fused together innovatively by adopting a one-step hydrothermal method, and the obtained spatially-separated double-vacancy titanium dioxide homojunction catalyst is high in catalytic efficiency and is particularly suitable for photocatalytic hydrolysis hydrogen production; in addition, the spatially separated double-vacancy titanium dioxide homojunction catalyst is low in price and suitable for large-scale application.
Drawings
FIG. 1 is an electron microscope scan of the composite material prepared in comparative example 1;
FIG. 2 is an electron micrograph of the composite obtained in example 1;
FIG. 3 is an electron micrograph of the composite obtained in example 2;
FIG. 4 is an electron micrograph of the composite obtained in example 3;
FIG. 5 is an electron micrograph of the composite obtained in example 4.
Detailed Description
The invention is further illustrated in the following figures and examples in order to better understand the nature of the invention for those skilled in the art. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or materials used in the present invention are commercially available products unless otherwise specified.
Blank example 1:
preparation of titanium vacancy-containing precursor:
(1) 70mL of absolute ethyl alcohol and 10mL of glycerol are continuously stirred for 0.5h and mixed uniformly to obtain a mixed solution.
(2) 2mL of tetrabutyl titanate was added to the mixture of (1), stirring was maintained, and stirring was continued for 0.5h until clear.
In each of the following examples, the titanium vacancy-containing precursor was utilized. Of course, it will be appreciated by those skilled in the art that the method of preparing the titanium vacancy-containing precursor is only a preferred mode of the invention, and that various parameters can be adjusted according to actual needs. The anhydrous ethanol in the titanium vacancy-containing precursor can also be replaced by other alcohols in the prior art, such as methanol, propanol or isopropanol and the like.
The oxygen vacancy-containing enclosures of the present invention are prepared by a hot water process. Oxygen vacancy containing TiO 2 TiO with shell wrapping titanium-containing vacancy 2 The inner core makes the two parts into a whole. The specific embodiment is as follows:
example 1
In this example, the specific steps for preparing the oxygen vacancy-containing outer shell are as follows:
0.1mL of deionized water was added to the continuously stirred precursor mixed solution containing titanium vacancies prepared in blank example 1 (about 82 mL) and stirred for 0.5h until uniform. The mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and stirred continuously for 0.5 h. The reaction kettle is put into an oven to be heated to 180 ℃ and kept for 24 h. And (3) after the reaction kettle is naturally cooled to room temperature, washing the product with absolute ethyl alcohol, centrifuging for a plurality of times, and keeping the temperature of 60 ℃ in a vacuum drying oven for overnight drying to obtain white powder. The white powder obtained was put in a tube furnace in an air atmosphere at 5 ℃/min -1 The temperature of the mixture is constant and calcined for 1 hour after the heating rate is up to 470 ℃, and the space-separated double-vacancy titanium dioxide homojunction catalyst is obtained after natural cooling.
Example 2
In this example, the specific steps for preparing an oxygen vacancy containing shell are as follows:
to a continuously stirred precursor mixture solution containing titanium vacancies prepared as blank example 1 (about 82 mL), 0.2mL of deionized water was added and stirred for 0.5h until well mixed. The mixture was transferred to 100mL Teflon linerThe hydrothermal reaction kettle is continuously stirred for 0.5 h. The reaction kettle is put into an oven to be heated to 180 ℃ and kept for 24 h. And (3) after the reaction kettle is naturally cooled to room temperature, washing the product with absolute ethyl alcohol, centrifuging for a plurality of times, and keeping the temperature of 60 ℃ in a vacuum drying oven for overnight drying to obtain white powder. The white powder obtained was put in a tube furnace in an air atmosphere at 5 ℃/min -1 The temperature of the mixture is constant and calcined for 1 hour after the heating rate is up to 470 ℃, and the space-separated double-vacancy titanium dioxide homojunction catalyst is obtained after natural cooling.
Example 3
In this example, the specific steps for preparing an oxygen vacancy containing shell are as follows:
0.5mL of deionized water was added to the continuously stirred precursor mixture solution containing titanium vacancies prepared in blank example 1 (about 82 mL) and stirred for 0.5h until uniform. The mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and stirred continuously for 0.5 h. The reaction kettle is put into an oven to be heated to 180 ℃ and kept for 24 h. And (3) after the reaction kettle is naturally cooled to room temperature, washing the product with absolute ethyl alcohol, centrifuging for a plurality of times, and keeping the temperature of 60 ℃ in a vacuum drying oven for overnight drying to obtain white powder. The white powder obtained was put in a tube furnace in an air atmosphere at 5 ℃/min -1 The temperature of the mixture is constant and calcined for 1 hour after the heating rate is up to 470 ℃, and the space-separated double-vacancy titanium dioxide homojunction catalyst is obtained after natural cooling.
Example 4
In this example, the specific steps for preparing an oxygen vacancy containing shell are as follows:
1mL of deionized water was added to the continuously stirred precursor mixture solution containing titanium vacancies prepared in blank example 1 (about 82 mL) and stirred for 0.5h until uniformly mixed. The mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and stirred continuously for 0.5 h. The reaction kettle is put into an oven to be heated to 180 ℃ and kept for 24 h. And (3) after the reaction kettle is naturally cooled to room temperature, washing the product with absolute ethyl alcohol, centrifuging for a plurality of times, and keeping the temperature of 60 ℃ in a vacuum drying oven for overnight drying to obtain white powder. The white powder obtained was put in a tube furnace in an air atmosphere at 5 ℃/min -1 The temperature of the mixture is constant and calcined for 1 hour after the heating rate is up to 470 ℃, and the space-separated double-vacancy titanium dioxide homojunction catalyst is obtained after natural cooling.
Comparative example 1
The procedure for the preparation of the titanium vacancy-containing titanium dioxide catalyst alone was repeated for the preparation of the spatially separated double-vacancy titanium dioxide homojunction catalyst of example 1, except that deionized water was not added at the time of the preparation.
The SEM images of the catalysts prepared in comparative example 1 and examples 1-4 are shown in fig. 1-5, respectively. As can be seen from fig. 1, the morphology of the catalyst of comparative example 1 is a rough, spiky surface. As can be seen from fig. 2-5: with the addition of deionized water, the rough and thorn-shaped surface of the catalyst is covered to form a smooth ball; however, with a large increase in deionized water, the smooth surface of the catalyst gradually disappeared and the particle stacks pressed together to form a doughy structure.
Application example 1
Photocatalytic hydrogen production tests were carried out using the vacancy-containing materials obtained in examples 1 to 4 and comparative example 1, respectively, while maintaining room temperature (25. + -. 1 ℃ C.) under irradiation of a metal halide lamp containing AM 1.5.
The experimental conditions were: 100mL of 30% strength methanol solution was taken in the photoreactor, 20mg of vacancy-containing material was added, stirred ultrasonically for 0.5h, and bubbled under argon for 0.5 h. 200 mul of chloroplatinic acid solution containing 0.5wt% of platinum was added dropwise under magnetic stirring and irradiated under a high pressure mercury lamp for 0.5h to carry platinum. And (4) sealing the photoreactor to discharge argon for hydrogen production experiment. The mixture is magnetically stirred for 0.5h in the dark to reach the adsorption-desorption balance. The on illumination intensity is 100mw/cm 2 The metal halide lamp is used for photocatalytic hydrogen production, sampling is carried out at regular time, and the concentration of hydrogen in the container is detected by gas chromatography.
The result of photocatalytic hydrogen production after 3 hours is shown in table 1, and materials containing different vacancies have certain difference on photocatalytic hydrogen production. The highest hydrogen production rate of the photocatalytic hydrogen production of the embodiment 3 is fastest, and the hydrogen production of the embodiment 3 is about 2 times of that of the comparative example 1. The hydrogen production amounts of the embodiments 1-4 are all higher than that of the comparative example 1, which shows that the oxygen vacancy is constructed on the basis of the titanium-containing vacancy, so that a homojunction can be formed, and the photocatalytic hydrogen production capability of the material is obviously improved. A pn junction consisting predominantly of titanium and oxygen vacancies is capable of efficiently separating photoexcited electron-hole pairs and subsequently transporting them across the interface. In this structure, the difference in fermi levels causes band bending at the interface to provide a very strong internal electric field for efficient charge transfer and separation, which helps photoexcited electrons and holes to move in opposite directions, enhancing photocatalytic hydrogen generation capability.
Figure DEST_PATH_IMAGE002
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled 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 invention.

Claims (10)

1. A spatially separated double-vacancy titanium dioxide homojunction catalyst is characterized by comprising titanium-vacancy-containing TiO 2 Inner core and TiO with oxygen-containing vacancy coated on outer side of inner core 2 The double-vacancy of the catalyst is a titanium vacancy and an oxygen vacancy.
2. The process of claim 1, wherein the one-step hydrothermal preparation comprises first synthesizing a titanium vacancy-containing precursor and then synthesizing an oxygen vacancy-containing TiO 2 The one-step hydrothermal process of (1).
3. The method for preparing the spatially-separated double-vacancy titanium dioxide homojunction catalyst according to claim 2, wherein the one-step hydrothermal method comprises the following specific steps:
1) mixing glycerol and lower alcohols, stirring uniformly, adding titanium salt into the mixed solution, and stirring fully to obtain a first mixture;
2) dropwise adding deionized water into the first mixture, and stirring uniformly to obtain a second mixture; and transferring the second mixture into a hydrothermal reaction kettle, stirring, putting the hydrothermal reaction kettle into an oven, heating for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing and drying the product, and calcining at high temperature to obtain the spatially separated double-vacancy titanium dioxide homogeneous catalyst.
4. The process of claim 3, wherein the titanium salt comprises at least one of titanium acetate, titanium oxalate, tetrabutyl titanate and titanium sulfate, and the lower alcohol comprises at least one of methanol, ethanol, propanol and isopropanol.
5. The method for preparing the spatially-separated double-vacancy titanium dioxide homojunction catalyst of claim 3, wherein in step 1), the volume ratio of the glycerol to the lower alcohol is 5-40 mL: 40-75 mL, preferably 10-15 mL: 65-70 mL; the volume of glycerol and the amount of titanium salt are (5-20) mL: (5-10) mmol, preferably (10-15) mL: (6-7) mmol.
6. The preparation method of the spatially separated double-vacancy titanium dioxide homojunction catalyst according to claim 3, wherein in the step 2), the heating temperature of the oven is 100-300 ℃, preferably 180-200 ℃, and the heating time is 1-48 hours, preferably 20-30 hours; in the step 2), high-temperature calcination is carried out in an air atmosphere, the calcination temperature is 350-500 ℃, and the calcination time is 1-5 hours;
the volume ratio of the deionized water to the first mixture in the step 2) is 0.1-1: 80-82, preferably 0.2-0.5: 80-82.
7. Use of a spatially separated double-vacancy titanium dioxide homojunction catalyst of claim 1 in photocatalytic hydrogen production.
8. The use of claim 7, wherein said catalyst is used to photocatalyze an aqueous solution containing a sacrificial agent comprising at least one of methanol, isopropanol, triethanolamine, formic acid, and ascorbic acid to produce hydrogen.
9. The application of claim 8, wherein the specific application method is as follows: adding the catalyst material into a sacrificial agent aqueous solution, adding a chloroplatinic acid solution after bubbling argon, irradiating the obtained mixed solution under a high-pressure mercury lamp for 0.5-1h to carry platinum, then discharging argon to perform a hydrogen production experiment, magnetically stirring for 0.5-1h in a dark place to achieve adsorption-desorption balance, and turning on a metal halide lamp to perform photocatalytic hydrogen production.
10. The use of claim 9, wherein: the sacrificial agent aqueous solution is a methanol aqueous solution, and the volume concentration of the aqueous solution is 10-70%, preferably 30%; the ratio of the mass of the catalyst to the volume of the aqueous sacrificial agent solution is (10-30) mg: 100mL, preferably 20 mg: 100 mL; the mass ratio of the platinum element to the catalyst in the chloroplatinic acid solution is 0.5-2: 20, preferably 1: 20.
CN202210423640.8A 2022-04-21 2022-04-21 Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof Active CN114984937B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210423640.8A CN114984937B (en) 2022-04-21 2022-04-21 Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210423640.8A CN114984937B (en) 2022-04-21 2022-04-21 Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114984937A true CN114984937A (en) 2022-09-02
CN114984937B CN114984937B (en) 2023-11-21

Family

ID=83025070

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210423640.8A Active CN114984937B (en) 2022-04-21 2022-04-21 Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114984937B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117886353A (en) * 2024-03-15 2024-04-16 陕西燃气集团富平能源科技有限公司 Method for preparing defective TiO by biological template method 2 Method for manufacturing micro-tube and defective TiO 2 Micro-tube and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108745347A (en) * 2018-05-08 2018-11-06 陕西科技大学 Pt atom carried titanium dioxide catalysis material and preparation method thereof
CN113908829A (en) * 2020-07-09 2022-01-11 中国科学院城市环境研究所 High-dispersion platinum-titanium dioxide photocatalyst and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108745347A (en) * 2018-05-08 2018-11-06 陕西科技大学 Pt atom carried titanium dioxide catalysis material and preparation method thereof
CN113908829A (en) * 2020-07-09 2022-01-11 中国科学院城市环境研究所 High-dispersion platinum-titanium dioxide photocatalyst and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LUN PAN, ET AL: "Constructing TiO2 p-n homojunctionforphotoelectrochemicaland photocatalytichydrogengeneration", NANOENERGY, vol. 28, pages 297 *
SHYAMSUNDAR GHOSH，ET AL: "Evidence of oxygen and Ti vacancy induced ferromagnetism in post-annealed undoped anatase TiO2 nanocrystals: A spectroscopic analysis", JOURNAL OF SOLID STATE CHEMISTRY, vol. 275, pages 1 - 2 *
SI-MING WU， ET AL: "Homojunction of Oxygen and Titanium Vacancies and its Interfacial n–p Effect", ADV. MATER., pages 1 - 7 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117886353A (en) * 2024-03-15 2024-04-16 陕西燃气集团富平能源科技有限公司 Method for preparing defective TiO by biological template method 2 Method for manufacturing micro-tube and defective TiO 2 Micro-tube and application thereof

Also Published As

Publication number Publication date
CN114984937B (en) 2023-11-21

Similar Documents

Publication Publication Date Title
CN110773213B (en) One-dimensional cadmium sulfide/two-dimensional titanium carbide composite photocatalyst and preparation method and application thereof
CN109248694B (en) Preparation method and application of non-noble metal copper indium sulfide/zinc indium sulfide composite photocatalyst
CN108607593B (en) Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof
CN107983371B (en) Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof
WO2021232751A1 (en) Porous coo/cop nanotubes, preparation method therefor and use thereof
CN112427045A (en) CdS/g-C synthesized by hydrothermal method and having Z-shaped heterojunction3N4Preparation method of composite photocatalyst material
CN110961123A (en) All-solid-state direct Z-type ZnIn prepared by hydrothermal method2S4-MoSe2High-efficiency photocatalyst
CN112844412A (en) Sulfur indium zinc-MXene quantum dot composite photocatalyst and preparation method and application thereof
CN113209993A (en) Preparation method of La-doped petal-shaped BiOBr photocatalytic material
CN113289659B (en) Preparation method and application of sulfonic functional group modified carbon nitride photocatalytic material
CN114984937A (en) Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof
CN116726973A (en) Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof
CN111644185A (en) Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects
CN115999614A (en) Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst
CN113600225B (en) Heterojunction composite material and application thereof
CN113697783B (en) Porous g-C 3 N 4 Preparation method and application of nano-sheet
CN113101946B (en) NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof
CN112916014B (en) All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof
CN114618526A (en) Cadmium sulfide/platinum/sodium tantalate nanocube composite photocatalyst and preparation method and application thereof
CN114762829A (en) Simple preparation method of Z-type heterojunction photocatalytic material
CN111151305A (en) Copper doped ultra-thin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production
CN112958124B (en) Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof
CN116371425B (en) CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst
CN114849737B (en) Flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst and application thereof
CN115739163B (en) Sulfide-nitride heterojunction composite 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