CN112774659B - Graphene/indium oxide hydride composite photocatalyst and preparation method thereof - Google Patents
Graphene/indium oxide hydride composite photocatalyst and preparation method thereof Download PDFInfo
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 124
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C01B2203/1041—Composition of the catalyst
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Abstract
The invention belongs to the technical field of semiconductor photocatalysis, and particularly relates to a graphene/indium oxide hydride composite materialA photocatalyst and a preparation method thereof. The invention provides a graphene/indium oxide hydride composite photocatalyst and a preparation method thereof, and the graphene/indium oxide hydride composite photocatalyst is characterized in that: by means of high-temperature high-pressure hydrogenation treatment on indium oxide (In) 2 O 3 ) Surface introduction of defect state structure to obtain hydrogenated In 2 O 3 (H‑In 2 O 3 ) The hydrogenated In obtained 2 O 3 Further compounding with graphene nanosheets to prepare graphene/hydrogenated In 2 O 3 The composite photocatalyst realizes the modification of the indium oxide photocatalyst, solves the problems of poor oxidation reduction capability, easy recombination of a photon-generated carrier, insufficient visible light response and the like of the indium oxide photocatalyst to a greater extent, and greatly improves the photocatalytic hydrogen production activity and photocatalytic stability of the indium oxide. The graphene/indium oxide hydride composite photocatalyst and the preparation method thereof provided by the invention provide a new thought and a new way for designing and developing a novel efficient visible-light-driven photocatalyst.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalysis, and particularly relates to a graphene/indium oxide hydride composite photocatalyst and a preparation method thereof.
Background
The technology for realizing photocatalytic decomposition of hydrogen produced by utilizing solar energy is an effective means for solving the problems of global fossil energy shortage and environmental pollution at present. The general idea is that the photocatalytic water splitting hydrogen production process mainly involves the following key steps: absorption of photocatalyst spectrum, separation and transmission of photon-generated carriers, photocatalytic interface reaction and the like. Obviously, the photocatalytic hydrogen production efficiency depends greatly on the kind of photocatalyst, the photogenerated carrier separation efficiency and the surface reactivity. In recent years, TiO 2 And CdS, etc. are sequentially reported for photocatalytic decomposition of water to produce hydrogen. But TiO 2 2 The semiconductor can only respond to ultraviolet light, and the ultraviolet light only accounts for 4% of the whole sunlight spectral range, and the sunlight utilization rate is still low. And CdS semiconductorAlthough the material can respond to visible light, the stability of the material is poor, and the material is not beneficial to being put into practical application. Therefore, it is necessary to develop a hydrogen production material by photocatalytic decomposition of water with high efficiency and stability in response to visible light.
Recent studies have found that an indium-based catalyst, In which indium oxide (In) is present, has good catalytic performance 2 O 3 ) It is favored because of its low cost and ready availability. In 2 O 3 The forbidden band width can respond to visible light (about 2.80eV), and the photocatalyst has the advantages of good chemical and thermal stability, non-precious metals and the like, so that the photocatalyst can be an ideal photocatalyst for preparing hydrogen by photocatalytic decomposition of water. But In 2 O 3 Has the problems of weaker self-oxidation-reduction capability, easy recombination of photon-generated carriers, lower photocatalytic hydrogen production activity and the like, for example, Chinese patent application 201811129561.6 discloses In with high catalytic activity 2 O 3 And preparation method and application thereof, and prepared pure-phase In 2 O 3 The maximum hydrogen production rate of the photocatalytic water decomposition is only 1.987 mu mol g -1 h -1 . It can be seen that pure phase In is required 2 O 3 And the modified or compounded material is further used for improving the photoresponse range and the photocatalytic hydrogen production performance.
Hydrotreating is a new semiconductor modification means that has been developed in recent years, and is a means that treats a semiconductor material in a high-temperature and high-pressure hydrogen atmosphere to generate defect-state structures such as oxygen vacancies on the surface of the semiconductor material, and the presence of these surface-state defect structures can effectively improve the separation efficiency of photogenerated carriers and thus greatly improve the photocatalytic activity of the photogenerated carriers. For example, many groups of subjects at home and abroad adopt a hydrogenation treatment mode to prepare a plurality of oxide photocatalysts (including TiO) 2 、ZnO、SrTiO 3 、BiVO 4 、BiFeO 3 Etc.) are successfully introduced into the surface, and the oxygen vacancy defects on the surface can improve the spectral absorption performance of the oxide photocatalyst to a certain extent and can also effectively promote the separation of photon-generated carriers, thereby greatly improving the photocatalytic activity of the oxide photocatalyst. Therefore, In is treated by means of hydrogenation treatment 2 O 3 Modification of semiconductor materialsIt is expected to improve In 2 O 3 Photocatalytic activity of (1). In addition, researches find that the semiconductor photocatalyst and the graphene two-dimensional nanosheet are compounded, and the graphene with a large specific surface area can be used as a carrier of an excellent catalyst, so that more catalyst particles can be adsorbed, the activity and selectivity of the photocatalyst are greatly improved, and the photocatalytic stability can be improved to a certain extent; meanwhile, the excellent conductivity of the graphene is beneficial to the effective separation of photo-generated electrons and holes, so that the photocatalytic efficiency of the photocatalyst can be further improved.
The invention provides an improved In 2 O 3 The method for semiconductor photocatalytic activity is characterized by that firstly, In is undergone the process of high-temp. high-pressure hydrogenation treatment 2 O 3 The surface of the photocatalyst is introduced with a defect state structure to prepare and obtain hydrogenated In 2 O 3 (H-In 2 O 3 ) Photocatalyst, and then hydrogenating In obtained 2 O 3 The photocatalyst is further compounded with the graphene two-dimensional nanosheet to prepare graphene/hydrogenated In 2 O 3 A composite photocatalyst, from which it is expected that In is increased to a large extent synergistically by both high-temperature and high-pressure hydrogenation treatment and graphene composite means 2 O 3 The photocatalytic hydrogen production activity and the photocatalytic stability of the semiconductor.
Disclosure of Invention
The invention aims to treat indium oxide (In) by high-temperature and high-pressure hydrogenation treatment and graphene compounding 2 O 3 ) The semiconductor photocatalyst is modified, so that the indium oxide hydride nanoparticles are uniformly distributed on the surface of the two-dimensional graphene nanosheet, and the efficient graphene/indium oxide hydride composite photocatalyst is prepared. According to the invention, firstly, the indium oxide semiconductor photocatalyst is subjected to high-temperature and high-pressure hydrogenation treatment to obtain the hydrogenated indium oxide photocatalyst, then the graphene/hydrogenated indium oxide composite photocatalyst is constructed in a graphene compounding manner, the modification of the indium oxide semiconductor photocatalyst is realized, the problems of poor oxidation-reduction capability of the indium oxide photocatalyst, easiness in compounding of a photon-generated carrier and the like are solved to a greater extent, and meanwhile, the indium oxide photocatalyst is improvedThe spectrum absorption performance is improved, so that the photocatalytic hydrogen production activity and the photocatalytic stability of the indium oxide photocatalyst are effectively improved.
The invention provides a graphene/indium oxide hydride composite photocatalyst and a preparation method thereof, and is characterized by being realized by the following technical scheme:
(1) firstly, the indium oxide (In) is prepared by calcining indium hydroxide powder at high temperature 2 O 3 ) The powder comprises the following specific processes: dissolving a certain amount of indium chloride powder in a solvent with a volume ratio of 3: 1, stirring uniformly to form an indium chloride solution with the molar concentration of 0.2-0.5M; simultaneously, mixing an ammonium hydroxide aqueous solution (28-30%) and absolute ethyl alcohol according to a volume ratio of 1:3, uniformly mixing to form an ammonium hydroxide solution; then, quickly adding an ammonium hydroxide solution with the same volume into the indium chloride solution, stirring and mixing to generate a white precipitate immediately, placing the obtained suspension into an 80-DEG oil bath, stirring for 30 minutes, taking out the suspension from the oil bath, and naturally cooling to room temperature; centrifuging the suspension at a high speed to collect precipitates, cleaning the precipitates with deionized water and absolute ethyl alcohol, and then transferring the precipitates to a vacuum oven for drying for 12 hours at 60 ℃ to obtain white indium hydroxide powder; finally calcining the obtained indium hydroxide powder In air at 700 ℃ for 5 hours, and naturally cooling to prepare light yellow indium oxide (In) 2 O 3 ) And (3) powder.
(2) Under the premise of obtaining the indium oxide powder, the indium oxide powder is modified by a high-temperature high-pressure hydrogenation treatment method to prepare hydrogenated indium oxide (H-In) 2 O 3 ) Powder, wherein the hydrogenation treatment process comprises the following specific steps: weighing indium oxide powder with a certain mass (0.5-2.0 g), putting the indium oxide powder into a hydrogenation reaction device, sealing the device, vacuumizing to below 10Pa, heating the device to a set hydrogenation temperature (200-400 ℃) at a certain heating rate (5-10 ℃/min), and starting to fill high-purity hydrogen (the purity is more than 99.999%) into the device under the condition of keeping the set hydrogenation temperature unchanged until a set hydrogen pressure (0.1-1.0 MPa) is reached; then carrying out hydrogenation reaction for a period of time (1-24 hours) under the conditions of the set hydrogenation temperature and the set hydrogen pressure;and after the reaction is finished, naturally cooling the device to room temperature, releasing the internal hydrogen pressure, and taking out the sample to prepare the indium hydroxide powder sample.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: dispersing graphene two-dimensional nanosheets with a certain mass in deionized water, and preparing to form a uniformly dispersed graphene aqueous solution with the concentration of 0.5-1 mg/mL; and (3) adding the hydrogenated indium oxide powder sample obtained in the step (2) into a graphene aqueous solution according to a certain mass ratio, and carrying out ultrasonic treatment for 2-4 h to obtain a mixture of graphene and hydrogenated indium oxide with a mass ratio of 1: 100-10: 100 of graphene/indium oxyhydroxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/hydrogenated indium oxide suspension to obtain the graphene/hydrogenated indium oxide composite photocatalyst.
The invention has the advantages and positive effects that:
the method combines high-temperature high-pressure hydrogenation treatment and graphene compounding to oxidize indium (In) 2 O 3 ) The photocatalyst powder is modified to prepare the graphene/indium oxide hydride composite photocatalyst, and the graphene/indium oxide hydride composite photocatalyst has the advantages of obvious modification effect, low cost and the like. Compared with a simple graphene composite modification means, the modification means combining high-temperature high-pressure hydrogenation treatment and graphene composite can improve indium oxide (In) to a greater extent 2 O 3 ) The photocatalytic activity of the photocatalyst is due to the fact that, on the one hand, the high-temperature and high-pressure hydrotreating process is carried out on indium oxide (In) 2 O 3 ) The photocatalyst surface generates a large number of surface defect state structures, the surface defects can form photogenerated carrier capture traps, separation of photogenerated charges is promoted, recombination of photogenerated electron-hole pairs is reduced, and on the other hand, the graphene/hydrogenated indium oxide composite photocatalyst formed after graphene recombination can further effectively promote separation of the photogenerated carriers and reduce recombination of the photogenerated carriers, and meanwhile, the stability of the hydrogenation induced surface defect structure can be improved, so that the photocatalyst is large in sizeGreatly improve indium oxide (In) 2 O 3 ) Photocatalytic activity and photocatalytic stability.
Drawings
FIG. 1 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) An XRD spectrogram of the composite photocatalyst;
FIG. 2 shows indium (In) oxide (a) prepared In example 1 2 O 3 ) (b) hydrogenated indium oxide (H-In) 2 O 3 ) And (c) graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A Transmission Electron Microscope (TEM) image of the composite photocatalyst;
FIG. 3 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A Raman spectrum (Raman) spectrum and an Electronic Paramagnetic Resonance (EPR) spectrum of the composite photocatalyst;
FIG. 4 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A solid Diffuse Reflection Spectrum (DRS) spectrogram of the composite photocatalyst;
FIG. 5 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A photocatalytic hydrogen production activity curve diagram of the composite photocatalyst changing along with illumination time under the illumination of a white light LED lamp;
FIG. 6 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A photocatalytic hydrogen production rate histogram of the composite photocatalyst under the irradiation of a white light LED lamp;
FIG. 7 shows (a) hydrogenated indium oxide (H-In) prepared In example 1 2 O 3 ) And (b) graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) And testing the photocatalytic hydrogen production circulation stability of the composite photocatalyst under the irradiation of the white light LED lamp.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
(1) firstly, the indium oxide (In) is prepared by calcining indium hydroxide powder at high temperature 2 O 3 ) The powder comprises the following specific processes: firstly, dissolving 3.6g of indium chloride (16.2mmol) in a mixed solvent of absolute ethyl alcohol (18mL) and deionized water (54mL) in a volume ratio of 1:3, and uniformly stirring to form an indium chloride solution with a molar concentration of 0.225M; meanwhile, 18mL of ammonium hydroxide (28-30%) and 54mL of absolute ethanol are mixed uniformly to form an ammonium hydroxide solution. Then, all the prepared ammonium hydroxide solution is quickly added into the indium chloride solution to generate a white precipitate immediately, and the obtained suspension is placed in an oil bath at the temperature of 80 ℃ to be stirred for 30 minutes; then taking the suspension out of the oil bath, and naturally cooling to room temperature; centrifuging the suspension at a high speed of 8000r/s, collecting white precipitate, cleaning the precipitate with deionized water and absolute ethyl alcohol, and transferring to a vacuum oven for drying at 60 ℃ for 12 hours to obtain white indium hydroxide powder; finally calcining the obtained indium hydroxide powder In air at 700 ℃ for 5 hours, and naturally cooling to prepare light yellow indium oxide (In) 2 O 3 ) And (3) powder.
(2) Under the premise of obtaining the indium oxide powder, the indium oxide powder is modified by a high-temperature high-pressure hydrogenation treatment method to prepare hydrogenated indium oxide (H-In) 2 O 3 ) Powder, and the hydrogenation treatment process comprises the following specific steps: weighing 1.0g of indium oxide powder, placing the indium oxide powder into a hydrogenation reaction device, sealing the device, vacuumizing to below 10Pa, heating the device to the hydrogenation temperature of 300 ℃ at a certain heating rate of 5 ℃/min, and starting to fill high-purity hydrogen (the purity is more than 99.999%) into the device under the condition of keeping the set hydrogenation temperature unchanged until the set hydrogen pressure is 0.1 MPa; then at the set hydrogenation temperature and settingCarrying out hydrogenation reaction for 1 hour under the condition of hydrogen pressure; after the reaction is finished, after the device is naturally cooled to room temperature, releasing the internal hydrogen pressure, taking out the sample to obtain an indium hydroxide powder sample marked as H-In 2 O 3 。
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: under the condition of stirring, adding 40mg of hydrogenated indium oxide powder sample obtained in the step (2) into 4mL of graphene aqueous solution with the concentration of 0.5mg/mL, and carrying out ultrasonic treatment for 2h to obtain uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 5: 100 of graphene/indium hydroxide composite photocatalyst marked as graphene/H-In 2 O 3 。
Example 2:
(1) indium oxide (In) 2 O 3 ) The powder was prepared as in example 1.
(2) Hydrogenated indium oxide (H-In) 2 O 3 ) The powder was prepared as in example 1.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: under the condition of stirring, adding 40mg of the hydrogenated indium oxide powder sample obtained in the step (2) into 0.8mL of graphene aqueous solution with the concentration of 0.5mg/mL, and carrying out ultrasonic treatment for 2h to obtain a uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 1: 100 of the graphene/hydrogenated indium oxide composite photocatalyst.
Example 3:
(1) indium oxide (In) 2 O 3 ) The powder was prepared as in example 1.
(2) Hydrogenated indium oxide (H-In) 2 O 3 ) The powder was prepared as in example 1.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: under the condition of stirring, adding 40mg of hydrogenated indium oxide powder sample obtained in the step (2) into 8mL of graphene aqueous solution with the concentration of 0.5mg/mL, and carrying out ultrasonic treatment for 2h to obtain uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 10: 100 of the graphene/hydrogenated indium oxide composite photocatalyst.
Example 4:
(1) indium oxide (In) 2 O 3 ) The powder was prepared as in example 1.
(2) Under the premise of obtaining the indium oxide powder, the indium oxide powder is modified by a high-temperature high-pressure hydrogenation treatment method to prepare hydrogenated indium oxide (H-In) 2 O 3 ) Powder, and the hydrogenation treatment process comprises the following specific steps: weighing 1.0g of indium oxide powder, placing the indium oxide powder into a hydrogenation reaction device, sealing the device, vacuumizing to below 10Pa, heating the device to the hydrogenation temperature of 300 ℃ at a certain heating rate of 5 ℃/min, and starting to fill high-purity hydrogen (the purity is more than 99.999%) into the device under the condition of keeping the set hydrogenation temperature unchanged until the set hydrogen pressure is 0.5 MPa; then carrying out hydrogenation reaction for 10 hours under the conditions of set hydrogenation temperature and set hydrogen pressure; and after the reaction is finished, naturally cooling the device to room temperature, releasing the internal hydrogen pressure, and taking out the sample to prepare the indium hydroxide powder sample.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: 40mg of the indium hydroxide powder sample obtained in step (2) was added to a concentration of 3mL with stirringCarrying out ultrasonic treatment for 4h in 0.8mg/mL graphene aqueous solution to obtain a uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 6: 100 of the graphene/hydrogenated indium oxide composite photocatalyst.
Example 5:
(1) indium oxide (In) 2 O 3 ) The powder was prepared as in example 1.
(2) Under the premise of obtaining the indium oxide powder, the indium oxide powder is modified by a high-temperature high-pressure hydrogenation treatment method to prepare hydrogenated indium oxide (H-In) 2 O 3 ) Powder, and the hydrogenation treatment process comprises the following specific steps: weighing 0.5g of indium oxide powder, placing the indium oxide powder into a hydrogenation reaction device, sealing the device, vacuumizing to below 10Pa, heating the device to the hydrogenation temperature of 400 ℃ at a certain heating rate of 5 ℃/min, and starting to fill high-purity hydrogen (the purity is more than 99.999%) into the device under the condition of keeping the set hydrogenation temperature unchanged until the set hydrogen pressure is 1.0 MPa; then carrying out hydrogenation reaction for 24 hours under the conditions of set hydrogenation temperature and set hydrogen pressure; and after the reaction is finished, naturally cooling the device to room temperature, releasing the internal hydrogen pressure, and taking out the sample to prepare the indium hydroxide powder sample.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: under the condition of stirring, adding 20mg of hydrogenated indium oxide powder sample obtained in the step (2) into 2mL of graphene aqueous solution with the concentration of 0.5mg/mL, and carrying out ultrasonic treatment for 3h to obtain uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 5: 100 of the graphene/hydrogenated indium oxide composite photocatalyst.
Example 6:
(1) firstly calcining indium hydroxide powder at high temperaturePreparing to obtain indium oxide (In) 2 O 3 ) The powder comprises the following specific processes: firstly, 7.072g of indium chloride (16.2mmol) is dissolved in a mixed solvent of absolute ethyl alcohol (20mL) and deionized water (60mL) with the volume ratio of 1:3, and the indium chloride solution with the molar concentration of 0.4M is formed after the indium chloride solution is uniformly stirred; meanwhile, 20mL of ammonium hydroxide (28-30%) and 60mL of absolute ethyl alcohol are uniformly mixed to form an ammonium hydroxide solution. Then, quickly adding the prepared ammonium hydroxide solution into the indium chloride solution to generate a white precipitate immediately, and placing the obtained suspension into an oil bath at 80 ℃ to stir for 30 minutes; then taking the suspension out of the oil bath, and naturally cooling to room temperature; centrifuging the suspension at a high speed of 8000r/s, collecting white precipitate, cleaning the precipitate with deionized water and absolute ethyl alcohol, and transferring to a vacuum oven for drying at 60 ℃ for 12 hours to obtain white indium hydroxide powder; finally calcining the obtained indium hydroxide powder In air at 700 ℃ for 5 hours, and naturally cooling to prepare light yellow indium oxide (In) 2 O 3 ) And (3) powder.
(2) Under the premise of obtaining the indium oxide powder, the indium oxide powder is modified by a high-temperature high-pressure hydrogenation treatment method to prepare hydrogenated indium oxide (H-In) 2 O 3 ) Powder, wherein the hydrogenation treatment process comprises the following specific steps: weighing 1.0g of indium oxide powder, putting the indium oxide powder into a hydrogenation reaction device, sealing the device, vacuumizing and pumping to below 10Pa, heating the device to hydrogenation temperature of 300 ℃ at a certain heating rate of 5 ℃/min, and starting to fill high-purity hydrogen (the purity is more than 99.999%) into the device under the condition of keeping the set hydrogenation temperature unchanged until the set hydrogen pressure is 0.5 MPa; then carrying out hydrogenation reaction for 10 hours under the conditions of set hydrogenation temperature and set hydrogen pressure; and after the reaction is finished, naturally cooling the device to room temperature, releasing the internal hydrogen pressure, and taking out the sample to prepare the indium hydroxide powder sample.
(3) In the presence of a catalyst to obtain the above hydrogenated indium oxide (H-In) 2 O 3 ) Under the premise of powder, the graphene/indium oxide hydride composite photocatalyst is prepared by ultrasonic dispersion and a freeze-drying method, and the specific operation flow is as follows: stirring the obtained 40mg indium hydroxide powder of step (2)Adding the final sample into 2mL of graphene aqueous solution with the concentration of 0.8mg/mL, and carrying out ultrasonic treatment for 2h to obtain a uniformly dispersed graphene/indium oxide hydride suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/indium hydroxide suspension to obtain the graphene/indium hydroxide suspension, wherein the mass ratio of the graphene to the indium hydroxide is 4: 100 of the graphene/hydrogenated indium oxide composite photocatalyst.
The photocatalytic performance of the pure indium oxide, hydrogenated indium oxide and graphene/hydrogenated indium oxide composite photocatalyst prepared by the invention is tested by adopting a photocatalytic hydrogen production test system self-made in a laboratory to test the photocatalytic hydrogen production performance by decomposing water, and the specific process and steps are as follows: adding 5mL of deionized water into a 15mL quartz photocatalytic reaction glass tube, taking 1mL of triethanolamine as a sacrificial agent and 5mg of catalyst powder, adding 1 wt% of chloroplatinic acid as a cocatalyst, continuously filling nitrogen into the quartz glass tube for 40 minutes after uniform ultrasonic dispersion to discharge air, then sealing the system, then illuminating the system by taking a white LED lamp as a light source, detecting hydrogen production concentrations in systems at different time periods through a gas chromatograph, obtaining the hydrogen production amount of different samples in photocatalytic decomposition water under the illumination condition, and further calculating the photocatalytic hydrogen production rate.
FIG. 1 shows indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) XRD spectrogram of the composite photocatalyst. As can be seen from the figure, the main diffraction peaks of the samples are basically consistent, and each diffraction peak completely corresponds to a cubic phase indium oxide standard card (JCPDS No.06-0416), which indicates that the main components of the samples are cubic phase indium oxide, and the crystal phase structure of the samples is not changed by hydrogenation modification. Further, graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) Has no obvious diffraction peak of graphene, which is mainly due to graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst has less graphene loading and weaker graphene diffraction peak, so that no obvious diffraction peak exists.
FIG. 2 shows indium (In) oxide (a) prepared In example 1 2 O 3 ) (b) hydrogenated indium oxide(H-In 2 O 3 ) And (c) graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) Transmission Electron Microscopy (TEM) image of the composite photocatalyst. As can be seen from the figure, indium oxide (In) 2 O 3 ) The sample is granular, the size is 20-80 nm, the dispersibility is good, and only a small amount of agglomeration exists; and hydrogenating indium oxide (H-In) 2 O 3 ) Sample morphology and indium oxide (In) 2 O 3 ) Approximately the same, without significant change. From graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst is obviously observed in a transmission electron microscope image, a plurality of nano particles with the particle size of 20-80 nm are uniformly distributed on the surfaces of the two-dimensional nanosheets, and the nano particles and the two-dimensional nanosheets are considered to be indium hydroxide nano particles and graphene two-dimensional nanosheets respectively, so that the indium hydroxide nano particles and the two-dimensional graphene nanosheets are obviously in good heterojunction contact, and the generation, separation and migration processes of photo-generated carriers are facilitated.
FIG. 3 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A Raman spectrum (Raman) spectrum and an electronic paramagnetic resonance spectrum (EPR) spectrum of the composite photocatalyst. As can be seen In FIG. 3a, the sample indium oxide (In) 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst is 307, 366, 495 and 631cm -1 All peak positions appear to be attributed to cubic phase In 2 O 3 Confirming the sample hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The cubic phase In is still remained In the composite photocatalyst 2 O 3 Structure, consistent with XRD results; and graphene/H-In for the sample 2 O 3 ) Composite photocatalyst, 1346 and 1587cm -1 Two Raman characteristic peaks (a D peak and a G peak) belonging to graphene appear at the peak positions, and the sample graphene/indium oxide hydride is proved(graphene/H-In 2 O 3 ) Existence of graphene two-dimensional nanosheets in the composite photocatalyst. As can be seen from the EPR spectrum corresponding to FIG. 3b, the sample indium oxide (In) 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst generates a typical Lorentz characteristic absorption peak curve near a magnetic field g-2.003, the occurrence of the absorption characteristic peak is closely related to the unpaired electron number of an oxygen atom in the oxide, and the existence of an oxygen vacancy defect state structure in the oxide is confirmed; after high-temperature and high-pressure hydrogenation treatment, the EPR characteristic peak intensity of the hydrogenated indium oxide sample is obviously enhanced, which shows that the surface oxygen vacancy defect concentration of the indium oxide sample is greatly increased after the high-temperature and high-pressure hydrogenation treatment; and after the indium hydroxide and the graphene are compounded, the surface oxygen vacancy defect concentration is reduced to a large extent, which shows that the compounding of the graphene is favorable for the stable existence of a surface defect state structure of the indium hydroxide. The EPR result further proves that a large amount of oxygen vacancy defect state structures can be generated on the surface of an indium oxide sample in the high-temperature and high-pressure hydrogenation treatment process, and the stability of the surface defect state structures of hydrogenated indium oxide can be improved to a certain extent by compounding of graphene.
FIG. 4 is the indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) And (3) a solid Diffuse Reflection Spectrum (DRS) spectrum of the composite photocatalyst. As is clear from the figure, indium oxide (In) 2 O 3 ) Has an absorption edge of about 480nm, and indium oxide (H-In) is hydrogenated 2 O 3 ) Has an absorption edge of about 500nm, and graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The absorption edge of the composite photocatalyst is extended to about 650 nm; relative to pure indium oxide (In) 2 O 3 ) Sample, hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst shows relatively obvious spectral absorption performance in the whole visible light region, and the graphene/indium oxide hydride (A), (B) and (C)graphene/H-In 2 O 3 ) The sample had the best visible light absorption properties. The DRS test result shows that the visible light absorption capacity of the indium oxide can be improved by hydrogenation in a mode of generating a surface defect state structure, and the visible light absorption capacity of the hydrogenated indium oxide can be further improved by compounding graphene through the visible light adsorption characteristic of the graphene.
FIGS. 5 and 6 are indium oxide (In) prepared In example 1 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) A photocatalytic hydrogen production activity curve chart of the composite photocatalyst changing along with illumination time under the irradiation of a white light LED lamp and a photocatalytic hydrogen production rate histogram. As can be seen, indium oxide (In) 2 O 3 ) Hydrogenated indium oxide (H-In) 2 O 3 ) And graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) The composite photocatalyst can generate hydrogen through photocatalytic decomposition of water under the irradiation of a white light LED lamp, the hydrogen production amount is sequentially and linearly increased along with the extension of illumination time, and the corresponding photocatalytic hydrogen production rates are respectively 5.3, 32.4 and 86 mu mol/h/g; as can be seen, the photocatalytic hydrogen production rate of the hydrogenated indium oxide is about 6 times of that of pure indium oxide, and graphene/hydrogenated indium oxide (graphene/H-In) 2 O 3 ) The hydrogen production rate of the photocatalytic decomposition water of the composite photocatalyst reaches the maximum, and is about 16 times of the hydrogen production rate of pure indium oxide. The photocatalytic hydrogen production test result shows that the photocatalytic hydrogen production activity can be effectively improved by carrying out hydrogenation modification on indium oxide, and the photocatalytic hydrogen production activity can be further remarkably improved after the indium oxide hydride and graphene are compounded, because the separation and migration processes of photon-generated carriers of an indium oxide sample can be effectively improved in the hydrogenation treatment and graphene compounding processes, the transmission rate of charges on the photon-generated carrier interface is reduced, the carrier density of the sample is improved, and the photocatalytic hydrogen production activity of the indium oxide sample is greatly improved.
FIG. 7 shows (a) hydrogenated indium oxide (H-In) prepared In example 1 2 O 3 ) And (b) graphene/indium oxide hydride (graphene/H-In) 2 O 3 ) Irradiation of composite photocatalyst on white light LED lampAnd (5) testing the stability of the photocatalytic hydrogen production cycle. As can be seen from the figure, the sample is hydrogenated indium oxide (H-In) 2 O 3 ) With the increase of the number of photocatalytic cycles, the photocatalytic hydrogen production activity is correspondingly reduced, which is probably caused by unstable structure of surface oxygen vacancy defects generated by hydrogenation induction; graphene/H-In formed after indium hydroxide and graphene are compounded 2 O 3 ) With the increase of the photocatalytic cycle times, the photocatalytic hydrogen production activity of the composite photocatalyst is basically kept unchanged, and the composite photocatalyst has good photocatalytic stability, so that the photocatalytic stability of indium oxide hydride can be improved to a greater extent through graphene compounding.
Claims (5)
1. The application of the graphene/indium oxide hydride composite photocatalyst is characterized in that the graphene/indium oxide hydride composite photocatalyst is used for photocatalytic decomposition of water to prepare hydrogen;
the graphene/hydrogenated indium oxide composite photocatalyst is prepared by the following technical scheme:
(1) dissolving indium chloride powder in a volume ratio of 3: 1, stirring uniformly to form an indium chloride solution, and simultaneously mixing an ammonium hydroxide aqueous solution with a mass percentage concentration of 28-30% and absolute ethyl alcohol according to a volume ratio of 1:3, uniformly mixing to form an ammonium hydroxide solution; then, quickly adding an ammonium hydroxide solution with the same volume into the indium chloride solution, stirring and mixing to generate a white precipitate immediately, placing the obtained suspension into an 80-DEG oil bath, stirring for 30 minutes, taking out the suspension from the oil bath, and naturally cooling to room temperature; centrifuging the suspension at a high speed to collect precipitates, cleaning the precipitates with deionized water and absolute ethyl alcohol, and then transferring the precipitates to a vacuum oven for drying for 12 hours at 60 ℃ to obtain white indium hydroxide powder; finally calcining the obtained indium hydroxide powder In air at 700 ℃ for 5 hours, and naturally cooling to prepare light yellow indium oxide (In) 2 O 3 ) Powder;
(2) putting 0.5-2.0 g of indium oxide powder prepared in the step (1) into a hydrogenation reaction device, wherein the device is compactSealing, vacuumizing to below 10Pa, heating the device to a set hydrogenation temperature at a certain heating rate, starting to fill high-purity hydrogen with the purity of more than 99.999 percent into the device under the condition of keeping the set hydrogenation temperature unchanged until the set hydrogen pressure is reached, and then carrying out hydrogenation reaction for a period of time under the conditions of the set hydrogenation temperature and the set hydrogen pressure; after the reaction is finished, after the device is naturally cooled to room temperature, releasing the internal hydrogen pressure, and taking out the sample to prepare the hydrogenated indium oxide (H-In) 2 O 3 ) A powder;
(3) dispersing graphene two-dimensional nanosheets in deionized water to prepare a uniformly dispersed graphene aqueous solution; adding the hydrogenated indium oxide powder prepared in the step (2) into a graphene aqueous solution according to a certain mass ratio, and carrying out ultrasonic treatment for a period of time to obtain a uniformly dispersed graphene/hydrogenated indium oxide suspension; and finally, carrying out vacuum freeze-drying treatment on the graphene/hydrogenated indium oxide suspension to obtain the graphene/hydrogenated indium oxide composite photocatalyst.
2. The use of the graphene/indium oxide hydride composite photocatalyst prepared according to claim 1 is characterized in that: the graphene/indium hydroxide composite photocatalyst is formed by uniformly distributing indium hydroxide nanoparticles on a graphene two-dimensional nanosheet, wherein the particle size of the indium hydroxide nanoparticles is 20-80 nm.
3. The use of the graphene/indium oxide hydride composite photocatalyst according to claim 1, wherein: the molar concentration of the indium chloride solution in the step (1) is 0.2-0.5M.
4. The use of the graphene/indium oxide hydride composite photocatalyst according to claim 1, wherein: the temperature rise rate in the step (2) is 5-10 ℃/min, the hydrogenation temperature is 200-400 ℃, the hydrogen pressure is 0.1-1.0 MPa, and the hydrogenation reaction time is 1-24 hours.
5. The use of the graphene/indium oxide hydride composite photocatalyst according to claim 1, wherein: the concentration of the graphene aqueous solution in the step (3) is 0.5-1 mg/mL, the ultrasonic treatment time is 2-4 h, and the mass ratio of graphene to indium hydroxide in the graphene/indium hydroxide suspension is 1: 100-10: 100.
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