CN116422323A - Preparation method of visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst - Google Patents
Preparation method of visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst Download PDFInfo
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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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Abstract
The invention belongs to the technical field of photocatalysis, and discloses a preparation method of a visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst. Adding tetrabutyl titanate, sodium hydroxide and graphene oxide after stirring for the first time, adding rhodium chloride and water, heating an autoclave from room temperature to a reaction temperature, washing and drying after the reaction is completed to obtain graphene oxide/rhodium-strontium titanate precursor powder, annealing to obtain graphene oxide/rhodium-strontium titanate powder, and using the graphene oxide/rhodium-strontium titanate powder for full water decomposition under visible light. According to the invention, by constructing the graphene/strontium titanate heterojunction, the absorption of the strontium titanate to visible light is greatly enhanced, the utilization rate of sunlight is increased, and meanwhile, the conductivity of the strontium titanate is improved, so that the full water decomposition performance of the strontium titanate is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to photocatalysis full water splitting, and in particular relates to a preparation method of a visible light driven graphene oxide/rhodium-strontium titanate composite full water splitting photocatalyst.
Background
Excessive consumption of fossil energy causes serious energy and environmental problems, and simultaneously promotes research on green alternative energy. Hydrogen is recognized as an ideal green energy source because of its low density, high calorific value, easy storage, no toxicity and the like. Meanwhile, the combustion product of the hydrogen gas is only water, and the emission of greenhouse gases is effectively avoided, so that the realization of efficient, clean and low-energy-consumption hydrogen production is significant in the current development. Photocatalytic technology has received considerable attention for its advantages of cleanliness, safety, sustainability and long life. In the photocatalytic system, the photocatalyst is the core of the whole reaction, and plays a decisive role in the whole water separation efficiency. It is well known that suitable ribbon structures are standard for excellent photocatalysts for their ability to absorb and utilize light, their abundant active sites as reaction centers, and their efficient separation of photo-generated charge hole pairs. However, few photocatalysts are able to meet these criteria. Therefore, it is very necessary to study a photocatalyst with high efficiency.
In recent years, strontium titanate (abbreviated as STO) has been widely used in photocatalysis, sensors, dye-sensitized solar cells (DSCC) and supercapacitors because of its excellent characteristics of high dielectric constant, resistance to photochemical corrosion, relatively stable performance, and non-toxicity.
However, there are some disadvantages that the band gap of the strontium titanate catalyst is too wide (3.2 eV), and only ultraviolet light and photo-generated electron-hole pair separation rate can be absorbed and utilized, so that the catalyst has low energy consumption; strontium titanate catalysts have insufficient active sites and often require cocatalysts.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst. Has the advantages of two aspects: 1. through heterostructure construction technology, the graphene oxide and strontium titanate form a heterojunction. 2. The active site modification technology is adopted to modify the catalyst by rhodium metal, so that the active site is increased. By adopting a method combining heterostructure construction technology and active site modification technology, graphene oxide and a traditional ultraviolet light catalyst are combined to form a heterojunction, so that the light response range of a target catalyst is enlarged, and the sunlight utilization rate is improved. The metal is used for modifying the target catalyst, so that the active site of the target catalyst is improved, and the separation and transfer of electrons and holes are promoted. Solves the problems that the strontium titanate catalyst can not absorb and utilize visible light, has low separation rate of photo-generated electron-hole pairs and too few active sites.
The present invention achieves the above technical object by the following means.
A preparation method of a visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst comprises the following steps:
(1) Preparation of graphite oxide by Hummers method
A250 ml reaction bottle is filled in an ice water bath, a proper amount of concentrated sulfuric acid is added, a solid mixture of 2g of graphite powder and 1 g of sodium nitrate is added under stirring, 6 g of potassium permanganate is added for a plurality of times, the reaction temperature is controlled to be not higher than 20 ℃, stirring is carried out for a period of time, then the temperature is raised to about 35 ℃, stirring is continued for 30 minutes, a proper amount of deionized water is slowly added, and after continuous stirring for 20 minutes, a proper amount of hydrogen peroxide solution is added to reduce residual oxidant, so that the solution turns into bright yellow. Filtered while hot and washed with 5% hydrochloric acid solution and deionized water until no sulfate was detected in the filtrate. And finally, placing the filter cake in a vacuum drying oven at 60 ℃ for full drying and preserving for standby.
(2) Preparation of graphene oxide/rhodium-strontium titanate
Firstly, adding strontium chloride and rhodium chloride into a Teflon lining stainless steel autoclave according to a certain proportion, then adding water into the autoclave, adding tetrabutyl titanate after first stirring, then adding sodium hydroxide, adding graphene oxide after second stirring, heating the autoclave from room temperature to a reaction temperature, washing for many times through a centrifugal machine after the reaction is completed, and drying to obtain graphene oxide/rhodium-strontium titanate precursor powder, and finally annealing at a certain temperature to obtain graphene oxide/rhodium-strontium titanate powder.
In the step (2), the dosage proportion of strontium chloride, rhodium chloride, water, tetrabutyl titanate, sodium hydroxide and graphene oxide is 2g:50mg:30mL:3.4mL:0.8g:10-120mg.
In the step (2), the time of the first stirring is 20 minutes, and the time of the second stirring is 30 minutes.
In the step (2), the reaction temperature was 200℃and the reaction time was 24 hours.
In step (2), the drying temperature was 60 ℃.
In the step (2), the annealing temperature is 200 ℃ and the time is 2 hours.
The graphene oxide/rhodium-strontium titanate composite material prepared by the method is used for full water dissolution under visible light.
The beneficial effects of the invention are as follows:
1. according to the invention, by constructing the graphene/strontium titanate heterojunction, the absorption of the strontium titanate to visible light is greatly enhanced, the utilization rate of sunlight is increased, and meanwhile, the conductivity of the strontium titanate is improved, so that the full water decomposition performance of the strontium titanate is improved.
2. According to the invention, rhodium metal is used as an electron acceptor through rhodium metal modification, so that the active site is greatly increased, and the separation and transfer of electrons and holes are promoted, thereby improving the full water decomposition performance of strontium titanate.
The absorption and utilization of the strontium titanate catalyst to visible light are promoted, and the breakthrough of zero total water decomposition performance of the strontium titanate catalyst under visible light is realized.
Drawings
FIG. 1 shows the full water splitting performance of each substance under visible light, (a) shows the full water splitting performance of strontium titanate monomer, graphene oxide/strontium titanate, graphene oxide/rhodium-strontium titanate of example 2 under visible light (lambda is more than or equal to 420 nm), and (b) shows the full water splitting performance of graphene oxide/rhodium-strontium titanate prepared by different graphene oxide addition amounts under visible light (lambda is more than or equal to 420 nm).
In fig. 2, (c) is an XRD pattern of graphene oxide, strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2, and (d) is an XPS pattern of graphene oxide/rhodium-strontium titanate of example 2.
Fig. 3 is SEM, TEM, HRTEM and EDS mapping diagrams of graphene oxide/rhodium-strontium titanate of example 2.
Fig. 4 (f) is a raman diagram of graphene oxide, strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2, and (g) is an impedance diagram of strontium titanate, graphene oxide/strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2.
Fig. 5 (h) shows the photoelectric flow diagrams of strontium titanate, graphene oxide/strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2, and (i) shows the LSV graphs of strontium titanate, graphene oxide/strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2.
Fig. 6 (j) shows solid uv-vis absorption graphs of graphene oxide, strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2, (k) shows steady-state fluorescence graphs of strontium titanate, graphene oxide/strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2, and (l) shows transient fluorescence graphs of strontium titanate, graphene oxide/strontium titanate, and graphene oxide/rhodium-strontium titanate of example 2.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
EXAMPLE 1.1% graphene oxide/rhodium-strontium titanate (1% GO/Rh-STO)
2g of strontium chloride, 50mg of rhodium chloride were added to a Teflon lined stainless steel autoclave (50 ml). Then 30ml of water was added to the autoclave. After stirring for 20 minutes, 3.4ml of tetrabutyl titanate and then 0.8g of sodium hydroxide were added. After stirring for 30 minutes, 20mg of graphene oxide was added. Thereafter, the autoclave was heated from room temperature to 200℃and maintained for 24 hours. After the reaction is completed, washing for a plurality of times by a centrifugal machine, and drying at 60 ℃ to obtain graphene oxide/rhodium-strontium titanate precursor powder. Finally, annealing for 2 hours in the environment of 200 ℃ to obtain graphene oxide/rhodium-strontium titanate powder.
0.1 g of the catalyst is dispersed in 100 ml of water, the water is transferred into a 300 ml quartz photocatalysis reactor, the reactor is connected with a photocatalysis activity evaluation system (medium teaching gold source CEL-PAEM-D8), the system is vacuumized, the temperature of the reaction system is maintained by constant temperature circulating water (6 ℃), and the water is decomposed into hydrogen and oxygen under the irradiation of a xenon lamp with a filter (lambda is larger than or equal to 420nm and 300W xenon lamp).
EXAMPLE 2.2% graphene oxide/rhodium-strontium titanate (2% GO/Rh-STO)
2g of strontium chloride, 50mg of rhodium chloride were added to a Teflon lined stainless steel autoclave (50 ml). Then 30ml of water was added to the autoclave. After stirring for 20 minutes, 3.4ml of tetrabutyl titanate and then 0.8g of sodium hydroxide were added. After stirring for 30 minutes, 40 mg of graphene oxide was added. Thereafter, the autoclave was heated from room temperature to 200℃and maintained for 24 hours. After the reaction is completed, washing for a plurality of times by a centrifugal machine, and drying at 60 ℃ to obtain graphene oxide/rhodium-strontium titanate precursor powder. Finally, annealing for 2 hours in the environment of 200 ℃ to obtain graphene oxide/rhodium-strontium titanate powder.
0.1 g of the catalyst is dispersed in 100 ml of water, the water is transferred into a 300 ml quartz photocatalysis reactor, the reactor is connected with a photocatalysis activity evaluation system (medium teaching gold source CEL-PAEM-D8), the system is vacuumized, the temperature of the reaction system is maintained by constant temperature circulating water (6 ℃), and the water is decomposed into hydrogen and oxygen under the irradiation of a xenon lamp with a filter (lambda is larger than or equal to 420nm and 300W xenon lamp).
EXAMPLE 3.4% graphene oxide/rhodium-strontium titanate (4% GO/Rh-STO)
2g of strontium chloride, 50mg of rhodium chloride were added to a Teflon lined stainless steel autoclave (50 ml). Then 30ml of water was added to the autoclave. After stirring for 20 minutes, 3.4ml of tetrabutyl titanate and then 0.8g of sodium hydroxide were added. After stirring for 30 minutes, 80 mg of graphene oxide was added. Thereafter, the autoclave was heated from room temperature to 200℃and maintained for 24 hours. After the reaction is completed, washing for a plurality of times by a centrifugal machine, and drying at 60 ℃ to obtain graphene oxide/rhodium-strontium titanate precursor powder. Finally, annealing for 2 hours in the environment of 200 ℃ to obtain graphene oxide/rhodium-strontium titanate powder.
0.1 g of the catalyst is dispersed in 100 ml of water, the water is transferred into a 300 ml quartz photocatalysis reactor, the reactor is connected with a photocatalysis activity evaluation system (medium teaching gold source CEL-PAEM-D8), the system is vacuumized, the temperature of the reaction system is maintained by constant temperature circulating water (6 ℃), and the water is decomposed into hydrogen and oxygen under the irradiation of a xenon lamp with a filter (lambda is larger than or equal to 420nm and 300W xenon lamp).
EXAMPLE 4.6% graphene oxide/rhodium-strontium titanate (6% GO/Rh-STO)
2g of strontium chloride, 50mg of rhodium chloride were added to a Teflon lined stainless steel autoclave (50 ml). Then 30ml of water was added to the autoclave. After stirring for 20 minutes, 3.4ml of tetrabutyl titanate and then 0.8g of sodium hydroxide were added. After stirring for 30 minutes, 120mg of graphene oxide was added. Thereafter, the autoclave was heated from room temperature to 200℃and maintained for 24 hours. After the reaction is completed, washing for a plurality of times by a centrifugal machine, and drying at 60 ℃ to obtain graphene oxide/rhodium-strontium titanate precursor powder. Finally, annealing for 2 hours in the environment of 200 ℃ to obtain graphene oxide/rhodium-strontium titanate powder.
0.1 g of the catalyst is dispersed in 100 ml of water, the water is transferred into a 300 ml quartz photocatalysis reactor, the reactor is connected with a photocatalysis activity evaluation system (medium teaching gold source CEL-PAEM-D8), the system is vacuumized, the temperature of the reaction system is maintained by constant temperature circulating water (6 ℃), and the water is decomposed into hydrogen and oxygen under the irradiation of a xenon lamp with a filter (lambda is larger than or equal to 420nm and 300W xenon lamp).
First, a full water splitting performance test was performed on a photocatalyst sample in an aqueous solution, as shown in fig. 1. As shown in FIG. (a), pure STO does not completely decompose water under visible light (lambda. Gtoreq.420 nm) because it can only absorb and utilize ultraviolet light. However, the overall water splitting of the GO/STO heterostructure can work under visible light. The optimal GO/Rh-STO nanocomposite material shows excellent photocatalytic overall water splitting performance, and H under visible light (lambda is more than or equal to 420 nm) 2 The rate of formation was 55.83. Mu. Mol g -1 ·h -1 ，O 2 The rate of formation was 23.26. Mu. Mol g -1 ·h -1 It is demonstrated that the construction of heterostructures and modification of Rh metal active sites enhance the visible light utilization and photocatalytic performance of STO. As shown in panel (b), H of GO/Rh-STO sample 2 And O 2 The rate of formation increases with the amount of GOThe possible reason for the increase and then decrease is that excess GO reduces the active sites to which the STO is exposed, resulting in a decrease in overall water splitting rate. Notably, the 2% GO/Rh-STO photocatalyst showed the highest H under visible light (lambda. Gtoreq.420 nm) 2 Production Rate (55.83. Mu. Mol. G) -1 ·h -1 ) And O 2 Rate of formation (23.26. Mu. Mol. G) -1 ·h -2 )。
In FIG. 2, as shown in FIG. (c), STO nanoplatelets exhibit good crystallinity with diffraction peaks corresponding to the (100), (110), (111), (200), (211) and (220) planes of the STO structure, respectively, which peaks are characteristic of STO and are consistent with JCPDS card No.35-0734[34 ]. The XRD pattern of the STO nanoplatelets has distinct and very sharp peaks, indicating good crystal structure development. The XRD pattern of GO shows a strong and sharp peak centered at 2θ=10.40, which corresponds to the interplanar spacing of GO sheets. The observed 2 theta of GO can be attributed to the (001) reflecting surface, which is generally determined by the synthesis process of GO and the number of water layers in the crystal plane space [35] [36]. As is evident from the XRD pattern of GO/Rh-STO, the strong peaks of GO have been significantly reduced, indicating that the aggregation of GO sheets has been significantly reduced. Characteristic GO and STO diffraction peaks can be clearly seen in the XRD spectrum of the GO/Rh-STO nanocomposite, which demonstrates the uniform presence of GO and STO nanoplatelets in the nanocomposite. Thus, XRD studies established successful synthesis of STO and GO/Rh-STO nanocomposites. Panel (d) is an XPS full spectrum of the GO/Rh-STO sample, showing characteristic peaks of Ti, sr, rh, C and O elements, indicating successful preparation of GO/Rh-STO. The microstructure and morphological characteristics of the prepared catalyst were analyzed by SEM, TEM, HRTEM and EDS maps.
In fig. 3, panel (e) shows SEM and TEM images of GO/Rh-STO heterostructures showing GO-encapsulated STO nanoparticles. HRTEM images of the GO/Rh-STO heterostructure show the heterostructure interface between GO and STO, confirming the formation of the GO/Rh-STO heterojunction. Furthermore, the clean lattice space of 0.223nm matches well with the (111) plane of the STO and the lattice of the STO is not visible in the GO-wrapped region. Furthermore, HAADF and EDS pattern images showed all elements of Sr, ti, O, rh and C in the GO/Rh-STO composite catalyst, which further confirmed the formation of the GO/Rh STO composite catalyst. The above results confirm the formation of GO/Rh-STO heterostructures and Rh metal active sites.
In FIG. 4, as in FIG. (f), the molecular framework structure of the sample was further analyzed using Fourier transform infrared (FT-IR) spectroscopy. For GO, at 3395cm -1 The broad absorption peak near the position comes from the telescopic vibration absorption peak of O-H, at 1716cm -1 The absorption peak occurring near the position is derived from the telescopic vibration absorption peak of c=o at 1572cm -1 Characteristic absorption peaks of water appear near the location, at 1226cm -1 The absorption peak occurring near the position comes from the telescopic vibration absorption peak of c—o. After the GO and the STO are compounded, 3395cm and 1057cm of GO -1 Intensity of corresponding peak is reduced by 1716cm -1 The peak at disappeared, indicating that GO was reduced to graphene during the hydrothermal reaction. The graph (g) shows Electrochemical Impedance Spectroscopy (EIS), and it can be seen that the arc radius of the EIS of the GO/Rh-STO sample is significantly smaller than that of the pure STO, which indicates that the former has lower interface transmission resistance than the latter, and is more favorable for the transmission and separation of carriers.
In fig. 5, graph (h) shows photocurrent responses of the prepared STO, GO/STO and GO/Rh-STO heterostructures, which all exhibit stable photocurrent signals over 6 periods. Notably, the photocurrent intensity of the GO/Rh-STO samples was stronger than that of pure STO and GO/STO, indicating that GO/STO heterostructures and Rh active site modifications have better charge-hole pair separation. As shown in the graph (i), the Linear Sweep Voltammetry (LSV) showed a current density of 10mA cm -2 When the over potential (0.85V) of the GO/Rh-STO is smaller than that of the pure STO (0.89V) and the GO/ST (0.86V), the construction of a heterostructure and the modification of an active site show that the electron transmission barrier of the STO interface is effectively reduced, and the photocatalytic full water-splitting capacity is further improved.
In FIG. 6, as shown in FIG. (j), the UV-vis DRS of pure STO shows an absorption edge at 385nm, and surprisingly the GO/STO photocatalyst has a much higher absorption capacity for visible light than pure STO.
To further study the carrier transport capacity and separation efficiency of the photocatalyst sample, PL spectra and TS-PL decay were performed on the sameAnd (5) subtracting the test. Graph (k) shows the PL emission spectrum of the photocatalyst sample at 480nm at 385nm excitation wavelength, with a significant decrease in fluorescence intensity compared to STO for the GO/Rh-STO sample, meaning that the photogenerated carrier separation efficiency of the latter is much higher than STO. This is because the construction of the heterostructure promotes electron transfer and electron trapping by the Rh metal atom to effectively suppress photo-generated electron-hole recombination. FIG. 1 shows the results of STO, GO/STO and GO/Rh-STO samples at lambda ex =385 nm and λ em Transient fluorescence decay curve for conditions of 480nm and fluorescence lifetime obtained by double exponential fitting. As can be seen from the figure, the average decay life of the GO/STO sample (1.6 ns) and the GO/Rh-STO sample (1.9 ns) is longer compared to the pure STO (1.1 ns), which further demonstrates that the separation and transfer efficiency of the photo-generated carriers are promoted, which is beneficial for improving the photo-catalytic performance.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (7)
1. The preparation method of the visible light driven graphene oxide/rhodium-strontium titanate composite full-hydrolysis photocatalyst is characterized by comprising the following steps of:
(1) Preparing graphite oxide by adopting a Hummers method for standby;
(2) Preparation of graphene oxide/rhodium-strontium titanate:
firstly, adding strontium chloride and rhodium chloride into a Teflon lining stainless steel autoclave according to a certain proportion, then adding water into the autoclave, adding tetrabutyl titanate after first stirring, then adding sodium hydroxide, adding graphene oxide after second stirring, heating the autoclave from room temperature to a reaction temperature, washing for many times through a centrifugal machine after the reaction is completed, and drying to obtain graphene oxide/rhodium-strontium titanate precursor powder, and finally annealing at a certain temperature to obtain graphene oxide/rhodium-strontium titanate powder.
2. The method according to claim 1, wherein in the step (2), the dosage ratio of strontium chloride, rhodium chloride, water, tetrabutyl titanate, sodium hydroxide and graphene oxide is 2g:50mg:30mL:3.4mL:0.8g:10-120mg.
3. The method according to claim 1, wherein in the step (2), the time of the first stirring is 20 minutes and the time of the second stirring is 30 minutes.
4. The process according to claim 1, wherein in step (2), the reaction temperature is 200℃and the reaction time is 24 hours.
5. The process according to claim 1, wherein in step (2), the drying temperature is 60 ℃.
6. The method according to claim 1, wherein in the step (2), the annealing temperature is 200℃and the time is 2 hours.
7. Use of the graphene oxide/rhodium-strontium titanate powder produced by the production method according to any one of claims 1 to 6 for full water decomposition under visible light.
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