CN115090290A - Co-based bimetallic oxide loaded GQDs composite photocatalyst and preparation method and application thereof - Google Patents
Co-based bimetallic oxide loaded GQDs composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
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- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000967 suction filtration Methods 0.000 claims description 22
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
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- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 5
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 5
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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Abstract
The invention provides a Co-based bimetallic oxide loaded GQDs composite photocatalyst as well as a preparation method and application thereof, belonging to the technical field of photocatalytic materials. According to the method, a Co-based bimetallic oxide and a C-source small molecular substance are taken as synthesis raw materials, the Co-based bimetallic oxide and the C-source small molecular substance are coupled under a high-temperature environment by adopting a one-step solvothermal method, and Graphene Quantum Dots (GQDs) are successfully synthesized and loaded on the surface of the Co-based bimetallic oxide in situ. The whole preparation process does not need strong acid oxidant participation, does not need post-treatment such as dialysis and the like to remove non-carbon impurities, has simple preparation steps, cheap and easily obtained synthetic raw materials, and green and environment-friendly synthesis mode. The composite photocatalyst prepared by the invention has stronger photocatalytic activity and stability, and can be applied to the fields of hydrogen production by decomposing water under visible light, organic pollutant degradation, carbon dioxide reduction and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a Co-based bimetallic oxide loaded GQDs composite photocatalyst as well as a preparation method and application thereof.
Background
The photocatalysis technology can convert solar energy into chemical energy such as hydrogen energy and the like through photoelectric conversion, and has good application prospect. The photocatalysis technology is an environment-friendly technology which is green and energy-saving, and the participation of a semiconductor catalysis material is indispensable in the process of generating hydrogen by decomposing water through photocatalysis.
Currently, the semiconductor catalytic materials that have been studied for use are carbon materials, metal oxides, metal sulfides, graphite phase nitrogen carbides, double metal hydroxides, and the like. The Graphene Quantum Dots (GQDs) have the advantages of good dispersibility, capability of providing more abundant active sites and the like. The most extensive preparation method of the Graphene Quantum Dots (GQDs) is a Hummers method, namely, in the reaction process, a powdery carbon material is mixed with strong acid and strong oxidant, the carbon material is oxidized into Graphene (GO) under the action of the strong oxidant, then the graphene is further oxidized and cut in size to finally obtain the GQDs, and the non-carbon impurities are removed through post-treatment such as dialysis. However, in the preparation process of the method, strong acid and strong oxidizer such as sulfuric acid and potassium permanganate are needed, the experimental conditions are harsh, the time consumption is long, and the non-carbon impurities are removed by post-treatment such as dialysis, and the preparation process is very complicated.
Bimetallic oxides, such as Co-based bimetallic oxides, have unique surface properties, and have the advantages of catalytic active sites, higher electrical conductivity, less environmental hazard, and the like. However, the Co-based bimetallic oxide material is limited by its own energy band structure, and its spectral response range is narrow, so that it cannot fully utilize the visible light with a large proportion in solar energy, resulting in low photocatalytic hydrogen production activity and low stability.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a Co-based bimetallic oxide supported GQDs composite photocatalyst, which is prepared by adopting a one-step solvothermal method to enable Co-based bimetallic oxide (MCo) 2 O 4 ) Reacts with C-source micromolecular substances, successfully synthesizes and in-situ loads Graphene Quantum Dots (GQDs) on the surface of Co-based bimetallic oxide, and prepares the graphene quantum dotsThe process is simple, convenient and environment-friendly.
The invention also provides a Co-based bimetallic oxide loaded GQDs composite photocatalyst prepared by the preparation method, and the composite photocatalyst has stronger photocatalytic activity and higher stability.
The invention also provides an application of the Co-based bimetallic oxide loaded GQDs composite photocatalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a Co-based bimetallic oxide loaded GQDs composite photocatalyst comprises the following steps:
(1) preparation of Co-based bimetallic oxide (MCo) 2 O 4 ): dissolving a predetermined amount of cobalt salt, oxysalt of metal M and urea in deionized water, performing ultrasonic treatment, stirring and mixing uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting at 150-220 ℃ for 4-8h, performing suction filtration after the reaction is finished, drying and grinding the precipitate obtained by suction filtration to obtain powdered MCo 2 O 4 A precursor; mixing powdered MCo 2 O 4 The precursor is put into a tube furnace for calcination to obtain MCo 2 O 4 (ii) a Wherein, the metal M is one of Ni, Fe and Mn;
(2) synthesized Co-based bimetallic oxide supported GQDs composite photocatalyst (MCo) 2 O 4 /GQDs): MCo prepared in the step (1) 2 O 4 Mixing with C source small molecular substance at a predetermined ratio, transferring into a reaction kettle with polytetrafluoroethylene lining, reacting at 150-240 deg.C for 4-8h, vacuum filtering, oven drying the precipitate, and grinding to obtain powdered MCo 2 O 4 /GQDs。
Preferably, in the step (1), the cobalt salt is selected from one of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate.
Preferably, in the step (1), the oxysalt of the metal M is selected from one of nickel nitrate hexahydrate, manganese acetate tetrahydrate, and ferric nitrite hexahydrate.
Preferably, in the step (1), the cobalt salt, the oxysalt of the metal M, and the urea account for 30% -50%, 30% -70%, and 0% -30% of the total solute of the mixed solution, respectively.
Preferably, in the step (1), the temperature rise rate of the tube furnace is 2-3 ℃/min, the temperature is 400-.
Preferably, in the step (2), the MCo 2 O 4 And C source small molecular substance in a mass ratio of 1: (0.5-1.5), wherein the C source small molecular substance is selected from one of citric acid, starch and glucose.
The Co-based bimetallic oxide supported GQDs composite photocatalyst prepared by the preparation method.
An application of the Co-based bimetallic oxide loaded GQDs composite photocatalyst in water decomposition and hydrogen production under visible light.
An application of the Co-based bimetallic oxide loaded GQDs composite photocatalyst in degrading organic pollutants under visible light.
An application of the Co-based bimetallic oxide loaded GQDs composite photocatalyst in catalytic reduction of carbon dioxide under visible light.
Compared with the prior art, the invention has the beneficial effects that: the invention is Co-based bimetallic oxide (MCo) 2 O 4 ) And C source small molecular substance as synthetic raw material, and making Co-base bimetal oxide (MCo) by adopting one-step solvothermal method under high-temperature environment 2 O 4 ) And coupling with C-source small molecular substances, and successfully synthesizing and in-situ loading Graphene Quantum Dots (GQDs) on the surface of the Co-based bimetallic oxide. The whole preparation process does not need strong acid oxidant participation, does not need post-treatment such as dialysis and the like to remove non-carbon impurities, has simple preparation steps, cheap and easily obtained synthetic raw materials, green and environment-friendly synthesis mode and no pollution to the environment.
Composite photocatalyst MCo prepared by the preparation method of the invention 2 O 4 /GQDs and Co-based bimetallic oxides (MCo) 2 O 4 ) In contrast, it has a larger specific surface area and can provide more reactive sites, at MCo 2 O 4 Upper uniform loadAfter 10-20nm of GQDs, MCo is ensured due to the photosensitivity of the GQDs nano-particles 2 O 4 Under the irradiation of visible light, GQDs passes through GQDs and Co-based bimetallic oxide (MCo) 2 O 4 ) Due to the synergistic effect of the GQDs and the Co-based bimetallic oxide (MCo2O4), the close contact between the GQDs and the Co-based bimetallic oxide is beneficial to shortening the transfer path of electrons, so that the speed of electron transfer is accelerated, and the catalytic activity and the stability of the composite photocatalyst are improved. The visible light catalytic hydrogen production experiment and the circulation stability determination experiment prove that the composite photocatalyst MCo 2 O 4 the/GQDs have strong photocatalytic activity and stability, and can be applied to the fields of hydrogen production by decomposing water under visible light, organic pollutant degradation, carbon dioxide reduction and the like.
Drawings
FIG. 1 shows a composite photocatalyst MCo 2 O 4 XPS and XRD test results of/GQDs.
FIG. 2 shows a composite photocatalyst MCo 2 O 4 GQDs and MCo 2 O 4 Scanning Electron Microscope (SEM) comparison of (a).
FIG. 3 shows a composite photocatalyst MCo 2 O 4 The photocatalytic hydrogen production effect of GQDs under visible light is shown in the figure.
Detailed Description
The technical solutions and effects of the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings of the present invention.
The invention provides a preparation method of a Co-based bimetallic oxide loaded GQDs composite photocatalyst, which comprises the following steps:
(1) preparation of Co-based bimetallic oxide (MCo) 2 O 4 ): dissolving a predetermined amount of cobalt salt, oxysalt of metal M and urea in deionized water, performing ultrasonic treatment, stirring and mixing uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting at 150-220 ℃ for 4-8h, performing suction filtration after the reaction is finished, drying and grinding the precipitate obtained by suction filtration to obtain powdered MCo 2 O 4 A precursor; mixing the powderMCo (g) 2 O 4 The precursor is put into a tube furnace for calcination to obtain MCo 2 O 4 (ii) a Wherein, the metal M is one of Ni, Fe and Mn;
(2) synthesized Co-based bimetallic oxide supported GQDs composite photocatalyst (MCo) 2 O 4 /GQDs): MCo prepared in the step (1) 2 O 4 Mixing with C source small molecular substance at a predetermined ratio, transferring into a reaction kettle with polytetrafluoroethylene lining, reacting at 150-240 deg.C for 4-8h, vacuum filtering, oven drying the precipitate, and grinding to obtain powdered MCo 2 O 4 /GQDs。
During the reaction, MCo 2 O 4 The graphene quantum dots are coupled with C-source micromolecule substances, C can be formed after the C-source micromolecule substances are dehydrated, so that a basic skeleton of the graphene quantum dots can be formed, and GQDs particles are synthesized and loaded at MCo in situ 2 O 4 A surface. During the preparation, the reactant is MCo 2 O 4 With C source micromolecule substance, strong acid oxidant is not needed, and post-treatment such as dialysis is not needed to remove non-carbon impurities, the preparation steps are simple, the synthesis mode is green and environment-friendly, and no pollution is caused to the environment.
Further, in the step (1), the cobalt salt is selected from one of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate.
Further, in the step (1), the oxysalt of the metal M is selected from one of nickel nitrate hexahydrate, manganese acetate tetrahydrate, and iron nitrite hexahydrate.
Further, in the step (1), the cobalt salt, the oxysalt of the metal M, and the urea account for 30% -50%, 30% -70%, and 0% -30% of the total solute of the mixed solution, respectively.
Further, in the step (1), the temperature rise rate of the tubular furnace is 2-3 ℃/min, the temperature is 400-.
Further, in the step (2), the MCo 2 O 4 And C source small molecular substance in a mass ratio of 1: (0.5-1.5), wherein the C source small molecule substance is selected from citric acid and starchPowder and glucose.
1. The preparation examples are as follows;
example 1
Weighing 1mmol of nickel nitrate hexahydrate and 1mmol of cobalt nitrate hexahydrate, dissolving the nickel nitrate hexahydrate and the 1mmol of cobalt nitrate hexahydrate in 20mL of deionized water, weighing 3mmol of urea, adding the urea into the deionized water, performing ultrasonic treatment and stirring to mix uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting for 6 hours at 180 ℃, performing suction filtration after the reaction is finished, drying and grinding a precipitate obtained by the suction filtration to obtain a powdery Co-based bimetallic oxide precursor, putting the powdery Co-based bimetallic oxide precursor into a tubular furnace, controlling the heating rate to be 3 ℃/min, and calcining for 3 hours at 400 ℃ to obtain the Co-based bimetallic oxide (NiCo-based bimetallic oxide) 2 O 4 ) (ii) a Mixing the prepared Co-based bimetallic oxide and citric acid according to the mass ratio of 1: 1, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 200 ℃, performing suction filtration after the reaction is finished, drying and grinding the precipitate obtained by suction filtration to obtain the Co-based bimetallic oxide supported GQDs composite photocatalyst (NiCo) 2 O 4 /GQDs)。
Example 2
Weighing 1mmol of nickel nitrate hexahydrate and 1mmol of cobalt nitrate hexahydrate, dissolving in 20mL of deionized water, weighing 3mmol of urea, adding into the deionized water, performing ultrasonic treatment, stirring and mixing uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting for 8h at 160 ℃, performing suction filtration after the reaction is finished, drying and grinding a precipitate obtained by the suction filtration to obtain a powdery Co-based bimetallic oxide precursor, putting the powdery Co-based bimetallic oxide precursor into a tubular furnace, controlling the heating rate to be 3 ℃/min, and calcining for 3h at 400 ℃ to obtain the Co-based bimetallic oxide (NiCo) 2 O 4 ) (ii) a Mixing the prepared Co-based bimetallic oxide and citric acid according to the mass ratio of 1: 1, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, reacting for 7 hours at 190 ℃, performing suction filtration after the reaction is finished, drying and grinding the precipitate obtained by suction filtration to obtain the Co-based bimetallic oxide supported GQDs composite photocatalyst (NiCo) 2 O 4 /GQDs)。
Example 3
Weighing 1g of manganese acetate tetrahydrate and 1g of cobalt acetate tetrahydrate, dissolving the manganese acetate tetrahydrate and the 1g of cobalt acetate tetrahydrate in 70mL of ethylene glycol, then weighing 0.6g of urea, adding the urea into deionized water, carrying out ultrasonic treatment and stirring uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting for 18h at 180 ℃, carrying out suction filtration after the reaction is finished, drying and grinding a precipitate obtained by suction filtration to obtain a powdery Co-based bimetallic oxide precursor, putting the Co-based bimetallic oxide precursor into a tubular furnace, controlling the heating rate to be 3 ℃/min, and calcining for 2h at 400 ℃ to obtain the Co-based bimetallic oxide (MnCo-based bimetallic oxide) 2 O 4 ) (ii) a Mixing the prepared Co-based bimetallic oxide and starch according to the mass ratio of 1: 1, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 200 ℃, performing suction filtration after the reaction is finished, drying and grinding precipitates obtained by suction filtration to obtain the Co-based bimetallic oxide loaded GQDs composite photocatalyst (MnCo) 2 O 4 /GQDs)。
Example 4
Weighing 0.5g of cobalt nitrate hexahydrate and 1g of ferric nitrite hexahydrate, dissolving in 100mL of deionized water, performing ultrasonic treatment and stirring to uniformly mix to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting for 20h at 160 ℃, performing suction filtration after the reaction is finished, drying and grinding a precipitate obtained by suction filtration to obtain a powdery Co-based bimetal oxide precursor, putting the Co-based bimetal oxide precursor into a tubular furnace, controlling the temperature rise rate to be 2 ℃/min, and calcining for 6h at 450 ℃ to obtain the Co-based bimetal oxide (FeCo-based bimetal oxide) 2 O 4 ) (ii) a Mixing the prepared Co-based bimetallic oxide and citric acid according to the mass ratio of 1: 1, transferring the mixture into a reaction kettle, reacting for 6 hours at 200 ℃, performing suction filtration after the reaction is finished, drying and grinding a precipitate obtained by suction filtration to obtain the Co-based bimetallic oxide supported GQDs composite photocatalyst (FeCo) 2 O 4 /GQD s)。
2. Characterization experiment
X-ray photoelectron spectroscopy (XPS) of different photocatalysts was tested by Kratos Axis Ultra DLD (Al K α); the crystal phase structure of the composite photocatalyst is tested by X-ray diffraction (XRD); the topographical features (SE M) of the different photocatalysts were tested by a thermal field emission scanning electron microscope integrated system (SIGMA 500).
As shown in FIG. 1, (a) in FIG. 1 is MCo 2 O 4 XPS survey of/GQDs (M ═ Ni, Mn, Fe); (b) is NiCo 2 O 4 And NiCo 2 O 4 C1s contrast plot for/GQDs; (c) is NiCo 2 O 4 A fine map of Ni 2p of (a); (d) is NiCo 2 O 4 Fine map of Co 2p of (a); (e) is NiCo 2 O 4 Fine map sum of O1s of (a); (f) is NiCo 2 O 4 And NiCo 2 O 4 XRD diffraction pattern of/GQDs.
Composite photocatalyst MCo for different lights 2 O 4 XPS test was performed on/GQDs (M ═ Ni, Mn, Fe), and the results showed MCo by full spectrum analysis of each photo-composite photocatalyst (FIG. 1(a)) 2 O 4 Successful preparation of/GQDs (M ═ Ni, Mn, Fe). As can be seen from fig. 1(b), the Graphene Quantum Dots (GQDs) are mainly formed by sp2 hybridized carbon atoms, wherein one part of the main peak at 284.8eV is used for data-corrected contaminated carbon, and the other part is C ═ C bond belonging to GQDs, and NiCo 2 O 4 Peak area of/GQDs at 284.8eV with NiCo 2 O 4 The relative ratio is enhanced, and the successful preparation of GQDs is proved. Through the fine spectrogram analysis of C, the change of binding energy shift appears, and the success of in-situ loading of GQ Ds to the bimetallic oxide NiCo in a one-step hydrothermal mode can be further explained 2 O 4 The two produce stronger interaction. As is clear from FIG. 1(c), the diffraction peaks appearing in the fine spectrum of Ni 2p correspond to Ni 2+ (854.05eV,871.30eV) and Ni 3+ (861.7eV,877.8 eV); as is clear from FIG. 1(d), the diffraction peaks obtained by fine analysis of Co 2p correspond to Co 2+ (780.5eV,799.7eV) and Co 3+ (779.16eV,794,4eV), confirming that both exist in the form of mixed valence (+2, + 3); meanwhile, as shown in FIG. 1(e), when the fine pattern of O1s was analyzed, it was found that surface chemisorption of oxygen corresponded to a binding energy of 531.7 eV. As can be seen from FIG. 1(f), the first and second electrodes are formed byNiCo 2 O 4 And NiCo 2 O 4 XRD test on/GQDs, NiCo 2 O 4 Diffraction peaks at about 2 θ -31.1 °, 36.7 °, 44.6 °, 59.1 ° and 65.0 °, matching NiCo 2 O 4 The cubic phase (JCPDS #20-781) further confirms the successful preparation of the composite photocatalyst. No diffraction peak belonging to GQDs is found in the composite photocatalyst because the diffraction peak of the GQDs is not obvious, which indicates that the addition of the GQDs cannot be applied to NiCo 2 O 4 The crystal form characteristics of (a) have an influence.
By the pair of composite photocatalyst MCo 2 O 4 The morphology characteristics of the GQDs (M ═ Ni, Mn and Fe) are analyzed, and the successful loading of the GQDs in MCo can be further explained 2 O 4 The above. Referring to FIG. 2, in FIG. 2 (a) is NiCo 2 O 4 The (b) is NiCo 2 O 4 The morphology of/GQDs is shown in the specification, and (c) is FeCo 2 O 4 The (d) is FeCo 2 O 4 The morphology characteristic diagram of GQDs. As can be seen in connection with FIGS. 2 (a) - (b), NiCo 2 O 4 In the form of a lamellar structure in NiCo 2 O 4 The sheet structure is loaded with a plurality of GQDs particles with the particle size of 10-20 nm. As can be seen in conjunction with (c) - (d) of FIG. 2, FeCo 2 O 4 Presents a smooth rod-shaped structure, and has a relatively uniform GQDs loading 10-20nm on FeCo 2 O 4 A rod-shaped structure.
From the XPS, XRD and SEM analyses of the different samples prepared in the above examples, it can be seen that the graphene quantum dots are successfully synthesized and loaded in situ on the Co-based bimetallic oxide by the one-step solvothermal method, and the two substances are in intimate contact, indicating that the photo-composite catalyst MCo 2 O 4 the/GQDs are successfully prepared.
3. Test on the Activity of composite photocatalyst
Photocatalytic hydrogen production experiment and circulation stability determination
The photocatalytic hydrogen production experiment is carried out in a multi-channel photocatalytic reaction system, and a light source is a 5W LED lamp. 10mg of the photo-composite catalyst MCo 2 O 4 PerGQDs, 20mg of Eosin (EY) and 30mL of Triethanolamine (TEOA) in water (10%, v/v%) were addedIn a quartz reaction flask, after sonication, stirring and nitrogen displacement, gas chromatography (Ruili SP-2100a,13X molecular sieves, TCD, N) was used 2 Carrier gas) was quantitatively analyzed for hydrogen gas generated in the reaction flask.
Referring to FIG. 3, MCo is shown in FIG. 3(a) 2 O 4 Hydrogen production comparison diagram of/GQDs (M ═ Ni, Mn, Fe), (b) NiCo 2 O 4 The cyclic hydrogen production result of GQDs. The following conclusions can be clearly drawn from fig. 3 (a): at MC o 2 O 4 When GQDs is supported on (M ═ Ni, Mn, Fe), the activity of the photocatalyst is greatly improved. It can be seen that when in FeCo 2 O 4 After GQDs are loaded, the hydrogen yield is increased from 19 mu mol to 106 mu mol through the irradiation of visible light for 5 h; MnCo 2 O 4 After GQDs are loaded, the hydrogen yield is increased from 12 mu mol to 82 mu mol through the irradiation of visible light for 5 h; NiCo 2 O 4 After GQDs are loaded, the hydrogen yield is increased from 91 mu mol to 300 mu mol by irradiation of visible light for 5 h. Experiments prove that GQDs are synthesized and loaded to MCo in situ 2 O 4 The novel composite photocatalyst formed on (M ═ Ni, Mn and Fe) provides more reactive active sites for photocatalytic water splitting to produce hydrogen. Under the irradiation of visible light, the synergistic effect of the photocatalyst, the sensitizer and the sacrificial agent in the hydrogen production system promotes the separation of photo-generated electrons and hole pairs, accelerates the electron transmission rate and improves the activity of photocatalytic hydrogen production.
As can be seen from FIG. 3(b), the composite photocatalyst MCo 2 O 4 The cycle stability measurement is carried out on the GQDs, and the result shows that the composite photocatalyst MCo is obtained after 4 cycles 2 O 4 The hydrogen production performance activity of GQDs is not obviously reduced, which shows that the composite photocatalyst MCo 2 O 4 the/GQDs still maintain better activity. Further proves that the composite photocatalyst MCo is prepared by a one-step hydrothermal green synthesis method 2 O 4 the/GQDs has stronger photocatalytic activity and stability.
The composite photocatalyst MCo prepared by the preparation method of the invention 2 O 4 /GQDs and Co-based bimetallic oxides (MCo) 2 O 4 ) Compared with the prior art, the composite material has larger specific surface area and can provide moreMultiple reactive sites, at MCo 2 O 4 After the GQDs particles with the particle size of 10-20nm are uniformly loaded, MCo is ensured because the GQDs nano-particles have photosensitivity 2 O 4 Under the irradiation of visible light, GQDs passes through GQDs and Co-based bimetallic oxide (MCo) 2 O 4 ) The synergistic effect between the two components can expand the spectral response range of the composite photocatalyst to improve the utilization rate of visible light, and in addition, GQDs and Co-based bimetallic oxides (MCo) 2 O 4 ) The close contact between the two components is also beneficial to shortening the transfer path of electrons, thereby accelerating the speed of electron transmission and being beneficial to improving the catalytic activity and stability of the composite photocatalyst.
The invention provides application of a Co-based bimetallic oxide loaded GQDs composite photocatalyst, and the Co-based bimetallic oxide loaded GQDs composite photocatalyst can be used for photocatalytic decomposition of water to produce hydrogen, degradation of organic pollutants and reduction of carbon dioxide under the irradiation of visible light.
The principle of the photocatalytic hydrogen production technology is that solar energy is absorbed by a photocatalytic material and is effectively transmitted to water molecules, so that water is subjected to photolysis to generate hydrogen and oxygen. When the composite photocatalyst is used for hydrogen production through hydrolysis, GQDs and MCo in the composite photocatalyst 2 O 4 Due to the synergistic effect of the components, the composite photocatalyst has a larger specific surface area, so that more reactive active sites can be provided, and when the composite photocatalyst is irradiated by visible light, the catalyst has a wider response range to the visible light, so that the utilization rate of the visible light is improved, and the composite photocatalyst is favorable for shortening the transfer path of electrons, accelerating the speed of electron transmission, further accelerating the response speed to the visible light, and enhancing the photocatalytic activity of the composite photocatalyst.
The principle of the photocatalytic degradation technology is that after being irradiated by light, a photocatalyst absorbs energy, and the organic pollutants adsorbed on the photocatalyst are catalyzed and oxidized by electron transition so as to be degraded or mineralized. When the composite photocatalyst is used for degrading organic pollutants, GQDs and MCo in the composite photocatalyst 2 O 4 The synergistic effect between the two components increases the specific surface area of the photocatalytic material and the reactionThe active sites accelerate the migration of photo-generated electrons and holes, are beneficial to promoting the adsorption of organic pollutants and the transfer and separation of charges, and simultaneously, the GQDs is used as a sensitizer to ensure that the composite photocatalyst has a wider response range to visible light and improve the degradation efficiency of the composite photocatalyst.
Photocatalytic CO 2 Reduction means that the photocatalyst is excited by photons or light with proper wavelength to generate electron-hole pairs, so that CO is converted 2 Converting into active species to participate in the reaction process. Conventional photocatalytic reduction of CO 2 The yield is low and the difficulties are mainly limited use of solar energy and low separation efficiency of photo-generated electrons/holes. When the composite photocatalyst is used for carbon dioxide reduction, GQDs and MCo in the composite photocatalyst 2 O 4 The synergistic effect between the two components increases the specific surface area of the photocatalytic material, increases the active sites of the reaction, accelerates the speed of electron transmission, enables the photocatalytic material to utilize visible light in solar energy to the maximum extent and improves the separation efficiency of photoproduction electrons/holes, thereby improving CO 2 The photocatalytic reduction rate of (2).
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a Co-based bimetallic oxide loaded GQDs composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of Co-based bimetallic oxide (MCo) 2 O 4 ): dissolving a predetermined amount of cobalt salt, oxysalt of metal M and urea in deionized water, performing ultrasonic treatment, stirring and mixing uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting at 150-220 ℃ for 4-8h, performing suction filtration after the reaction is finished, drying and grinding the precipitate obtained by suction filtration to obtain powdered MCo 2 O 4 A precursor; mixing powdered MCo 2 O 4 Putting the precursor into a tube furnace for calcining to obtainMCo 2 O 4 (ii) a Wherein, the metal M is one of Ni, Fe and Mn;
(2) synthetic Co-based bimetallic oxide supported GQDs composite photocatalyst (MCo) 2 O 4 /GQDs): MCo prepared in the step (1) 2 O 4 Mixing with C source micromolecule substance at a predetermined ratio, transferring into a reaction kettle with polytetrafluoroethylene lining, reacting at 150-240 deg.C for 4-8 hr, vacuum filtering, drying the precipitate, and grinding to obtain powdered MCo 2 O 4 /GQDs。
2. The method for preparing a Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 1, wherein the Co-based bimetallic oxide supported GQDs composite photocatalyst comprises the following components: in the step (1), the cobalt salt is selected from one of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate.
3. The method for preparing a Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 1, wherein the Co-based bimetallic oxide supported GQDs composite photocatalyst comprises the following components: in the step (1), the oxysalt of the metal M is selected from one of nickel nitrate hexahydrate, manganese acetate tetrahydrate and ferric nitrite hexahydrate.
4. The method for preparing a Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 1, wherein the Co-based bimetallic oxide supported GQDs composite photocatalyst comprises the following components: in the step (1), the cobalt salt, the oxysalt of the metal M and the urea account for 30-50%, 30-70% and 0-30% of the total solute of the mixed solution by mass percent respectively.
5. The method for preparing the Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the temperature rise rate of the tubular furnace is 2-3 ℃/min, the temperature is 400-450 ℃, and the calcination time is 2-6 h.
6. The method for preparing a Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 1, wherein the Co-based bimetallic oxide supported GQDs composite photocatalyst comprises the following components: in the step (2), the MCo 2 O 4 And C source small molecular substance in a mass ratio of 1: (0.5-1.5), wherein the C-source small molecular substance is selected from one of citric acid, starch and glucose.
7. A Co-based bimetallic oxide supported GQDs composite photocatalyst prepared by the preparation method as claimed in any one of claims 1 to 6.
8. An application of the Co-based bimetallic oxide supported GQDs composite photocatalyst as defined in claim 7 in hydrogen production by decomposing water under visible light.
9. The application of the Co-based bimetallic oxide supported GQDs composite photocatalyst as claimed in claim 7 in degrading organic pollutants under visible light.
10. The application of the Co-based bimetallic oxide supported GQDs composite photocatalyst as defined in claim 7 in catalytic reduction of carbon dioxide under visible light.
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