CN112473712A - CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof - Google Patents
CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention discloses CeO treated by different atmospheres2/g‑C3N4Heterojunction material, preparation method and application thereof, belonging to material preparation and photocatalytic reduction of CO2The technical field of resource utilization. The preparation method comprises (1) mixing solid CeO2Adding the mixture into ultrapure water, and performing ultrasonic dispersion to obtain a dispersion liquid A; the solid g-C3N4Adding the mixture into ultrapure water, and performing ultrasonic dispersion to obtain a dispersion liquid B; dripping the dispersion liquid B into the dispersion liquid A, uniformly mixing reactants, heating and stirring until water is removed to obtain a solid; (2) and fully grinding the solid, calcining the solid in the atmosphere of air, nitrogen and hydrogen respectively, and cooling the solid to room temperature after the calcination is finished to obtain the heterojunction material. The invention adopts the preparation method of heterojunction materials treated by different atmospheresThe preparation process is simple and convenient, and the raw materials are cheap; the heterojunction material has strong practicability and high environmental stability, and can be used for reducing CO in photocatalysis2Has potential application prospect in the aspect.
Description
Technical Field
The invention belongs to material preparation and photocatalytic reduction of CO2The technical field of resource utilization, in particular to CeO treated by different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof.
Background
Carbon dioxide (CO)2) As a major greenhouse gas in the atmosphere, is considered a serious threat to the ecological environment. Currently, many researchers have considered exploring how to effectively utilize carbon dioxide. Based on the unique performance of solar energy conversion, the photocatalysis technology is taken as a clean and efficient carbon dioxide photoreduction technology. In recent years, graphitic carbo-nitrides (g-C)3N4) Is a potential photocatalyst with narrow band gap and high stability, and has been widely applied to photocatalytic VOC degradation, water decomposition and CO2Photoreduction, and the like. However, g-C3N4The recombination rate of the photogenerated carriers is relatively high and the number of exposed active adsorption sites is low, which results in low photocatalytic efficiency. Cerium oxide (CeO)2) Due to its rich oxygen defects, impressive redox capabilities and low cost, it shows good prospects in industrial applications. For photocatalysis, CeO2Oxygen vacancies at the surface can enhance its light absorption capability. Further, CeO2Is an alkaline metal oxide, and can not only increase CO2Adsorption capacity of (2), and also reduction of CO2The reduction potential of (1).
In order to increase the activity of photocatalysts, several strategies have been found, such as doping with other elements or with themThe other semiconductors are compounded. Among them, heat treatment under different atmospheres is also an effective and promising method for promoting electron-hole separation. By exposure to different atmospheres (e.g. N)2,O2,H2Etc.) treatment of g-C3N4It may be allowed to form a carbon vacancy or an amino site, thereby improving the separation efficiency of electron-hole pairs. Meanwhile, CeO can be adjusted by heat treatment under different atmospheres2Concentration of oxygen vacancies above or preparation of CeO in different forms2Thereby improving the photocatalytic performance of the material. However, the photocatalytic performance of semiconductor materials promoted by heat treatment only using different atmospheres has yet to be improved.
The light absorption performance of the composite material and the rapid separation and transfer of the photo-generated electron pair can be remarkably improved by constructing the heterojunction, and the photo-reduction/oxidation capability of the composite material can also be enhanced. Thus, CeO was constructed2/g-C3N4The heterojunction structure can provide more active sites, effectively enhance the light absorption capacity, reduce the recombination rate of photo-generated electron hole pairs and improve the reduction capacity of a conduction band. However, CeO treated so far with an oxidizing, inert and reducing atmosphere has not been used2/g-C3N4Photocatalyst preparation and photocatalytic CO2Reduction applications are reported.
Disclosure of Invention
In view of the problems in the prior art, one technical problem to be solved by the present invention is to provide CeO treated with different atmospheres2/g-C3N4The preparation method of the heterojunction material is characterized in that the heterojunction material with different properties is prepared by calcining under different gas atmosphere conditions, the preparation process is green and simple, the cost is low, and the prepared composite material has strong practicability. Another technical problem to be solved by the invention is to provide CeO treated in different atmospheres2/g-C3N4Heterojunction material having excellent environmental stability, in which Ce is co-present3+、Ce4+And can be used as a photocatalyst with excellent performance. The technical problem to be solved by the invention is to provide CeO treated in different atmospheres2/g-C3N4Photocatalytic reduction of CO from heterojunction materials2The catalyst has the advantages of high utilization rate of visible light, good transmission effect of photoproduction charges and strong reduction capability in catalytic application, and solves the problem of CO2Has potential application prospect in the aspect of environmental problems such as greenhouse effect and the like.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
CeO treated with different atmospheres2/g-C3N4The preparation method of the heterojunction material specifically comprises the following steps:
(1) solid CeO2Adding into ultrapure water, and ultrasonically dispersing uniformly to obtain a dispersion liquid A; the solid g-C3N4Adding into ultrapure water, and ultrasonically dispersing uniformly to obtain a dispersion liquid B; dripping the dispersion liquid B into the dispersion liquid A, uniformly mixing reactants, heating and stirring until water is removed to obtain a solid;
(2) fully and uniformly grinding the solid, respectively calcining in air, nitrogen and hydrogen atmospheres, naturally cooling to room temperature after calcining is finished, and respectively obtaining CeCN and CeCN-N2、CeCN-H2A heterojunction material.
The CeO treated by different atmospheres2/g-C3N4Preparation method of heterojunction material and solid CeO2The preparation of (1): introducing air into the tube furnace, and reacting Ce (NO) at 550-600 DEG C3)3·6H2Calcining O for 4-6 h to obtain CeO2。
The CeO treated by different atmospheres2/g-C3N4Method for preparing heterojunction material, solid g-C3N4The preparation of (1): introducing air into a muffle furnace, and calcining urea for 4-6 hours at 550-600 ℃ to obtain g-C3N4。
The CeO treated by different atmospheres2/g-C3N4The preparation method of the heterojunction material comprises the steps that the concentration of the dispersion liquid A is 0.5-1.0 g/L, the concentration of the dispersion liquid B is 9.0-9.5 g/L, and the ultrasonic dispersion time is 0.5-1 h.
The CeO treated by different atmospheres2/g-C3N4Preparation method of heterojunction material and solid CeO2And solids g-C3N4The mass ratio of (A) to (B) is 1: 10-1: 15; the reaction temperature of the dispersion liquid A and the dispersion liquid B is 100-200 ℃.
The CeO treated by different atmospheres2/g-C3N4In the step (3), the calcining temperature is 450-550 ℃; the gas flow rate is 150-250 mL/min.
CeO treated in different atmospheres prepared by the above preparation method2/g-C3N4A heterojunction material.
CeO treated in different atmospheres as described above2/g-C3N4Photocatalytic reduction of CO from heterojunction materials2The use of (1).
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) CeO treated in different atmospheres according to the invention2/g-C3N4The preparation process of the heterojunction material is green and simple, low in cost and strong in practicability, and the heterojunction material has excellent environmental stability and solves CO2Has potential application prospect in the aspect of environmental problems such as greenhouse effect and the like.
(2) CeO treated in different atmospheres according to the invention2/g-C3N4Coexistence of Ce in the heterojunction material3+、Ce4+In which Ce is3+And Ce4+Is in the form of a reversible electron pair, which can extend the lifetime of the charge; ce4+Capable of trapping electrons to prevent rapid recombination of electron-hole pairs; ce3+Can enhance the reducing capability of the system, thereby being beneficial to realizing CO under visible light2And (4) reducing.
(3) CeO treated in different atmospheres according to the invention2/g-C3N4The heterojunction material can be used as a photocatalyst with excellent performance, and N is used for preparing the heterojunction material2Atmosphere calcination of prepared CeCN-N2Can generate amino with positive charge, and the formed built-in electric field can be constructed into a Z-type photocatalysis system. The system has strongerReduction potential and medium-strong alkaline site, which is beneficial to enhancing the reactant CO2The molecular adsorption/activation is beneficial to improving the utilization rate of visible light, promoting the transmission and reduction capability of photo-generated charges and finally effectively improving the photocatalytic performance of the composite material. Thus, CeO treated with different atmospheres2/g-C3N4The heterojunction material has wide prospect in the fields of Z-shaped photocatalytic system construction and catalytic practical application.
Drawings
FIG. 1 is an XRD of the prepared sample, wherein FIG. 1A is an XRD pattern and FIG. 1B is a partial enlarged view of XRD;
FIG. 2 is a TEM spectrum of the prepared sample, in which FIG. 2A is a TEM spectrum of CeCN, and FIG. 2B is CeCN-N2TEM spectrum of (5), FIG. 2C is CeCN-H2A TEM spectrum of;
FIG. 3 is a PL (FIG. 3A) spectrum and a photocurrent (FIG. 3B) of the prepared sample;
FIG. 4 is a O1s XPS (FIG. 4A) plot and an EPR (FIG. 4B) plot of the prepared samples;
FIG. 5 is a diagram showing the band gap structure of the prepared sample;
FIG. 6 is a graph of the prepared samples under full spectrum illumination for CO2And (5) reducing the effect graph.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Preparation of N2Atmosphere treated CeO2/g-C3N4A composite material comprising the steps of:
(1) preparation of CeO2Catalyst: weighing 10g Ce (NO)3)3·6H2Placing O into a crucible, covering the crucible with a crucible cover, horizontally placing into a tube furnace, calcining in air atmosphere, heating to 570 ℃, reacting for 5h at the temperature, and cooling to room temperature after calcination to obtain CeO2A catalyst;
(2) preparation of g-C3N4Photocatalyst: weighing 10g of urea and putting into a cruciblePutting the crucible in a muffle furnace horizontally with a crucible cover, calcining in air atmosphere, heating to 570 ℃, reacting for 5h at the temperature, and cooling to room temperature after calcination to obtain g-C3N4A photocatalyst;
(3) 0.07g of CeO2Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid A;
(4) 0.93g g-C3N4Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid B;
(5) slowly dropping the dispersion liquid B into the dispersion liquid A drop by drop, stirring for 1h after dropping, uniformly mixing reactants, placing the reaction liquid in a fume hood, heating by an oil bath at 100 ℃, fully stirring, and reacting until water is removed to obtain a solid;
(6) grinding the obtained solid uniformly, and introducing N into a tube furnace2Heating the calcination to 570 ℃, wherein the gas flow rate is 220 mL/min; naturally cooling to room temperature after the reaction is finished to obtain the CeCN-N2A heterojunction material.
Example 2
Preparation of air atmosphere treated CeO2/g-C3N4A composite material comprising the steps of:
(1) preparation of CeO2Catalyst: weighing 10g Ce (NO)3)3·6H2Placing O into a crucible, covering the crucible with a crucible cover, horizontally placing into a tube furnace, calcining in air atmosphere, heating to 570 ℃, reacting for 5h at the temperature, and cooling to room temperature after calcination to obtain CeO2A catalyst;
(2) preparation of g-C3N4Photocatalyst: weighing 10g of urea, putting the urea into a crucible, covering the crucible with a crucible cover, horizontally placing the crucible into a muffle furnace, calcining in air atmosphere, raising the temperature to 570 ℃, reacting for 5 hours at the temperature, and cooling to room temperature after calcination to obtain g-C3N4A photocatalyst;
(3) 0.07g of CeO2Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid A;
(4) 0.93g g-C3N4Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid B;
(5) slowly dropping the dispersion liquid B into the dispersion liquid A drop by drop, stirring for 1h after dropping, uniformly mixing reactants, placing the reaction liquid in a fume hood, heating by an oil bath at 100 ℃, fully stirring, and reacting until water is removed to obtain a solid;
(6) uniformly grinding the obtained solid powder, introducing air into a tubular furnace, calcining, heating to 570 ℃, and controlling the gas flow rate to be 220 mL/min; and naturally cooling to room temperature after the reaction is finished to obtain the CeCN heterojunction material.
Example 3
Preparation of Hydrogen atmosphere treated CeO2/g-C3N4A composite material comprising the steps of:
(1) preparation of CeO2Catalyst: weighing 10g Ce (NO)3)3·6H2Placing O into a crucible, covering the crucible with a crucible cover, horizontally placing into a tube furnace, calcining in air atmosphere, heating to 570 ℃, reacting for 5h at the temperature, and cooling to room temperature after calcination to obtain CeO2A catalyst;
(2) preparation of g-C3N4Photocatalyst: weighing 10g of urea, putting the urea into a crucible, covering the crucible with a crucible cover, horizontally placing the crucible into a muffle furnace, calcining in air atmosphere, raising the temperature to 570 ℃, reacting for 5 hours at the temperature, and cooling to room temperature after calcination to obtain g-C3N4A photocatalyst;
(3) 0.07g of CeO2Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid A;
(4) 0.93g g-C3N4Adding the mixture into 50mL of ultrapure water, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid B;
(5) slowly dropping the dispersion liquid B into the dispersion liquid A drop by drop, stirring for 1h after dropping, uniformly mixing reactants, placing the reaction liquid in a fume hood, heating by an oil bath at 100 ℃, fully stirring, and reacting until water is removed to obtain a solid;
(6) uniformly grinding the obtained solid powder, introducing hydrogen into a tubular furnace, calcining, heating to 570 ℃, and controlling the gas flow rate to be 220 mL/min; naturally cooling to room temperature after the reaction is finished to obtain the CeCN-H2A heterojunction material.
FIG. 1 shows CeCN, CeCN-N2，CeCN-H2，CeO2And g-C3N4X-ray diffraction pattern (XRD) of the sample. As can be seen from FIG. 1A, the samples CeCN, CeCN-N2And CeCN-H2Shows similar diffraction peaks, wherein the peaks appearing at 13.1 ° and 27.3 ° are respectively attributed to g-C3N4The (100) and (002) planes of (a); the peaks at 28.7 °, 33.3 °, 47.8 ° and 56.8 ° were CeO, respectively2(111) Characteristic peaks of (200), (220) and (311) crystal planes. FIG. 1B is an enlarged view of a portion of FIG. 1A, as seen in FIG. 1B, and g-C3N4In contrast, samples CeCN, CeCN-N2And CeCN-H2The diffraction peak at 27.3 ° showed a slight shift to higher angles, indicating that the interlayer distance was narrowed, and CeO2And g-C3N4There is an interface effect between them.
FIG. 2 shows the material CeCN (FIG. 2A), CeCN-N2(FIG. 2B) and CeCN-H2(FIG. 2C) Transmission Electron micrograph of CeO2g-C with nanoparticles dispersed in a two-dimensional layer3N4Above, and different pre-treatment atmospheres for CeO2/g-C3N4The morphology of the photocatalyst has no effect.
FIG. 3 is CeCN, CeCN-N2And CeCN-H2PL Spectrum (FIG. 3A) and photocurrent (FIG. 3B) of the material, as can be seen from FIG. 3A, with CeCN and CeCN-H2Compared with CeCN-N2The PL emission intensity of (A) is significantly reduced, indicating that CeCN-N2Has higher electron-hole separation efficiency, and the photo-generated charges are easy to be generated on CeCN and CeCN-H2And (4) recombining on the material. As can be seen from fig. 3B, the photocurrent of each material is in the order from high to low: i isCeCN-N2＞ICeCN＞ICeCN-H2The results show that CeCN-N2The method has the best photoproduction electron-hole separation efficiency, the best electron service life and better photocatalysis efficiency.
FIG. 4 shows the materials CeCN, CeCN-N2And CeCN-H2The O1s XPS (fig. 4A) and EPR (fig. 4B) of the sample, and as can be seen from fig. 4A, the O1s XPS spectrum is divided into three peaks: the binding energies 529.6eV, 531.9eV and 533.0eV, respectively, may be attributed to lattice oxygen (O)L) Chemical adsorption (O)C) And surface hydroxyl species or surface water-adsorbed oxygen species (O)S)。CeCN-N2And CeCN-H2O of (A) to (B)L/O(s+c)Lower than the CeCN photocatalyst, indicating a higher relative concentration of oxygen defects. CeCN-N2And CeCN-H2The lattice oxygen sites are transferred to a higher binding energy than the CeCN, indicating a decrease in the electron density of the lattice oxygen, which may be due to the CeCN-N2And CeCN-H2Resulting from the formation of oxygen defects on the sample.
FIG. 5 shows the materials CeCN, CeCN-N2And CeCN-H2The structure of the bandgap structure of (1). As can be seen from FIG. 5, for CeCN, a typical type-II is formed. For CeCN-N2Due to the built-in electron field at the interface (i.e., positively charged g-C)3N4) Photoinduced electrons are easier to go to g-C3N4Aggregate to form g-C with stronger reducing property3N4/CeO2A Z-type photocatalytic system. In contrast, for CeCN-H2Photoinduced electron transfer to CeO2And tends to recombine with holes resulting in an increase in the rate of recombination of photo-generated charges.
Example 4
Application of the photocatalyst prepared in examples 1-3 to CO2In the reduction, the experimental steps are as follows:
CO2the photoreduction reaction of (a) was carried out in a 50W Teflon-lined autoclave and irradiated by a 300W Xe lamp. The CeO prepared in examples 1 to 3 was taken2/g-C3N4Heterojunction material, CeO2Catalyst and g-C3N450mg of each photocatalyst was dispersed in 5mL of ultrapure water, and high-purity CO was added thereto2Gas with pressure up to 4bar to obtain suspension, stirring the suspension for 30min, and irradiating for 8 hr with full spectrum; the CO produced was determined by gas chromatography. The used sample was washed several times with distilled waterThen drying in an oven at 80 ℃; the experiment was carried out again using the above method, and the full spectrum irradiation was still carried out for 8 hours in this cycle experiment. Experimental results show that the prepared CeO2/g-C3N4The amount of CO produced by the heterojunction material has no obvious change, which shows that the prepared material has good light stability.
FIG. 6 is a graph of the prepared samples under full spectrum illumination for CO2FIG. 6 shows the reduction effect, and the order of activity is CeCN-N2>CeCN>CeCN-H2Showing that N is in comparison with the CeCN sample2Atmosphere treatment favors CO2Is photo-reduced with H2The heterojunction material after atmosphere treatment is in CO2The effect in the reduction treatment is not outstanding.
Claims (8)
1. CeO treated with different atmospheres2/g-C3N4The preparation method of the heterojunction material is characterized by comprising the following steps:
(1) solid CeO2Adding into ultrapure water, and ultrasonically dispersing uniformly to obtain a dispersion liquid A; the solid g-C3N4Adding into ultrapure water, and ultrasonically dispersing uniformly to obtain a dispersion liquid B; dripping the dispersion liquid B into the dispersion liquid A, uniformly mixing reactants, heating and stirring until water is removed to obtain a solid;
(2) fully and uniformly grinding the solid, respectively calcining in air, nitrogen and hydrogen atmospheres, naturally cooling to room temperature after calcining is finished, and respectively obtaining CeCN and CeCN-N2、CeCN-H2A heterojunction material.
2. CeO treated with different atmospheres according to claim 12/g-C3N4A method for preparing a heterojunction material, characterized in that solid CeO2The preparation of (1): introducing air into the tube furnace, and reacting Ce (NO) at 550-600 DEG C3)3·6H2Calcining O for 4-6 h to obtain CeO2。
3. CeO treated with different atmospheres according to claim 12/g-C3N4A method for producing a heterojunction material, characterized in that the solid g-C3N4The preparation of (1): introducing air into a muffle furnace, and calcining urea for 4-6 hours at 550-600 ℃ to obtain g-C3N4。
4. CeO treated with different atmospheres according to claim 12/g-C3N4The preparation method of the heterojunction material is characterized in that the concentration of the dispersion liquid A is 0.5-1.0 g/L, the concentration of the dispersion liquid B is 9.0-9.5 g/L, and the ultrasonic dispersion time is 0.5-1 h.
5. CeO treated with different atmospheres according to claim 12/g-C3N4A method for preparing a heterojunction material, characterized in that solid CeO2And solids g-C3N4The mass ratio of (A) to (B) is 1: 10-1: 15; the reaction temperature of the dispersion liquid A and the dispersion liquid B is 100-200 ℃.
6. CeO treated with different atmospheres according to claim 12/g-C3N4The preparation method of the heterojunction material is characterized in that in the step (3), the calcination temperature is 450-550 ℃; the gas flow rate is 150-250 mL/min.
7. CeO treated in different atmospheres prepared by the preparation method of any one of claims 1 to 62/g-C3N4A heterojunction material.
8. The different atmosphere treated CeO of claim 72/g-C3N4Photocatalytic reduction of CO from heterojunction materials2The use of (1).
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