CN115430446A - CePO 4 /g-C 3 N 4 Heterojunction material, preparation method and application thereof - Google Patents
CePO 4 /g-C 3 N 4 Heterojunction material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a CePO 4 /g‑C 3 N 4 Heterojunction material, preparation method and application thereof, belonging to material preparation and photocatalytic reduction of CO 2 The technical field of resource utilization. The invention firstly obtains g-C by heating and calcining urea 3 N 4 (ii) a Then in g-C 3 N 4 Adding Ce (NO) into the suspension in sequence 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 Hydrothermal reaction, cooling, water washing and ethanol washing, and drying overnight to obtain CePO 4 /g‑C 3 N 4 A heterojunction material. The preparation process is green and simple, the cost is low, the environment is protected, the practicability is high, and the prepared CePO 4 /g‑C 3 N 4 Heterojunction material beneficial to enhancing CO 2 The adsorption/activation effect of the composite photocatalyst has the advantages of high visible light utilization rate, good transmission effect of photo-generated charges, strong reduction capability, good economic benefit and environmental protection benefit, and provides guidance for designing a Z-type photocatalytic system.
Description
Technical Field
The invention belongs to material preparation and photocatalytic reduction of CO 2 The technical field of resource utilization, in particular to CePO 4 /g-C 3 N 4 Heterojunction material, preparation method and application thereof.
Background
In recent years, in order to solve the problems of rapid consumption of fossil fuels and global warming, many methods for reducing carbon emissions have been proposed. Among them, solutions for reducing carbon dioxide emissions or converting carbon dioxide into valuable carbon derivatives (e.g., methane, formic acid, methanol, etc.) in sustainable solar energy have received much attention. Thus, photocatalytic CO 2 Reduction technology is one of the fastest currently developing solutions in terms of its sustainability, environmental friendliness, and high efficiency.
At present, various semiconductors such as g-C 3 N 4 、ZnIn 2 S 4 、TiO 2 、WO 3 、MOF、CeO 2 、CdS、 SrTiO 3 Has been widely used in the field of photocatalysis. Wherein, the cerium phosphate (CePO) 4 ) As one of the most common rare earth phosphate materials, the rare earth phosphate material has the characteristics of special 4f-5d and 4f-4f electronic transition, excellent electrical conductivity, stronger covalent P-O bonding, high chemical stability and the like, and has wide application in the fields of fluorescence, ion exchange, catalytic materials, ceramic composite materials and the like. Graphitized carbon (g-C) 3 N 4 ) The material is considered to be a potentially valuable visible light catalytic material due to the advantages of narrow band gap, good stability and the like. However, g-C 3 N 4 There are two major drawbacks: (1) the photogenerated carrier recombination is relatively high; (2) The small specific surface area, which results in low photocatalytic efficiency.
The light absorption performance of the composite material and the rapid separation and transfer of the photo-generated electron pair can be effectively improved by constructing the heterojunction, and the photo-reduction/oxidation capability of the composite material can also be enhanced. However, so far, forConstruction of CePO 4 /g-C 3 N 4 Heterojunction structure and photocatalytic CO thereof 2 The reduction performance is reported less.
Disclosure of Invention
Aiming at the problems in the prior art, the first technical problem to be solved by the invention is to provide a CePO 4 /g-C 3 N 4 A heterojunction material; the second technical problem to be solved by the invention is to provide CePO 4 /g-C 3 N 4 A preparation method of the heterojunction material; the third technical problem to be solved by the invention is to provide CePO 4 /g-C 3 N 4 Photocatalytic reduction of CO from heterojunction materials 2 The use of (1).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
CePO 4 /g-C 3 N 4 The preparation method of the heterojunction material comprises the following steps:
1) Slowly adding urea into a crucible at room temperature, introducing air into a muffle furnace, heating and calcining to obtain g-C 3 N 4 ；
2) According to g-C 3 N 4 The dosage ratio of the ultra-pure water and the ultra-pure water is 0.1-1.5 g: 15mL, the ultrasonic dispersion is uniform, and g-C is formed 3 N 4 Suspending liquid; adding Ce (NO) 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 Are added in sequence to g-C 3 N 4 Stirring the suspension for 1 hour, and pouring the suspension into a reaction kettle for hydrothermal reaction at the temperature of 100-200 ℃ for 11-13 hours; naturally cooling to room temperature, washing with water and ethanol, and oven drying overnight to obtain CePO 4 /g-C 3 N 4 A heterojunction material.
Further, in the step 1), the dosage of the urea is 0-100 mg, the heating rate is 5-10 ℃/min, and the calcining temperature is 500-600 ℃.
Further, in step 2), g to C 3 N 4 The amount ratio of ultrapure water to ultrapure water was 0.43 g: 15mL.
Further, in step 2), ce (NO) 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 The dosage ratio of the components is 1.3g to 0.345g.
Further, in the step 2), the time of the ultrasonic reaction is 0.5-1 h.
Preferably, in the step 2), the time for ultrasonic reaction is 0.5h.
Preferably, in the step 2), the temperature of the hydrothermal reaction is 150 ℃, and the time of the hydrothermal reaction is 12h.
CePO prepared by the method 4 /g-C 3 N 4 A heterojunction material.
The CePO 4 /g-C 3 N 4 Photocatalytic reduction of CO from heterojunction materials 2 The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention CePO 4 /g-C 3 N 4 The preparation process of the heterojunction material is green and simple, low in cost, environment-friendly and high in practicability.
(2) CePO prepared by the invention 4 /g-C 3 N 4 Heterojunction material, compared with the existing P-CeO 2 /g-C 3 N 4 Material, CO 2 The photocatalytic conversion performance is obviously improved; the heterojunction material has excellent environmental stability and can be used in CO 2 Has potential application prospect in resource utilization and other aspects.
(3) The CePO prepared by the invention 4 /g-C 3 N 4 Application of heterojunction material in photocatalytic reduction of CO 2 In particular, has the advantages of high utilization rate of visible light, good transmission effect of photo-generated charges and strong reduction capability, and solves the problem of CO 2 Has potential application prospect in the aspect of environmental problems such as greenhouse effect and the like.
Drawings
FIG. 1 is an XRD pattern of a sample prepared according to the present application;
FIG. 2 is an FTIR spectrum of a sample prepared herein;
FIG. 3 is a TEM spectrum of a sample prepared herein; in the figure, A, B, C, D, E, F are CePO respectively 4 、Ce/CN、Ce/CN 0.5 、Ce/CN 0.25 、Ce/CN 0.3 And g-C 3 N 4 A sample;
FIG. 4 is the Ce/CN that is prepared by the present application 0.3 And CePO 4 P2P XPS (A) and O1s XPS (B) plots of the samples;
FIG. 5 is a graph of UV-vis DRS (A) spectrum, photocurrent (B) and EIS (C) for samples prepared according to the present application;
FIG. 6 shows a sample prepared according to the present application and P-CeO 2 /g-C 3 N 4 Sample to CO under full spectrum irradiation 2 Performance of the reduction is plotted.
Detailed Description
The invention is further described with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. In the following examples, unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
According to g-C 3 N 4 The dosage ratio of the ultra-pure water and the ultra-pure water is 0.325 g: 15mL, the ultrasonic dispersion is uniform, and g-C is formed 3 N 4 Suspending liquid; sequentially adding Ce (NO) 3 ) 3 ·6H 2 O (1.3 g) and NH 4 H 2 PO 4 (0.345 g) was added to the above g-C 3 N 4 Stirring the suspension for 1h, and pouring the suspension into a reaction kettle for hydrothermal reaction at the temperature of 150 ℃ for 12h; naturally cooling to room temperature, washing with water and ethanol, and drying at 80 deg.C overnight to obtain Ce/CN 0.25 A heterojunction material. Ce/CN 0.3 ，Ce/CN 0.5 Preparation of Ce/CN and the above-mentioned Ce/CN 0.25 The method of (1) is similar except for g-C 3 N 4 Of the mass of (c). Ce/CN 0.3 ，Ce/CN 0.5 Ce/CN respectively correspond to g-C 3 N 4 The mass of (A): 0.43g,0.65g and 1.3g.
Comparative example 1
At room temperature, mixing 10g urea is slowly added into a crucible, air is introduced into a muffle furnace to heat and calcine to obtain g-C 3 N 4 (ii) a The heating rate is 5-10 ℃/min, and the calcining temperature is 500-600 ℃.
Comparative example 2
According to Ce (NO) 3 ) 3 ·6H 2 O、NH 4 H 2 PO 4 The amount ratio of the Ce (NO) to the ultrapure water is 1.3 g: 0.345 g: 15mL 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 Respectively putting into ultrapure water, and ultrasonically dispersing uniformly to form Ce (NO) 3 ) 3 ·6H 2 O suspension and NH 4 H 2 PO 4 Suspension, NH 4 H 2 PO 4 Slowly dripping Ce (NO) into the suspension 3 ) 3 ·6H 2 Stirring the O suspension for 1h, and pouring the mixture into a reaction kettle to perform hydrothermal reaction at the temperature of 150 ℃ for 12h; naturally cooling to room temperature, washing with water and ethanol, and oven drying overnight to obtain CePO 4 。
Comparative example 3
P-CeO 2 /g-C 3 N 4 The preparation method of the composite material comprises the following steps:
(1) Preparation of g-C 3 N 4 Photocatalyst: 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, heating to 600 ℃, reacting for 4 hours at the temperature, and cooling to room temperature after calcination to obtain g-C 3 N 4 A sample;
(2) Mixing 0.6g g-C 3 N 4 And 0.5g Ce (NO) 3 ) 3 ·6H 2 Adding O into 25mL of ultrapure water, performing ultrasonic treatment for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid E;
(3) 0.008g of Na 3 PO 4 ·12H 2 Adding O into 25mL of ultrapure water, and fully stirring and uniformly mixing to obtain a dispersion liquid F;
(4) Slowly dropping the dispersion liquid F into the dispersion liquid E drop by drop, stirring for 1h after dropping, uniformly mixing reactants, transferring the reaction liquid into a 50mL stainless steel autoclave, carrying out constant-temperature thermal reaction at 180 ℃, and reacting for 14h;
(5) Naturally cooling to room temperature after the reaction is finished, respectively washing with ultrapure water and absolute ethyl alcohol for 5 times, and drying for 10 hours at the temperature of 60 ℃ in vacuum to obtain the P-CeO 2 /g-C 3 N 4 A heterojunction material.
FIG. 1 is Ce/CN 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 ，Ce/CN，CePO 4 And g-C 3 N 4 X-ray diffraction Pattern (XRD) of the sample, ce/CN, as seen in FIG. 1 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 Ce/CN and CePO 4 The samples showed similar diffraction peaks. But with g-C 3 N 4 With a reduction in the input, the diffraction peaks at 28 ° and 32 ° showed a tendency from weak to strong to weak, and a slight shift of the diffraction peak at 28 ° to a lower angle, indicating a broadening of the interlayer distance, and the CePO 4 And g-C 3 N 4 There is an interface effect between them.
FIG. 2 is Ce/CN 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 ，Ce/CN，CePO 4 And g-C 3 N 4 FTIR pattern of the sample, from which Ce/CN was known 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 CePO appeared in the Ce/CN samples 4 And g-C 3 N 4 The vibration peak of (1) indicates that the CePO is successfully prepared 4 /g-C 3 N 4 A composite material.
FIG. 3 is CePO 4 ，Ce/CN，Ce/CN 0.5 ，Ce/CN 0.25 ，Ce/CN 0.3 ，g-C 3 N 4 TEM of the sample (A, B, C, D, E, F in FIG. 3), ce/CN is shown in the figure 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 ， Ce/CN，CePO 4 All samples showed rod-like CePO 4 g-C supported on a sheet 3 N 4 The above.
The XPS results of FIG. 4 indicate the P, O species valence and CePO in the composite 4 Are similar to each other. The above results all indicate the successful preparation of CePO 4 /g-C 3 N 4 A composite material.
Example 2
CO 2 The photoreduction reaction of (a) was carried out in a 50W Teflon-lined autoclave and irradiated by a 300W Xe lamp. Different proportions of CePO 4 /g-C 3 N 4 The heterojunction material (50 mg) was spread evenly in a quartz reactor and dropped into 1mL of ultrapure water, to which high purity CO was added 2 Gas, pressure up to 4bar. The full spectrum was used for 8 hours. CO and CH produced 4 Measured by gas chromatography. In addition, cycling experiments were also performed, each cycle being performed for 8 hours. After each cycle, the used samples were washed several times with distilled water and then dried in an oven at 80 ℃.
FIG. 5 is Ce/CN 0.25 ，Ce/CN 0.3 ，Ce/CN 0.5 ，Ce/CN，CePO 4 And g-C 3 N 4 UV-vis DRS (A) spectra, photocurrent (B) plots, and EIS plots (C) for the samples. Ce/CN in comparison with other samples 0.3 Has large visible light response, maximum photocurrent intensity and minimum Nyquist circle radius, and shows that Ce/CN 0.3 Has higher electron-hole separation efficiency, the best electron life and better photocatalysis efficiency.
FIG. 6 is a graph of the prepared samples under full spectrum illumination for CO 2 FIG. A shows the reduction effect, and from this graph, ce/CN 0.3 Has the highest CO yield and CH 4 High selectivity with g-C 3 N 4 The input amount is reduced, the catalytic performance of the sample is changed from strong to weak, and the catalytic performance is in Ce/CN 0.3 The inflection point is formed, and the CO yield reaches 3.1 mu mol g -1 ·h -1 . Compared with the previous P-CeO 2 /g-C 3 N 4 The performance of the material, CO yield, is improved by about 6 times. CePO prepared by the patent 4 /g-C 3 N 4 Heterojunction in CO 2 Has potential application prospect in the aspect of resource utilization.
Claims (9)
1. CePO 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized by comprising the following steps of:
1) Heating and calcining urea in a muffle furnace to obtain g-C 3 N 4 ；
2) According to g-C 3 N 4 The dosage ratio of the ultra-pure water and the ultra-pure water is 0.1-1.5 g: 15mL, the ultrasonic dispersion is uniform, and g-C is formed 3 N 4 Suspending liquid; adding Ce (NO) 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 Are added in sequence to g-C 3 N 4 Stirring the suspension for 1h, and pouring the suspension into a reaction kettle for hydrothermal reaction at the temperature of between 100 and 200 ℃ for 11 to 13h; naturally cooling to room temperature, washing with water and ethanol, and oven drying overnight to obtain CePO 4 /g-C 3 N 4 A heterojunction material.
2. The CePO of claim 1 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 1), the dosage of urea is 0-100 mg, the heating rate is 5-10 ℃/min, and the calcining temperature is 500-600 ℃.
3. The CePO of claim 1 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 2), g-C 3 N 4 The amount ratio of the ultrapure water to the ultrapure water was 0.43 g: 15mL.
4. The CePO of claim 1 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 2), ce (NO) is added 3 ) 3 ·6H 2 O and NH 4 H 2 PO 4 The dosage ratio of the components is 1.3g to 0.345g.
5. The CePO of claim 1 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 2), the ultrasonic reaction time is 0.5-1 h.
6. The CePO of claim 5 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 2), the ultrasonic reaction time is 0.5h.
7. The CePO of claim 1 4 /g-C 3 N 4 The preparation method of the heterojunction material is characterized in that in the step 2), the temperature of the hydrothermal reaction is 150 ℃, and the time of the hydrothermal reaction is 12 hours.
8. CePO prepared by the process according to any one of claims 1 to 7 4 /g-C 3 N 4 A heterojunction material.
9. The CePO of claim 8 4 /g-C 3 N 4 Photocatalytic reduction of CO from heterojunction materials 2 The use of (1).
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