CN115212902A - All-inorganic halide perovskite composite material and preparation method and application thereof - Google Patents

All-inorganic halide perovskite composite material and preparation method and application thereof Download PDF

Info

Publication number
CN115212902A
CN115212902A CN202210508645.0A CN202210508645A CN115212902A CN 115212902 A CN115212902 A CN 115212902A CN 202210508645 A CN202210508645 A CN 202210508645A CN 115212902 A CN115212902 A CN 115212902A
Authority
CN
China
Prior art keywords
cspbbr
composite material
cspb
halide perovskite
inorganic halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210508645.0A
Other languages
Chinese (zh)
Other versions
CN115212902B (en
Inventor
王朋
高鹏
黄柏标
王泽岩
刘媛媛
郑昭科
程合锋
张倩倩
张晓阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN202210508645.0A priority Critical patent/CN115212902B/en
Publication of CN115212902A publication Critical patent/CN115212902A/en
Application granted granted Critical
Publication of CN115212902B publication Critical patent/CN115212902B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of photo-thermal catalytic materials, and particularly relates to an all-inorganic halide perovskite composite material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: reacting CsBr and PbBr 2 Proportionally mixing, grinding, and sintering at 300-450 deg.C for a certain time to obtain CsPbBr 3 A material; reacting CsPbBr 3 The CsPbBr is prepared by the material and water in an organic solvent by adopting an in-situ water etching method 3 CsPbBr radical 3 @CsPb 2 Br 5 A composite material. Prepared CsPbBr 3 @CsPb 2 Br 5 The composite material can effectively separate photoproduction electron-hole, and shows good photo-thermal catalysis CO 2 The hydrogenation performance is reduced, so the method has good practical application value.

Description

All-inorganic halide perovskite composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photo-thermal catalytic materials, and particularly relates to an all-inorganic halide perovskite composite material and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
CO 2 The conventional methods for reduction hydrogenation include a thermocatalysis method, a photocatalysis method and a photothermal catalysis method. Can be used for CO 2 The reduced photo-thermal catalytic material has the advantages of high photo-absorption efficiency, proper position of electric conduction and valence band in reaction, wide photo-absorption range, good long-term thermal stability and the like, and the selectable photo-thermal catalytic materials are relatively limited. Photo-thermal catalytic materials in common use, e.g. TiO 2 、MgO、CeO 2 、Al 2 O 3 And SiO 2 And the like, which are wide band gap semiconductors, have the problems of small light absorption range, low solar energy utilization rate and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an all-inorganic halide perovskite composite material and a preparation method and application thereof, and CsPbBr is used 3 Synthesizing CsPbBr by in-situ water etching as raw material 3 CsPbBr radical 3 @CsPb 2 Br 5 A composite material. Tests prove that the catalyst has good photo-thermal catalytic performance, so that the catalyst has good practical application value.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing an all-inorganic halide perovskite composite material, comprising the steps of:
reacting CsBr and PbBr 2 Proportionally mixing, grinding, and sintering at 300-450 deg.C for a certain time to obtain CsPbBr 3 A material;
reacting CsPbBr 3 The CsPbBr is prepared by the material and water in an organic solvent by adopting an in-situ water etching method 3 CsPbBr radical 3 @CsPb 2 Br 5 A composite material.
In a second aspect, the invention provides an all-inorganic halide perovskite composite material prepared by the preparation method.
In a third aspect, the invention provides the use of the all-inorganic halide perovskite composite material in a photo-thermal catalytic reaction;
especially in the photo-thermal catalytic carbon dioxide hydrogenation reaction.
The above-described one or more embodiments of the present invention achieve the following advantageous effects:
CsPbBr 3 @CsPb 2 Br 5 the preparation method of the composite material is simple, and has the advantages of mild reaction conditions, low cost, high yield and the like;
prepared CsPbBr 3 @CsPb 2 Br 5 The composite material can effectively separate photoproduction electron-hole, and shows good photo-thermal catalysis CO 2 The hydrogenation performance is reduced, so that the method has good practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows CO used in the photo-thermal catalysis experiment in example 1 of the present invention 2 A hydrogenation reactor system.
FIG. 2 shows (a) CsPbBr in example 1 of the present invention 3 @CsPb 2 Br 5 A general schematic of (a); (b) preparing an XRD spectrum of the sample; (c-d) CsPbBr 3 And (e-f) CsPbBr 3 @CsPb 2 Br 5 SEM image of (d).
FIG. 3 is a CsPb prepared in example 1 of the present invention 2 Br 5 XRD spectrum of (1).
FIG. 4 shows (a) CsPbBr in example 1 of the present invention 3 And CsPbBr 3 @CsPb 2 Br 5 XPS measurement spectrum of (a); (b-d) CsPbBr 3 And CsPbBr 3 @CsPb 2 Br 5 High resolution XPS spectra of Cs 3d, pb 4f, br 3 d.
FIG. 5 is a graph showing (a) a UV-vis diffuse reflectance spectrum in example 1 of the present invention; (b) Calculated CsPbBr 3 Light absorption of (2).
FIG. 6 shows the calculated CsPb in (a) UV-vis diffuse reflectance spectrum and (b) the calculated CsPb in example 1 of the present invention 2 Br 5 Light absorption of (2).
FIG. 7 shows photothermal CO of the catalyst obtained in (a-b) of example 1 of the present invention 2 Hydrogenation performance; (c-d) CsPbBr 3 @CsPb 2 Br 5 CO under different conditions 2 Hydrogenation performance; (e) CsPbBr under different catalytic conditions 3 @CsPb 2 Br 5 The yield of CO of (2); (f) Arrhenius diagram shows CsPbBr 3 @CsPb 2 Br 5 CO production in the dark and under light irradiation.
FIG. 8 shows CsPbBr in example 1 of the present invention 3 @CsPb 2 Br 5 In CO 2 And (4) measuring the stability in hydrogenation.
FIG. 9 shows (a) CO in example 1 of the present invention 2 XRD spectrograms before and after photo-thermal hydrogenation; (b) CsPbBr 3 @CsPb 2 Br 5 Photo-thermal CO 2 XRD pattern after hydrogenation.
FIG. 10 shows (a) CsPbBr in example 1 of the present invention 3 And CsPbBr 3 @CsPb 2 Br 5 The steady state luminescence spectrum of (a); (b) Under the excitation of 409nm laser, csPbBr 3 And CsPbBr 3 @CsPb 2 Br 5 PL attenuation spectrum at a given emission wavelength.
FIG. 11 shows (a) CsPbBr in example 1 of the present invention 3 @CsPb 2 Br 5 An in situ XRD spectrum at varying temperature and (b) a UV-DRS spectrum.
FIG. 12 shows CsPbBr in detail in example 1 (a) of the present invention 3 @CsPb 2 Br 5 Changing temperature in-situ XRD spectrogram;(b)CsPbBr 3 @CsPb 2 Br 5 normalized TGA spectrum of (a); (c) XRD spectra CsPbBr before and after 400 ℃ annealing 3 @CsPb 2 Br 5 。
FIG. 13 shows the calculation of CsPbBr in example 1 of the present invention 3 @CsPb 2 Br 5 Light absorption at varying temperatures.
FIG. 14 shows (a-d) CsPbBr in example 1 of the present invention 3 @CsPb 2 Br 5 Carrying out variable-temperature in-situ XPS; csPbBr 3 @CsPb 2 Br 5 In situ FT-IR spectroscopy under (e) dark and (f) photothermal conditions.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the present invention provides a method for preparing an all-inorganic halide perovskite composite material, comprising the steps of:
reacting CsBr and PbBr 2 Proportionally mixing, grinding, and sintering at 300-450 deg.C for a certain time to obtain CsPbBr 3 A material;
reacting CsPbBr 3 The CsPbBr is prepared by the material and water in an organic solvent by adopting an in-situ water etching method 3 CsPbBr radical 3 @CsPb 2 Br 5 A composite material.
In some embodiments, csBr and PbBr 2 The molar ratio of (A) to (B) is 1.
In some embodiments, the sintering temperature is 350-450 ℃ and the sintering time is 1-4h.
Preferably, the sintering temperature is 330-430 ℃, and the sintering time is 1.5-3h.
Further preferably, the sintering temperature is 380-420 ℃, and the sintering time is 1.5-2.5h.
In some embodiments, csPbBr 3 The mass ratio of the material to the water is 1.1-0.5, preferably 1. If the water addition amount is too small, the material will be carvedThe corrosion degree is not enough, and the optimal performance cannot be achieved; the water addition amount is too large, and the material can be decomposed due to excessive etching.
Preferably, the organic solvent is acetonitrile, isopropanol, cyclohexane, n-propanol, acetylene, toluene or acetone, which can disperse the perovskite well but not decompose, and preferably ethanol.
In some embodiments, the in situ water etching reaction time is 0.5-3h, preferably 1-2.5h, and more preferably 1.5-2.5h.
In some embodiments, the method further comprises the steps of washing and drying the prepared product.
Preferably, the washing is 2 to 3 times with acetonitrile and ethanol, respectively.
Preferably, the drying temperature is 50-120 ℃, and the drying time is 10-28h.
Further preferably, the drying temperature is 70-100 ℃, and the drying time is 10-15h.
In a second aspect, the invention provides an all-inorganic halide perovskite composite material prepared by the preparation method. The composite material is CsPbBr 3 As a support material with Cspb 2 Br 5 The heterojunction is formed together, and tests prove that the heterojunction has good photo-thermal catalytic performance.
In a third aspect, the invention provides the use of the all-inorganic halide perovskite composite material in a photo-thermal catalytic reaction;
especially in the photo-thermal catalytic carbon dioxide hydrogenation reaction.
In some embodiments, the application is in methane photo-thermal catalytic dry reforming.
The technical solution of the present invention will be described below with specific examples. The raw materials used in the following examples are commercially available, and the equipment used is conventional.
Examples
CsPbBr 3 @CsPb 2 Br 5 The preparation method of the composite material comprises the following steps:
preparation of CsPbBr 3 The specific conditions of the materials are as follows: csBr and PbBr 2 The molar ratio of materials is 1:1, mixing and grinding, and then sintering for 2h at 400 ℃ to prepare CsPbBr 3 ；
An appropriate amount of water was mixed with the above 1g of CsPbBr 3 Mixing in 100ml absolute ethyl alcohol, stirring to prepare CsPbBr 3 @CsPb 2 Br 5 A composite material. Over time, the color of the mixture changed from yellow to light yellow.
Different CsPb 2 Br 5 CsPbBr content ratio 3 @CsPb 2 Br 5 The composite material is named CsPbBr 3 @CsPb 2 Br 5 -X (X =1,2,3,4,5). The ratio was controlled by adding different water contents, 100 μ L,200 μ L,300 μ L,400 μ L,500 μ L, respectively corresponding to X =1,2,3,4,5.
These composites were collected by multiple washes and centrifugation and finally dried at 80 ℃ for 12h.
As shown in FIG. 2a, firstly, lead perovskite halide CsPbBr is synthesized by solid sintering method 3 . Then a small amount of water is dropped into CsPbBr 3 Preparation of CsPbBr in EtOH suspension 3 @CsPb 2 Br 5 。
The powder X-ray diffraction pattern of the resulting sample is shown in figure 2,b. Pristine CsPbBr by solid phase synthesis 3 Has a cubic structure (JCPDS: 18-364) and good crystallinity. CsPb 2 Br 5 After controlled dissolution of water and etching, three new diffraction peaks appeared at 11.66, 29.35 and 33.43, belonging to the (002), (213) and (310) crystal planes, respectively. The formation of the new material is due to CsBr in H 2 High solubility in O, partial dissolution of CsBr leads to CsPb 2 Br 5 And (4) generating.
FIG. 3 shows pure CsPb 2 Br 5 XRD spectrum of (1), obtained CsPb 2 Br 5 The diffraction peak of (a) matches well with the standard card.
CsPbBr 3 And CsPbBr 3 @CsPb 2 Br 5 Scanning electron microscopy images of the samples, as shown in FIGS. 2,c and f, show that pure CsPbBr 3 The surface of the particles is relatively smooth, and the average particle diameter is about30 μm. However, the morphology of the catalyst becomes rough and broken after water infiltration. This is also due to the dissolution of CsBr in water, and CsBr in CsPbBr 3 Resulting in a change in morphology.
To verify the surface elemental chemistry of the prepared samples, csPbBr was applied 3 And CsPbBr 3 @CsPb 2 Br 5 X-ray photoelectron spectroscopy (XPS) measurements were performed. The C1s peak at 284.8eV was used to calibrate the peak positions of the various elements. CsPbBr 3 And CsPbBr 3 @CsPb 2 Br 5 The XPS measurement spectrum (fig. 4 a) of (a) indicates the presence of Cs, pb and Br elements in the prepared sample. The high resolution XPS spectra of Cs 3d, pb 4f, and Br 3d are shown in FIG. 4,b-d. Apparently, csPbBr 3 @CsPb 2 Br 5 Cs and Br Peak positions of CsPbBr 3 There was no significant change in the comparison. 723.5eV and 737.5eV correspond to Cs 3d 5/2 And Cs 3d 3/2 The binding energy of (1). 3d of Br 5/2 And 3d 3/2 The peaks were 67.8eV and 68.8eV, respectively.
While CsPbBr in 4,c 3 @CsPb 2 Br 5 4f peak of Pb and CsPbBr 3 The 4f peak of Pb is slightly shifted to a higher binding energy (about 0.15 eV). This is due to the fact that in CsPbBr 3 Adding water to dissolve part CsBr, and partial CsPbBr in cubic phase 3 Conversion to tetragonal CsPb 2 Br 5 。
The ultraviolet-visible Diffuse Reflectance Spectrum (DRS) was further tested to investigate the prepared CsPbBr 3 、CsPb 2 Br 5 And CsPbBr 3 @CsPb 2 Br 5 Optical properties of the sample. As shown in FIG. 5, csPbBr 3 At 565 nm. The obtained CsPbBr 3 The band gap of (A) is 2.26eV. By etching with water, csPbBr is prepared 3 @CsPb 2 Br 5 Composite material, csPbBr 3 @CsPb 2 Br 5 The blue shift starting point of (a) is about 550 nm.
Pure CsPb 2 Br 5 The band gap of the UV-vis DRS of (1) is calculated to be about 3.3eV, as shown in FIG. 6. These results demonstrate CsPb 2 Br 5 Ratio CsPbBr 3 Has wider band gap and supports that water can directly drive CsPbBr 3 To CsPb 2 Br 5 The fact of transformation.
Testing the photo-thermal catalysis performance:
the prepared catalyst was subjected to catalytic test studies in an atmospheric quartz beaker reactor. The catalyst (0.2 g) was uniformly dispersed in the bottom of a round quartz beaker with a quartz window. The light source is a 300w Xe lamp (PLS-SXE 300 BUV). Pure Ar and CO are mixed 2 And H 2 The gas mixture of (2) is fed into the reactor in a volume ratio of 3. The reaction temperature was varied between 25-200 ℃. The analysis of the CO content was carried out by means of a gas chromatograph (GC-7920) and a flame ionization detector (FID, YQ1229 column).
Subsequently, for CsPbBr 3 、CsPb 2 Br 5 And CsPbBr 3 @CsPb 2 Br 5 Photothermal catalysis of CO by samples 2 The hydrogenation performance was evaluated. 200mg of catalyst were used and the reaction temperature was 200 ℃.
Fig. 7a and 7b show the photo-thermal catalytic CO production performance of different catalysts. As shown in FIGS. 7a-b, raw CsPbBr 3 The activity of photo-thermal catalysis for producing CO is poor, and is about 7.31mol g -1 h -1 。CsPbBr 3 @CsPb 2 Br 5 The yield of CO of the composite material is obviously improved under the same conditions. CsPbBr 3 @CsPb 2 Br 5 The CO yield of-3 is best, the CO yield is about 69mol g -1 h -1 。
In addition, for pure CsPb 2 Br 5 The samples were tested for performance and the CO yield was about 28.6mol g -1 h -1 。
Due to CsPbBr 3 @CsPb 2 Br 5 The-3 sample has the best CO production performance, so that CsPbBr is subjected to pure light, heat and photo-heat conditions respectively 3 @CsPb 2 Br 5 -3 samples the following independent experiments were performed. CO, as shown in FIGS. 7c and 7d 2 The performance of reduction hydrogenation is poor under the condition of single light or single heat. The yields of CO were 0.44. Mu. Mol g each -1 h -1 And 1.59. Mu. Mol g -1 h -1 . Photothermal activationThe two conditions are respectively improved by 156.8 times and 43.4 times, which shows that light and heat are applied to CO 2 The hydrogenation reduction has a synergistic effect. CsPbBr 3 @CsPb 2 Br 5 In CO 2 The cycle stability in hydrogenation was good (fig. 8). CsPbBr 3 @CsPb 2 Br 5 Photo-thermal CO 2 Comparison of XRD spectra before and after hydrogenation, as shown in FIG. 9, csPbBr 3 @CsPb 2 Br 5 There was neither significant phase transformation nor structural failure, and all diffraction peaks matched well with the standard card.
Photothermal catalysis mechanism analysis:
to explore the mechanism of separation of photogenerated carriers, csPbBr was studied 3 And CsPbBr 3 @CsPb 2 Br 5 Was tested for Photoluminescence (PL) spectra as shown in figure 10 a. CsPbBr at excitation wavelength of 409nm 3 @CsPb 2 Br 5 Having a photoluminescence intensity lower than that of pure CsPbBr 3 Indicating CsPbBr 3 @CsPb 2 Br 5 Efficient separation of photo-generated charges in a composite.
In addition, csPbBr was measured 3 And CsPbBr 3 @CsPb 2 Br 5 As shown in fig. 10b, as a Time Resolved Photoluminescence (TRPL) spectrum. The PL decay curve calculates the average carrier lifetime by means of a three exponential function. CsPbBr 3 @CsPb 2 Br 5 Has a lifetime of 4.688ns, which is lower than CsPbBr 3 7.494ns, indicating that the prepared CsPbBr 3 @CsPb 2 Br 5 The composite material can improve the transfer of photon-generated carriers and the separation efficiency of electron holes.
Thus, csPbBr synthesized by water etching 3 @CsPb 2 Br 5 The heterojunction can effectively inhibit the recombination of photon-generated carriers, improve the charge transfer efficiency and further improve the photocatalytic reaction.
Due to CO 2 The hydrogenation reaction is endothermic (Δ H =41 KJ/mol) and increasing the temperature can provide additional energy for the reaction, promoting the production of product. Increasing the temperature also increases the reaction rate and activates more CO 2 And H 2 The molecule, and at the same time, the presence of light is reducedActivation energy of the reaction.
To study CsPbBr 3 @CsPb 2 Br 5 In CO 2 Conversion in photothermal hydrogenation process, first to CsPbBr 3 @CsPb 2 Br 5 In situ XRD patterns at different temperatures were performed (fig. 11 a). Fig. 11a and 12a are in situ XRD spectra. CsPbBr 3 Upon heating to 150 ℃, a tetragonal to cubic phase transition occurs, consistent with literature reports. Meanwhile, the position of the characteristic peaks of XRD shifts to a small angle with an increase in temperature due to thermal expansion of the crystal lattice. Notably, csPb in the composite 2 Br 5 The intensity of the characteristic peak starts to decrease when the temperature rises to 350 c and almost disappears when the temperature rises to 400 c. This is probably due to CsPb 2 Br 5 The crystallinity is lost and the crystal structure tends to be amorphous.
Thermogravimetric analysis showed CsPbBr 3 @CsPb 2 Br 5 With good thermal stability (figure 12 b). Therefore, to further explore this phenomenon, the samples were heated to 400 ℃ and held for a period of time. After the sample cooled to room temperature, csPb can be observed again 2 Br 5 Indicating that this change is reversible (fig. 12 c). These results illustrate CsPbBr 3 @CsPb 2 Br 5 The change in the heterojunction during heating also demonstrates that the catalyst is stable at the reaction temperature of the present operation.
In addition, in-situ UV-vis DRS spectra at different temperatures are obtained, and the prepared CsPbBr is further understood 3 @CsPb 2 Br 5 Optical properties of the heterojunction. As shown in FIGS. 11b and 13, the absorption edge of the sample gradually red-shifted with increasing temperature, indicating CsPbBr 3 @CsPb 2 Br 5 The band gap of (a) becomes narrow. In general, the narrower the bandgap of the photocatalyst, the higher the light utilization efficiency, which may be CsPbBr 3 @CsPb 2 Br 5 Another reason for exhibiting better photocatalytic performance under photothermal conditions. In addition, in-situ XPS spectrum tests were performed at different temperatures, and CsPbBr was studied 3 @CsPb 2 Br 5 Elemental junctions at different temperaturesAnd (4) energy combination. As shown in fig. 14a-d, the 1s peak of C does not change during heating, and the binding energy of Cs 3d shifts significantly toward higher binding energies as the temperature is increased to 150 ℃. Similar changes in binding energy are also observed in Pb 4f and Br 3d, which may be related to phase transitions of the material. In the in-situ X-ray diffraction, when the temperature is increased from room temperature, the binding energy of each element of the sample shifts to the direction of high binding energy, and when the temperature exceeds 150 ℃, particularly as the temperature is continuously increased, the binding energy of Cs 3d, pb 4f and Br 3d hardly changes, which is consistent with the phenomenon that phase transformation occurs in the in-situ XRD spectrogram along with the change of the temperature.
To further understand the photothermal CO 2 Reaction details of the hydrogenation process are detected by in-situ Fourier transform infrared spectroscopy (FT-IR) under photo-thermal conditions. FIG. 14, e is CsPbBr 3 @CsPb 2 Br 5 CO under dark conditions 2 And H 2 Transient infrared spectroscopy in the mixture. At 1038cm -1 And 1064cm -1 Two peaks appear and their intensity increases with time, probably due to CO 2 Linear adsorption of species on the catalyst surface. Furthermore, 1201cm -1 The characteristics of (A) can be attributed to the bicarbonate species (HCO) 3 - ) And 1539cm -1 And 1670cm -1 The characteristics of (a) correspond to asymmetric and symmetric stretching vibrations (b-CO) of the bicarbonate, respectively 3 2- ). The intensity of these peaks increases with increasing dark reaction time, indicating that CO is present 2 Is adsorbed on the catalyst surface. 1384cm when the closed in situ cell is in photothermal conditions -1 There begins to peak and the peak intensity increases with increasing photothermal time, probably due to asymmetric stretching vibrations of the bidentate carbonate (fig. 14 f). In addition, 1559cm -1 The peak at (a) may correspond to tensile oscillations of the COOH groups (fig. 14 f). Also, the intensity increased with increasing photothermal time, indicating that formate was produced under photothermal conditions. Therefore, the photothermal synergistic effect can promote the generation of bidentate carbonate and formate, and finally improve the generation rate of CO.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of an all-inorganic halide perovskite composite material is characterized by comprising the following steps: the method comprises the following steps:
reacting CsBr and PbBr 2 Proportionally mixing, grinding, and sintering at 300-450 deg.C for a certain time to obtain CsPbBr 3 A material;
reacting CsPbBr 3 The CsPbBr is prepared by the material and water in an organic solvent by adopting an in-situ water etching method 3 CsPbBr radical 3 @CsPb 2 Br 5 A composite material.
2. The method of preparing an all-inorganic halide perovskite composite material as claimed in claim 1, wherein: csBr and PbBr 2 The molar ratio of (A) to (B) is 1.
3. The method of preparing an all-inorganic halide perovskite composite material according to claim 1, wherein: the sintering temperature is 350-450 ℃, and the sintering time is 1-4h.
4. The method of preparing an all-inorganic halide perovskite composite material as claimed in claim 1, wherein: csPbBr 3 The mass ratio of the material to the water is 1.1-0.5, preferably 1.
5. The method of preparing an all-inorganic halide perovskite composite material according to claim 1, wherein: the organic solvent is acetonitrile, isopropanol, cyclohexane, n-propanol, acetylene, toluene or acetone.
6. The method of preparing an all-inorganic halide perovskite composite material according to claim 1, wherein: the reaction time of the in-situ water etching method is 0.5-3h.
7. The method of preparing an all-inorganic halide perovskite composite material according to claim 1, wherein: also comprises the steps of washing and drying the prepared product.
8. The method of preparing an all-inorganic halide perovskite composite material according to claim 1, wherein: the washing is carried out for 2-3 times by respectively adopting acetonitrile and ethanol;
the drying temperature is 50-120 ℃, and the drying time is 10-28h.
9. An all-inorganic halide perovskite composite material, characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. Use of the all-inorganic halide perovskite composite material of claim 9 in photo-thermal catalytic reactions;
especially in the photo-thermal catalytic carbon dioxide hydrogenation reaction.
CN202210508645.0A 2022-05-11 2022-05-11 All-inorganic halide perovskite composite material and preparation method and application thereof Active CN115212902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210508645.0A CN115212902B (en) 2022-05-11 2022-05-11 All-inorganic halide perovskite composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210508645.0A CN115212902B (en) 2022-05-11 2022-05-11 All-inorganic halide perovskite composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115212902A true CN115212902A (en) 2022-10-21
CN115212902B CN115212902B (en) 2024-04-05

Family

ID=83608574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210508645.0A Active CN115212902B (en) 2022-05-11 2022-05-11 All-inorganic halide perovskite composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115212902B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950375A (en) * 2019-12-02 2020-04-03 山东省分析测试中心 CsPb2Br5Middle doped CsPbBr3Composite perovskite material and preparation method and application thereof
CN112442363A (en) * 2020-11-10 2021-03-05 厦门理工学院 All-inorganic perovskite nanocrystal and pseudo-peritectic synthesis method thereof
CN112892573A (en) * 2021-01-20 2021-06-04 陕西师范大学 Perovskite composite material coated by CN as well as preparation method and application thereof
CN113244935A (en) * 2021-05-17 2021-08-13 电子科技大学长三角研究院(湖州) In-situ generated perovskite heterojunction photocatalyst and preparation method thereof
CN113441159A (en) * 2021-07-30 2021-09-28 陕西科技大学 Nickel/titanium carbide photo-thermal catalytic material and preparation method and application thereof
US20210402380A1 (en) * 2020-06-23 2021-12-30 San Diego State University Foundation Perovskites for photocatalytic organic synthesis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950375A (en) * 2019-12-02 2020-04-03 山东省分析测试中心 CsPb2Br5Middle doped CsPbBr3Composite perovskite material and preparation method and application thereof
US20210402380A1 (en) * 2020-06-23 2021-12-30 San Diego State University Foundation Perovskites for photocatalytic organic synthesis
CN112442363A (en) * 2020-11-10 2021-03-05 厦门理工学院 All-inorganic perovskite nanocrystal and pseudo-peritectic synthesis method thereof
CN112892573A (en) * 2021-01-20 2021-06-04 陕西师范大学 Perovskite composite material coated by CN as well as preparation method and application thereof
CN113244935A (en) * 2021-05-17 2021-08-13 电子科技大学长三角研究院(湖州) In-situ generated perovskite heterojunction photocatalyst and preparation method thereof
CN113441159A (en) * 2021-07-30 2021-09-28 陕西科技大学 Nickel/titanium carbide photo-thermal catalytic material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TIANYUAN LIANG ET AL.: "In Situ Phase-Transition Crystallization of All-Inorganic Water- Resistant Exciton-Radiative Heteroepitaxial CsPbBr3−CsPb2Br5 Core−Shell Perovskite Nanocrystals", 《CHEMISTRY OF MATERIALS》 *

Also Published As

Publication number Publication date
CN115212902B (en) 2024-04-05

Similar Documents

Publication Publication Date Title
Qi et al. Photoinduced defect engineering: enhanced photothermal catalytic performance of 2D black In2O3− x nanosheets with bifunctional oxygen vacancies
Deng et al. Metal-organic framework-derived Ga-Cu/CeO2 catalyst for highly efficient photothermal catalytic CO2 reduction
Zang et al. Facile synthesis of composite g-C 3 N 4/WO 3: a nontoxic photocatalyst with excellent catalytic activity under visible light
Kulkarni et al. Nanostructured N-doped orthorhombic Nb 2 O 5 as an efficient stable photocatalyst for hydrogen generation under visible light
Yu et al. Dual modification of TiNb 2 O 7 with nitrogen dopants and oxygen vacancies for selective aerobic oxidation of benzylamine to imine under green light
Bi et al. Efficient solar-driven conversion of nitrogen to ammonia in pure water via hydrogenated bismuth oxybromide
CN107686120B (en) Method for catalytically synthesizing ammonia by gathering solar energy and catalyst thereof
US9764959B2 (en) Nanostructured metal oxide compositions for applied photocatalysis
EP3807220A1 (en) Photocatalyst and use thereof
Han et al. Synthesis of single-crystalline, porous TaON microspheres toward visible-light photocatalytic conversion of CO 2 into liquid hydrocarbon fuels
CN108786849B (en) Preparation and application of tin sulfide/titanium dioxide composite material
Verma et al. Autonomous self-optimizing defects by refining energy levels through hydrogenation in CeO 2–x polymorphism: a walking mobility of oxygen vacancy with enhanced adsorption capabilities and photocatalytic stability
Xing et al. Bi 2 Sn 2 O 7–TiO 2 nanocomposites for enhancing visible light photocatalytic activity
Yang et al. Light‐Induced Synthesis of Oxygen‐Vacancy‐Functionalized Ni (OH) 2 Nanosheets for Highly Selective CO2 Reduction
Li et al. Unleashing the Full Potential of Photo‐Driven CO Hydrogenation to Light Olefins over Carbon‐Coated CoMn‐Based Catalysts
Abdelbasir et al. Superior UV-light photocatalysts of nano-crystalline (Ni or Co) FeWO 4: Structure, optical characterization and synthesis by a microemulsion method
Li et al. Boosting CO production from visible-light CO 2 photoreduction via defects-induced electronic-structure tuning and reaction-energy optimization on ultrathin carbon nitride
Khatamian et al. Photocatalytic hydrogen generation over CdS–metalosilicate composites under visible light irradiation
Khore et al. A green approach: scalable dry media synthesis of a γ-TaON photocatalyst for solar H 2 production and rhodamine B degradation
CN115212902A (en) All-inorganic halide perovskite composite material and preparation method and application thereof
Han et al. An artful and simple synthetic strategy for fabricating low carbon residual porous gC 3 N 4 with enhanced visible-light photocatalytic properties
Zhang et al. Structural Heredity in Catalysis: CO2 Self‐Selective CeO2 Nanocrystals for Efficient Photothermal CO2 Hydrogenation to Methane
Yin et al. High photocatalytic performance over ultrathin 2D TiO 2 for CO 2 reduction to alcohols
US11433384B2 (en) Nitrogen-doped catalyst for oxidative coupling reaction of methane, manufacturing method of nitrogen-doped catalyst for oxidative coupling reaction of methane thereby, and method for oxidative coupling reaction of methane using the same
Hu et al. Roles of titania and plasmonic gold nanoparticles of different sizes in photocatalytic methane coupling at room temperature

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant