CN114985013A - Strain-modulated bismuth-based metal organic framework/bismuth oxybromide material and application thereof - Google Patents
Strain-modulated bismuth-based metal organic framework/bismuth oxybromide material and application thereof Download PDFInfo
- Publication number
- CN114985013A CN114985013A CN202210685283.2A CN202210685283A CN114985013A CN 114985013 A CN114985013 A CN 114985013A CN 202210685283 A CN202210685283 A CN 202210685283A CN 114985013 A CN114985013 A CN 114985013A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- based metal
- organic framework
- strain
- oxybromide
- 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
Links
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 60
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 57
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000007146 photocatalysis Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 14
- 230000033228 biological regulation Effects 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 30
- 239000001569 carbon dioxide Substances 0.000 abstract description 30
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000001994 activation Methods 0.000 abstract description 5
- 239000008204 material by function Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000003795 desorption Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013141 crystalline metal-organic framework Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a strain-modulated bismuth-based metal organic framework/bismuth oxybromide composite functional material, and belongs to the field of nano functional materials. The composite functional material is a bismuth-based metal-organic framework with compressive strain anchored on the surface of bismuth oxybromide, wherein the bismuth oxybromide is of a two-dimensional structure, the anchored bismuth-based metal-organic framework is of a thin-layer structure and has higher compressive strain, and the strain degree is as high as 7.85%. The composite material realizes the cascade of functions and the introduction of strain improves the adsorption and activation process of the material to carbon dioxide molecules. The theoretical mass ratio of the bismuth oxybromide to the bismuth-based metal organic framework is (2.0-4.9): 1. The composite functional material of the invention is used for photocatalysis of CO 2 In the reduction, the CO generation rate is as high as 21.96 mu mol g under the irradiation of visible light ‑1 h ‑1 And has a CO selectivity of 96.4%.
Description
Technical Field
The invention belongs to the field of functional composite materials, and particularly relates to a strain-modulated bismuth-based metal organic framework/bismuth oxybromide material and application thereof in photocatalytic carbon dioxide reduction.
Technical Field
Realized by clean and unlimited solar energyThe efficient reduction of carbon dioxide into fuel and high value-added chemicals is a technology capable of simultaneously solving environmental problems such as energy crisis, greenhouse gases and the like. In carbon dioxide (CO) 2 ) In a typical process of photoreduction, CO 2 The absorption and activation of (a), the excitation and transport and separation of photogenerated charges, and the desorption process of the target intermediate all determine the overall efficiency of the photocatalysis. The regulation of charge kinetics associated with charge generation, migration, separation has been extensively studied, however, there is little concern about the electronic structure regulation directly associated with the adsorption or desorption processes (kinetic processes). Therefore, either from the perspective of improving overall efficiency or from revealing complex CO 2 Regulating and controlling CO from the angle of photoreduction mechanism 2 Are more attractive and challenging to adsorb and photoactivate or accelerate the thermo-kinetic processes such as dissociation of specific intermediates. In recent years, porous crystalline Metal Organic Framework (MOF) materials have caused a hot tide of research in the field of energy transfer or charge transfer due to their flexible coordination environment, adjustable electronic structure and strong adsorption capacity to small molecules. The anchoring of metal framework materials on the photocatalyst surface allows the integration or concatenation of specific functions of different materials, e.g. MOF on CO 2 Adsorption of molecules and supply of photo-generated charges by the catalyst. In addition, the MOF/catalyst structure with integrated functions can be used as an ideal platform for further dynamic process modulation and catalytic mechanism research.
Due to the high correlation with the intrinsic variation of the electronic structure of the material surface, the strain regulation stands out in the advanced material design. Among the various strain regulation-induced features, the modulation of the adsorption energy of target molecules or intermediates is of great interest. By means of the designed MOF/catalyst material, a reasonable high-speed channel can be established for strain regulation and control of the surface of the catalytic site so as to optimize the catalytic reaction process and finally realize the catalytic material with excellent performance and high selectivity. However, no literature reports on strain regulation of functional composite MOF/catalysts to date.
Disclosure of Invention
The invention aims to provide a strain-modulated bismuth-based metal organic framework/bismuth oxybromide composite materialAnd the composite material integrates the functions of two monomer materials and higher CO 2 To carbon monoxide (CO) conversion.
In order to realize the purpose, the invention adopts the following technical scheme:
the strain-modulated bismuth-based metal organic framework/bismuth oxybromide material is characterized in that bismuth oxybromide has a two-dimensional (2D) structure, a thin-layer bismuth-based metal organic framework (Bi-MOF) is anchored on the surface, the surface of the Bi-MOF has higher strain, and the strain degree can reach 7.85%. The structure can integrate the functions of Bi-MOF and photocatalytic material bismuth oxybromide, wherein the Bi-MOF is used as a catalytic site for adsorbing, activating and converting CO 2 And bismuth oxybromide provides electrons with strong reduction capability, so that a functional cascade system is formed. The theoretical mass ratio of the bismuth oxybromide to the Bi-MOF is (2.0-4.9): 1.
The strain modulated bismuth-based metal organic framework/bismuth oxybromide material is characterized by being prepared by adopting an in-situ growth method and then carrying out light radiation, and comprises the following steps:
step S1, preparing a 2D bismuth oxybromide nanosheet monomer:
bismuth nitrate pentahydrate and potassium bromide are used as raw materials, and the bismuth nitrate pentahydrate and the potassium bromide are prepared by a hydrothermal method; the method specifically comprises the following steps: respectively dispersing bismuth nitrate pentahydrate (with mass concentration of 48.5g/L) and potassium bromide (with mass concentration of 11.5g/L) into 20mL of ethanol, fully stirring, mixing, transferring into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 16 hours at 160 ℃; and after the reaction is finished, cooling, separating, washing and drying the solid sample to obtain the 2D bismuth oxybromide nanosheet. The obtained bismuth oxybromide material (BiOBr) is used for the subsequent synthesis of composite nano materials.
Step S2, preparing the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material by an in-situ growth method, and strain regulation:
s2.1, ultrasonically dispersing the bismuth oxybromide prepared in the step 1 into 20mL of ethanol/N, N-dimethylformamide/deionized water mixed solution, adding a certain amount of trimesic acid, wherein the mass concentration of the bismuth oxybromide is 2g/L, the mass concentration of the trimesic acid is 1-3 g/L, and the volume ratio of the ethanol to the N, N-dimethylformamide to the deionized water is 1:1: 1.
S2.2, placing the solution in the step 2.1 into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating for 24 hours at 100 ℃; and after the reaction is finished, cooling, separating and washing the solid sample, then soaking in methanol for 6 hours, collecting and drying to obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material. And then, carrying out light radiation treatment (300W xenon lamp) on the obtained material for 10-40 hours to finally obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional material with surface compressive strain.
The invention also provides a bismuth-based metal organic framework/bismuth oxybromide composite photocatalytic material with surface strain cascade function for photocatalytic CO 2 Application in the field of reduction; specifically, under the irradiation of visible light (300W xenon lamp), the CO generation rate is as high as 21.96 mu mol g -1 h -1 And has a CO selectivity of over 96%; the performances are respectively 1.48,4.3 and 8.6 times of that of the composite material without strain modulation, pure bismuth oxybromide and pure bismuth-based metal organic framework.
Compared with the existing composite functional photocatalytic material, the invention has the beneficial effects that:
(1) according to the strain-modulated bismuth-based metal organic framework/bismuth oxybromide material, the bismuth-based metal organic framework is anchored on the surface of two-dimensional bismuth oxybromide in a thin layer form, and the structure realizes the cascade of specific functions of the two in the photocatalytic carbon dioxide reduction. Namely, the bismuth-based metal organic framework is taken as a site for adsorption activation and CO conversion 2 And bismuth oxybromide provides photogenerated electrons.
(2) The strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material disclosed by the invention induces and generates huge compressive strain on the bismuth-based metal-organic framework, improves the adsorption and activation behaviors of the material on carbon dioxide by strain regulation, promotes the desorption of CO, enables the material to have high conversion rate and high selectivity on a CO reduction product, and has a potential application prospect in the field of photocatalytic carbon dioxide reduction.
(3) The strain-modulated bismuth-based metal organic framework/bismuth oxybromide material does not need to add any sacrificial agent or cocatalyst in the carbon dioxide reduction, greatly saves the economic cost and has no pollution in the aspect of environment.
Drawings
FIG. 1 is an in situ Raman (in situ Raman) spectrum of a bismuth-based metal organic framework/bismuth oxybromide material strain modulation process of the present invention; in the figure, BiOBr-mof1 represents a bismuth-based metal organic framework/bismuth oxybromide material which is not subjected to strain modulation, the mass concentration of correspondingly added trimesic acid is 1g/L, s-BiOBr-mof1 represents the bismuth-based metal organic framework/bismuth oxybromide material which is subjected to strain modulation, and the light radiation time is 40 hours.
FIG. 2 shows Transmission Electron Microscope (TEM) and High Resolution Transmission Electron Microscope (HRTEM) photographs of a bismuth-based metal organic framework/bismuth oxybromide material with or without strain modulation according to the present invention, wherein a and b correspond to the composite material without strain modulation, and c and d correspond to the composite material after 40 hours of light irradiation treatment.
FIG. 3 is a carbon dioxide temperature programmed desorption diagram of the strain modulated bismuth-based metal organic framework/bismuth oxybromide material of the present invention.
FIG. 4 is a graph comparing the rate of formation of the carbon dioxide photocatalytic reduction product of the strain modulated bismuth-based metal organic framework/bismuth oxybromide material of the present invention.
FIG. 5 is a graph of the selectivity of the carbon dioxide photocatalytic reduction product of the strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material of the present invention.
The specific description is as follows:
the strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material of the present invention will be described in detail with reference to the accompanying drawings. Embodiments of the present invention will be described in detail below with reference to the drawings, but the scope of the present invention is not limited to these embodiments.
Example 1:
step S1, preparing a 2D bismuth oxybromide nanosheet monomer:
respectively dispersing bismuth nitrate pentahydrate (with mass concentration of 48.5g/L) and potassium bromide (with mass concentration of 11.5g/L) into 20mL of ethanol, fully stirring, mixing, transferring into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 16 hours at 160 ℃; and after the reaction is finished, cooling, separating, washing and drying the solid sample to obtain the 2D bismuth oxybromide nanosheet. The obtained bismuth oxybromide material is used for the subsequent synthesis of composite nano materials.
Step S2, preparing bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material by an in-situ growth method, and strain regulation:
s2.1 ultrasonically dispersing 200mg of the bismuth oxybromide prepared in the step 1 into 20mL of a mixed solution of ethanol/N, N-dimethylformamide/deionized water, and then adding 20mg of trimesic acid, wherein the volume ratio of the ethanol, the N, N-dimethylformamide to the deionized water is 1:1: 1.
S2.2, placing the solution in the step 2.1 into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating for 24 hours at 100 ℃; and after the reaction is finished, cooling, separating and washing the solid sample, then soaking in methanol for 6 hours, collecting and drying to obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material. And then, carrying out light radiation treatment on the obtained material (a 300W xenon lamp) for 40 hours to finally obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional material with surface compressive strain.
FIG. 1 is an in situ Raman diagram of the strain modulation process of a bismuth-based metal-organic framework/bismuth oxybromide material, which shows the characteristic vibration of the bismuth-based metal-organic framework and the characteristic vibration of bismuth oxybromide in the composite material, and indicates the successful anchoring of the bismuth-based metal-organic framework material on the surface of the bismuth oxybromide. In addition, the in-situ spectra showed a gradual blue shift of the characteristic vibrational peak of the bismuth-based metal-organic framework during light irradiation, indicating the generation of compressive strain of the bismuth-based metal-organic framework.
Fig. 2 is TEM and HRTEM photographs of the bismuth-based metal organic framework/bismuth oxybromide material with or without strain modulation of the present invention, it can be clearly seen that the bismuth-based metal organic framework is successfully anchored on the surface of the two-dimensional bismuth oxybromide nanosheet, the lattice spacing of the surface of the bismuth-based metal organic framework after the optical radiation treatment is changed from standard 0.33nm to 0.305nm, which intuitively illustrates the generation of compressive strain, which is calculated to be as high as 7.85%.
FIG. 3 is a carbon dioxide temperature programmed desorption diagram of the strain-modulated bismuth-based metal organic framework/bismuth oxybromide material of the present invention, wherein a decrease in the area of the composite material spectrum and a transition to a low temperature, relative to bismuth oxybromide alone, indicate a decrease in the adsorption capacity and an enhancement in the activation capacity of the strain-modulated bismuth-based metal organic framework/bismuth oxybromide material.
FIG. 4 shows the CO and CH of a strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material under visible light irradiation 4 A generated rate comparison graph. Wherein, CO is the main product, and the generation rate is as high as 21.96 mu mol g -1 h -1 The performances are respectively 1.48,4.3 and 8.6 times of those of the composite material without strain modulation, pure bismuth oxybromide and pure bismuth-based metal organic framework.
FIG. 5 shows the selectivity of the strain-modulated CO product of the bismuth-based metal-organic framework/bismuth oxybromide material, and the CO product selectivity of the synthesized composite material exceeds 96%.
Example 2:
example 2 is different from example 1 in that: and (3) adjusting the time of the light radiation treatment of the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material obtained in the step (2.2) to 10 hours. The rest of the procedure was the same as in example 1.
Example 3:
example 3 is different from example 1 in that: and (3) adjusting the time of the light radiation treatment of the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material obtained in the step 2.2 to be 20 hours. The rest of the procedure was the same as in example 1.
Example 4:
example 4 is different from example 1 in that: the time for carrying out light radiation treatment on the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material obtained in the step 2.2 is adjusted to be 30 hours. The remaining procedure was the same as in example 1.
Example 5:
example 5 differs from example 1 in that: adjusting the amount of trimesic acid in the step 2.1 to 60 mg; and (3) adjusting the time of the light radiation treatment of the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material obtained in the step (2.2) to 10 hours. The remaining procedure was the same as in example 1.
Claims (3)
1. A strain-modulated bismuth-based metal organic framework/bismuth oxybromide composite material is characterized in that: the bismuth oxybromide has a two-dimensional (2D) structure, a thin layer of bismuth-based metal organic framework (Bi-MOF) is anchored on the surface, and the surface of the Bi-MOF has higher strain, wherein the strain degree can reach 7.85%; the structure can integrate the functions of Bi-MOF and photocatalytic material bismuth oxybromide, wherein the Bi-MOF is used as a catalytic site for adsorbing, activating and converting CO 2 And the bismuth oxybromide provides electrons with strong reduction capability so as to form a functional cascade system, and the theoretical mass ratio of the bismuth oxybromide to the Bi-MOF is (2.0-4.9): 1.
2. A method of preparing a strain modulated bismuth based metal organic framework/bismuth oxybromide composite material as claimed in claim 1, characterized in that: the method comprises the following steps:
step S1, preparing a 2D bismuth oxybromide nanosheet monomer:
bismuth nitrate pentahydrate and potassium bromide are used as raw materials, and the bismuth nitrate pentahydrate and the potassium bromide are prepared by a hydrothermal method; the method specifically comprises the following steps: respectively dispersing bismuth nitrate pentahydrate (with mass concentration of 48.5g/L) and potassium bromide (with mass concentration of 11.5g/L) into 20mL of ethanol, fully stirring, mixing, transferring into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 16 hours at 160 ℃; and after the reaction is finished, cooling, separating, washing and drying the solid sample to obtain a 2D bismuth oxybromide nanosheet, wherein the obtained bismuth oxybromide material (BiOBr) is used for the subsequent synthesis of the composite nanomaterial.
Step S2, preparing the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material by an in-situ growth method, and strain regulation:
s2.1, ultrasonically dispersing the bismuth oxybromide prepared in the step 1 into 20mL of ethanol/N, N-dimethylformamide/deionized water mixed solution, adding a certain amount of trimesic acid, wherein the mass concentration of the bismuth oxybromide is 2g/L, the mass concentration of the trimesic acid is 1-3 g/L, and the volume ratio of the ethanol to the N, N-dimethylformamide to the deionized water is 1:1: 1.
S2.2, placing the solution in the step 2.1 into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating for 24 hours at 100 ℃; after the reaction is finished, cooling, separating and washing the solid sample, then immersing the solid sample in methanol for 6 hours, collecting and drying to obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional photocatalytic material; and then, carrying out light radiation treatment (300W xenon lamp) on the obtained material for 10-40 hours to finally obtain the bismuth-based metal organic framework/bismuth oxybromide composite functional material with surface compressive strain.
3. The strain-modulated bismuth-based metal organic framework/bismuth oxybromide composite material of claim 1 in photocatalysis of CO 2 Application in reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210685283.2A CN114985013B (en) | 2022-06-15 | 2022-06-15 | Strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210685283.2A CN114985013B (en) | 2022-06-15 | 2022-06-15 | Strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114985013A true CN114985013A (en) | 2022-09-02 |
| CN114985013B CN114985013B (en) | 2023-05-23 |
Family
ID=83034453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210685283.2A Active CN114985013B (en) | 2022-06-15 | 2022-06-15 | Strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114985013B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117563582A (en) * | 2023-10-27 | 2024-02-20 | 齐齐哈尔大学 | Bi/BiOBr@Bi-MOF heterojunction photocatalyst rich in oxygen vacancies and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211030A (en) * | 2011-04-11 | 2011-10-12 | 山东大学 | Nano silver/silver bromide/bismuth oxybromide heterogeneous visible light photo-catalytic material and preparation method thereof |
| CN110721747A (en) * | 2019-10-18 | 2020-01-24 | 张贵勇 | Metal organic framework photocatalytic hydrogen production composite material and preparation method thereof |
| CN111701601A (en) * | 2020-06-05 | 2020-09-25 | 南阳师范学院 | Bi4O5Br2Preparation method of self-assembled hollow flower ball and photocatalytic reduction of CO2Application of aspects |
| CN112675911A (en) * | 2021-02-08 | 2021-04-20 | 福州大学 | CTFs/Bi/BiOBr composite photocatalyst for sewage purification and carbon dioxide reduction under cooperation of visible light catalysis |
| CN112877714A (en) * | 2021-01-27 | 2021-06-01 | 浙江大学衢州研究院 | Double-defect ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof |
| CN112892608A (en) * | 2021-01-20 | 2021-06-04 | 江苏大学 | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof |
| CN113058655A (en) * | 2021-03-29 | 2021-07-02 | 杭州朗迈新材料有限公司 | Preparation method and application of BiOCl/Fe-MOFs composite catalytic material |
-
2022
- 2022-06-15 CN CN202210685283.2A patent/CN114985013B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211030A (en) * | 2011-04-11 | 2011-10-12 | 山东大学 | Nano silver/silver bromide/bismuth oxybromide heterogeneous visible light photo-catalytic material and preparation method thereof |
| CN110721747A (en) * | 2019-10-18 | 2020-01-24 | 张贵勇 | Metal organic framework photocatalytic hydrogen production composite material and preparation method thereof |
| CN111701601A (en) * | 2020-06-05 | 2020-09-25 | 南阳师范学院 | Bi4O5Br2Preparation method of self-assembled hollow flower ball and photocatalytic reduction of CO2Application of aspects |
| CN112892608A (en) * | 2021-01-20 | 2021-06-04 | 江苏大学 | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof |
| CN112877714A (en) * | 2021-01-27 | 2021-06-01 | 浙江大学衢州研究院 | Double-defect ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof |
| CN112675911A (en) * | 2021-02-08 | 2021-04-20 | 福州大学 | CTFs/Bi/BiOBr composite photocatalyst for sewage purification and carbon dioxide reduction under cooperation of visible light catalysis |
| CN113058655A (en) * | 2021-03-29 | 2021-07-02 | 杭州朗迈新材料有限公司 | Preparation method and application of BiOCl/Fe-MOFs composite catalytic material |
Non-Patent Citations (1)
| Title |
|---|
| SHUAI-RU ZHU等: ""In Situ Growth of Metal−Organic Framework on BiOBr 2D Material with Excellent Photocatalytic Activity for Dye Degradation"", 《CRYST. GROWTH DES.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117563582A (en) * | 2023-10-27 | 2024-02-20 | 齐齐哈尔大学 | Bi/BiOBr@Bi-MOF heterojunction photocatalyst rich in oxygen vacancies and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114985013B (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN111036243B (en) | Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof | |
| CN115007186B (en) | Carbon nitride-based site-specific double-single-atom catalyst, preparation and application thereof | |
| CN111701601A (en) | Bi4O5Br2Preparation method of self-assembled hollow flower ball and photocatalytic reduction of CO2Application of aspects | |
| CN113351210B (en) | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction | |
| CN113680361B (en) | Cobalt-ruthenium bimetallic monatomic photocatalyst as well as preparation method and application thereof | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN114177940B (en) | Preparation and application of monoatomic Cu anchored covalent organic framework material | |
| CN114985013B (en) | Strain-modulated bismuth-based metal-organic framework/bismuth oxybromide material and application thereof | |
| CN115400773B (en) | Molybdenum phosphide-red phosphorus composite photocatalyst and preparation method and application thereof | |
| CN114931965B (en) | Porous graphite-phase carbon nitride-supported non-noble metal bismuth catalyst, preparation and application thereof | |
| CN114870899A (en) | Photocatalytic CO 2 Composite photocatalyst for preparing synthesis gas by decomposition and preparation method thereof | |
| CN114345347A (en) | Cobalt ferrite cocatalyst, and preparation method and application thereof | |
| CN116371425B (en) | CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst | |
| CN117181250B (en) | Preparation method and application of broad spectrum response composite material based on black phosphorus nano-sheet | |
| CN112958124B (en) | Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof | |
| CN115770576B (en) | Nickel-titanium composite catalyst and preparation method and application thereof | |
| CN114797932B (en) | Bimetallic 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof | |
| CN115739163B (en) | Sulfide-nitride heterojunction composite photocatalyst and preparation method and application thereof | |
| CN116272937B (en) | TiO (titanium dioxide)2Preparation method and application of nanosheet material | |
| CN115999641B (en) | CeO (CeO) 2 Cu-TCPP composite photocatalyst and preparation method and application thereof | |
| CN115920945B (en) | Hydroxylated graphite phase carbon nitride photocatalyst and preparation method and application thereof | |
| CN117414870A (en) | Copper phthalocyanine-based Z-type photocatalyst, preparation method and application thereof in photocatalytic carbon dioxide reduction | |
| US20220169591A1 (en) | Preparing method of linear carbonate compounds | |
| CN117358260B (en) | Double-heterojunction structure photocatalyst and preparation method and application thereof |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240325 Address after: No. 8, 4th Floor, Building 3, No. 88, Jitai Fifth Road, Chengdu Hi-tech Zone, China (Sichuan) Pilot Free Trade Zone, Chengdu, Sichuan 610095 Patentee after: Chengdu Jinluo Technology Co.,Ltd. Country or region after: China Address before: 611731, No. 2006, West Avenue, Chengdu hi tech Zone (West District, Sichuan) Patentee before: University of Electronic Science and Technology of China Country or region before: China |