CN114471722B - Preparation method and application of three-dimensional DUT-67/RGO aerogel photocatalyst - Google Patents
Preparation method and application of three-dimensional DUT-67/RGO aerogel photocatalyst Download PDFInfo
- Publication number
- CN114471722B CN114471722B CN202210036106.1A CN202210036106A CN114471722B CN 114471722 B CN114471722 B CN 114471722B CN 202210036106 A CN202210036106 A CN 202210036106A CN 114471722 B CN114471722 B CN 114471722B
- Authority
- CN
- China
- Prior art keywords
- dut
- rgo
- photocatalyst
- preparation
- suspension
- 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.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004964 aerogel Substances 0.000 title claims abstract description 23
- 239000013432 DUT-67 Substances 0.000 title claims abstract 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 10
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000000017 hydrogel Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 25
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 14
- 230000001699 photocatalysis Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000012546 transfer Methods 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000005447 environmental material Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 10
- 238000000527 sonication Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000007540 photo-reduction reaction Methods 0.000 description 4
- 238000006552 photochemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of environmental material preparation, and discloses a preparation method and application of a three-dimensional DUT-67/RGO aerogel photocatalyst. Firstly, preparing a DUT-67 photocatalyst through solvothermal, then carrying out secondary hydrothermal reaction on the obtained product with ascorbic acid and GO to obtain a three-dimensional hydrogel photocatalyst, and then carrying out freeze drying to obtain the three-dimensional DUT-67/RGO aerogel photocatalyst. The presence of RGO and aerogel structures improves the photoelectrocharge separation efficiency of DUT-67, helps to provide more charges and increases their likelihood of participating in photocatalytic reactions, and DUT-67/RGO macrostructures have a multi-layer structure, which is very beneficial for charge transfer and CO 2 Rate of mass transfer per CO. At the same time benefit from CO 2 The increase in adsorption/activation capacity and efficient transfer and consumption of photogenerated electrons, DUT-67/RGO, shows significant CO conversion and selectivity in mild gas-solid reactions. The invention realizes the efficient selective reduction of CO by the DUT-67/RGO aerogel composite photocatalyst 2 For the purpose of CO.
Description
Technical Field
The invention belongs to the technical field of environmental material preparation, and relates to a preparation method of a three-dimensional DUT-67/RGO aerogel photocatalyst, which is applied to photocatalysis of CO 2 Is converted into the CO field.
Background
Carbon neutralization initiatives determine the great direction of global green low carbon transformation. Thus, low carbon cleaning technology has become a potential solution to eliminate carbon emissions. Wherein, the photocatalysis CO simulating natural photosynthesis 2 Conversion is a green technology that converts solar energy into chemical energy. CO 2 Typically at the interface of the photocatalyst. Heretofore, CO 2 The photo-reduction reaction of (2) is mostly carried out in a three-phase reaction mode, i.e., liquid, solid and gas. However, the three-phase reaction mode has two problems. First is the stability of the photocatalyst in the liquid phase. Second is CO 2 Solubility in the liquid phase results in CO 2 The adsorption quantity is low. As such, a two-phase reactionSystem in CO 2 The field of photoreduction is increasingly favored. That is, in the gas-solid mode, CO 2 Can be directly contacted with photocatalyst to solve the problem of CO 2 The problem of low adsorption capacity reduces the surface reaction barrier and eliminates the gas transmission resistance.
In order to fully play the advantages of the gas-solid reaction system, the structural design of the photocatalyst is particularly important. Based on the method, a three-dimensional (3D) graphene macrostructure is constructed for CO in a gas-solid reaction system 2 Is an effective strategy. The 3D graphene has the characteristics of large specific surface area, good electron conductivity, high mass transfer speed and the like. The porous network structure not only reduces the transmission resistance of the material and the contact resistance between layers, but also provides a special conductive channel for rapid transfer and conduction of charges. In addition, the internal network structure of the 3D graphene can also avoid agglomeration caused by masking of adsorption and reaction sites due to pi-pi interaction between two-dimensional graphene sheets, so that stronger adsorption capacity is shown. More importantly, the 3D graphene macrostructure has larger internal pores and can be used as an ideal carrier of materials such as hetero atoms, functional polymers, inorganic nano structures and the like, so that the unique photoreduction CO is formed 2 New material with performance.
CO 2 Is a multiple electron transfer process, and the target products have different reduction potentials. However, suitable photocatalysts are required to meet thermodynamic and kinetic requirements. Sometimes, it is difficult to achieve the desired reduction efficiency using a single photocatalyst, so two or more photocatalysts may be used in combination to achieve CO 2 Is improved. Zr-based Metal Organic Frameworks (MOFs) have a rich structure type and excellent stability, and are increasingly popular. DUT-67 (Dresden University of Technology-67) is reported to have a large specific surface area and sufficient negative conduction band sites to drive CO 2 The reduction reaction occurs. However, DUT-67 also has a problem of low photo-generated carrier separation efficiency. One potential solution to these challenges is to use the carrier effect of 3D graphene macrostructures to uniformly distribute DUT-67 across macrosWithin the viewing architecture and utilizing the synergistic effect of the macrostructure and DUT-67 to achieve CO 2 High efficiency and high selectivity catalytic conversion.
Disclosure of Invention
The invention constructs a series of 3D DUT-67/RGO aerogel macrostructure photocatalysts by utilizing simple hydrothermal and freeze drying, and is used for photocatalysis of CO under the irradiation of a xenon lamp 2 And (3) CO conversion application.
In order to achieve the technical purpose, the technical scheme adopted by the invention comprises the following steps:
(1) Preparation of DUT-67:
dissolving zirconium chloride in a mixed solution of N, N-dimethylformamide and N-methylpyrrolidone, then adding 2, 5-thiophenedicarboxylic acid into the solution, adding acetic acid after ultrasonic treatment, transferring the mixture into an autoclave lined with Teflon, and obtaining white powder, namely DUT-67 through solvothermal reaction;
(2) Preparation of Graphene Oxide (GO) suspension:
uniformly dispersing Graphene Oxide (GO) in deionized water by ultrasonic to obtain GO suspension;
(3) Preparation of DUT-67/RGO:
adding DUT-67 prepared in the step (1) and ascorbic acid into the GO suspension prepared in the step (2), obtaining a 3D DUT-67/RGO hydrogel material through hydrothermal reaction, and freeze-drying to obtain the 3D DUT-67/RGO aerogel photocatalyst.
In the step (1), the dosage ratio of zirconium chloride, 2, 5-thiophene dicarboxylic acid and acetic acid is 0.1165g:0.0585g:3.5mL; the volume ratio of N, N-dimethylformamide to N-methylpyrrolidone is 1:1, the solvothermal reaction is carried out at 120 ℃ for 48 hours.
In step (2), the concentration of GO suspension was 3mg/mL.
In the step (3), the dosage ratio of DUT-67, ascorbic acid and GO suspension is 25-125 mg:30mg:5mL;
in the step (3), the hydrothermal reaction is carried out at 180 ℃ for 3 hours and the freeze drying time is 24 hours.
3D DUT-67/RGO air coagulation prepared by the inventionGlue photocatalyst for photocatalytic reduction of CO 2 Is provided.
The beneficial effects of the invention are as follows:
(1) The invention constructs a series of 3D DUT-67/RGO aerogel macrostructure photocatalysts through simple hydrothermal and freeze drying. Benefiting from CO 2 The improvement of adsorption/activation ability and the effective transfer and consumption of photo-generated electrons, 15D/R shows remarkable CO conversion rate (10.6 mu mol g) in mild gas-solid reaction -1 h -1 ) And selectivity (99.6%).
(2) The presence of RGO and aerogel structures improves the photoelectrocharge separation efficiency of DUT-67, helps to provide more charges and increases their likelihood of participating in photocatalytic reactions, and DUT-67/RGO macrostructures have a multi-layer structure, which is very beneficial for charge transfer and CO 2 Rate of mass transfer per CO.
(3) The invention selects DUT-67/RGO aerogel as a photocatalyst, under the conditions of full spectrum irradiation and the existence of water molecules, photo-generated electrons are transferred from DUT-67 to RGO surface, and electrons accumulated on RGO surface and having strong reducing ability activate CO 2 The CO is reduced to CO, and the method is simple to operate and environment-friendly 2 Processing techniques.
Drawings
FIG. 1 is an XRD pattern (a) of GO, RGO, DUT-67 and DUT-67/RGO composite photocatalyst; raman plot of GO and 15D/R (b);
FIG. 2 is an SEM of GO (a), RGO (b) 15D/R (c, D); the illustrations are digital photographs of the samples, respectively.
FIG. 3 is a UV-vis diagram (a) of DUT-67 and 15D/R complex photocatalyst; band gap diagrams (b) for DUT-67 and 15D/R composite photocatalyst;
FIG. 4 is transient fluorescence (a) for DUT-67 and 15D/R; photocurrent response (b), impedance plot (c) and linear cyclic voltammogram (d) of DUT-67 and all composite photocatalysts.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1:
(1) Preparation of DUT-67: 0.1165g of zirconium chloride are dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, to which solution 0.0585g of 2, 5-thiophenedicarboxylic acid are added, after sonication to dissolve, 3.5mL of acetic acid are added, and the mixture is transferred to an autoclave lined with Teflon and held at 120℃for 48 hours. The white product was obtained by centrifugation, washed with DMF until the solution was colorless and dried under vacuum at 120 ℃ for 12 hours.
(2) Graphene Oxide (GO) suspension: 150mg of graphene oxide was uniformly dispersed in 50mL of deionized water by sonication, yielding a GO suspension with a concentration of 3mg/mL.
(3) Preparation of 5D/R: 25mg of DUT-67 in step (1) and 30mg of ascorbic acid were added to 5mL of GO suspension in step (2), the mixture was transferred to a Teflon-lined autoclave and kept at 180℃for 3 hours to give a 5D/R hydrogel material, which was then freeze-dried for 24 hours to give a 5D/R aerogel macrostructure.
Putting the 5D/R composite photocatalyst in the step (3) into a photochemical reaction instrument, and carrying out photocatalytic reduction on CO under full spectrum 2 Experiments prove that the photocatalyst reduces CO in four hours 2 The conversion efficiency of CO is 21.85 mu mol/g;
example 2:
(1) Preparation of DUT-67: 0.1165g of zirconium chloride are dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, to which solution 0.0585g of 2, 5-thiophenedicarboxylic acid are added, after sonication to dissolve, 3.5mL of acetic acid are added, and the mixture is transferred to an autoclave lined with Teflon and held at 120℃for 48 hours. The white product was obtained by centrifugation, washed with DMF until the solution was colorless and dried under vacuum at 120 ℃ for 12 hours.
(2) Graphene Oxide (GO) suspension: 150mg of graphene oxide was uniformly dispersed in 50mL of deionized water by sonication, yielding a GO suspension with a concentration of 3mg/mL.
(3) Preparation of 10D/R: 50mg of DUT-67 in step (1) and 30mg of ascorbic acid were added to 5mL of GO suspension in step (2), the mixture was transferred to a Teflon-lined autoclave and kept at 180℃for 3 hours to give a 10D/R hydrogel material, which was then freeze-dried for 24 hours to give a 10D/R aerogel macrostructure.
Putting the 10D/R composite photocatalyst in the step (3) into a photochemical reaction instrument, and carrying out photocatalytic reduction on CO under full spectrum 2 Experiments prove that the photocatalyst reduces CO in four hours 2 The conversion efficiency of converting CO is 27.75 mu mol/g;
example 3:
(1) Preparation of DUT-67: 0.1165g of zirconium chloride are dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, to which solution 0.0585g of 2, 5-thiophenedicarboxylic acid are added, after sonication to dissolve, 3.5mL of acetic acid are added, and the mixture is transferred to an autoclave lined with Teflon and held at 120℃for 48 hours. The white product was obtained by centrifugation, washed with DMF until the solution was colorless and dried under vacuum at 120 ℃ for 12 hours.
(2) Graphene Oxide (GO) suspension: 150mg of graphene oxide was uniformly dispersed in 50mL of deionized water by sonication, yielding a GO suspension with a concentration of 3mg/mL.
(3) Preparation of 15D/R: 75mg of DUT-67 in step (1) and 30mg of ascorbic acid were added to 5mL of GO suspension in step (2), the mixture was transferred to a Teflon-lined autoclave and kept at 180℃for 3 hours to give a 15D/R hydrogel material, which was then freeze-dried for 24 hours to give a 15D/R aerogel macrostructure.
Putting the 15D/R composite photocatalyst in the step (3) into a photochemical reaction instrument, and carrying out photocatalytic reduction on CO under full spectrum 2 Experiments prove that the photocatalyst reduces CO in four hours 2 The conversion efficiency of CO conversion is 42.41 mu mol/g;
example 4:
(1) Preparation of DUT-67: 0.1165g of zirconium chloride are dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, to which solution 0.0585g of 2, 5-thiophenedicarboxylic acid are added, after sonication to dissolve, 3.5mL of acetic acid are added, and the mixture is transferred to an autoclave lined with Teflon and held at 120℃for 48 hours. The white product was obtained by centrifugation, washed with DMF until the solution was colorless and dried under vacuum at 120 ℃ for 12 hours.
(2) Graphene Oxide (GO) suspension: 150mg of graphene oxide was uniformly dispersed in 50mL of deionized water by sonication, yielding a GO suspension with a concentration of 3mg/mL.
(3) Preparation of 20D/R: 100mg of DUT-67 in step (1) and 30mg of ascorbic acid were added to 5mL of GO suspension in step (2), the mixture was transferred to a Teflon-lined autoclave and kept at 180℃for 3 hours to give a 20D/R hydrogel material, which was then freeze-dried for 24 hours to give a 20D/R aerogel macrostructure.
Putting the 20D/R composite photocatalyst in the step (3) into a photochemical reaction instrument, and carrying out photocatalytic reduction on CO under full spectrum 2 Experiments prove that the photocatalyst reduces CO in four hours 2 The conversion efficiency of CO is 18.27 mu mol/g;
example 5:
(1) Preparation of DUT-67: 0.1165g of zirconium chloride are dissolved in 6.25mL of a mixed solution of N, N-dimethylformamide and 6.25mL of N-methylpyrrolidone, to which solution 0.0585g of 2, 5-thiophenedicarboxylic acid are added, after sonication to dissolve, 3.5mL of acetic acid are added, and the mixture is transferred to an autoclave lined with Teflon and held at 120℃for 48 hours. The white product was obtained by centrifugation, washed with DMF until the solution was colorless and dried under vacuum at 120 ℃ for 12 hours.
(2) Graphene Oxide (GO) suspension: 150mg of graphene oxide was uniformly dispersed in 50mL of deionized water by sonication, yielding a GO suspension with a concentration of 3mg/mL.
(3) Preparation of 25D/R: 125mg of DUT-67 in step (1) and 30mg of ascorbic acid were added to 5mL of GO suspension in step (2), the mixture was transferred to a Teflon-lined autoclave and kept at 180℃for 3 hours to give a 25D/R hydrogel material, which was then freeze-dried for 24 hours to give a 25D/R aerogel macrostructure.
Putting the 25D/R composite photocatalyst in the step (3) into photochemical reactionIn the reaction instrument, the photocatalytic reduction of CO is carried out under the full spectrum 2 Experiments prove that the photocatalyst reduces CO in four hours 2 The conversion efficiency of CO is 14.86 mu mol/g;
FIG. 1 (a) is an XRD pattern for GO, RGO, DUT-67 and DUT-67/RGO composite photocatalyst, with GO showing reflection at 9.9℃corresponding to the (002) crystal plane. With the disappearance of the GO diffraction peak after hydrothermal treatment, a new RGO broad diffraction peak appears. The XRD spectrum of the composite shows a typical diffraction peak of DUT-67. As DUT-67 increases, the intensity of the diffraction peaks also increases. The diffraction peak of RGO is not obvious, mainly because of low content and crystallinity. FIG. 1 (b) shows the Raman spectra of GO and 15D/R. In comparison with GO, the intensity ratio of D and G bands in 15D/R (I D /I G ) The G band in 15D/R was significantly shifted with improvement. Thus, during the reduction of GO to RGO, a strong interaction occurs between RGO and DUT-67, facilitating subsequent catalytic reactions.
FIG. 2 is (a) SEM of GO; (b) SEM of RGO; SEM of (c) and (D) 15D/R. As can be seen from fig. 2 (a), the GO powder exhibits a pruned morphology of the senbanba. After hydrothermal and freeze-drying of GO, an aerogel macrostructure with a height of about 0.7 cm and a diameter of about 1 cm is obtained (inset in fig. 2 b). From the microstructure, the morphology changed significantly. RGO exhibits a layered porous structure consisting of stacked thin layers (fig. 2 b). When DUT-67 is involved in the self-assembly process of RGOs, the macrostructure of 15D/R aerogel is fuller, more regular than RGOs (FIGS. 2c and 2D). In addition, due to the strong interaction between DUT-67 and RGO, DUT-67 is uniformly dispersed in different layers, the inter-layer spacing increases, better utilizing the electron conductivity of graphene to facilitate charge carrier transport, facilitating reactant/product transport.
FIG. 3 is a UV-vis diagram of (a) DUT-67 and 15D/R complex photocatalyst; (b) bandgap diagrams of DUT-67 and 15D/R complex photocatalyst. The light absorption capacity and band structure of DUTs-67 and 15D/R were investigated by UV-vis DRS. As shown in FIG. 3a, DUT-67 responds only in the ultraviolet region with the absorption edge at 326nm and the calculated band gap is about 3.89eV (FIG. 3 b). In contrast, 15D/R exhibited tailing absorption in the visible region, covering the entire visible region. In addition, bandgap of 15D/RAlso reduced (3.53 eV), indicating that 15D/R can more efficiently absorb solar energy and produce light for photo-reduction of CO 2 Is an electron of (a)
FIG. 4 is (a) transient fluorescence of DUT-67 and 15D/R; DUT-67 and all composite photocatalyst, (b) photocurrent response, (c) impedance plot, (d) linear cyclic voltammogram. In FIG. 4a, the life of DUTs-67 and 15D/R are fitted by a double exponential decay function. τ 1 And τ 2 Corresponding to radioactive and non-radioactive energy transfer, respectively. 15D/R display τ 1 Reduce τ 2 The increase is significant, indicating that RGO acts as a good electron acceptor and can extend the lifetime of photoelectrons by non-radiative quenching. The extended lifetime of the photogenerated electrons helps to provide more charge and increase the likelihood that they will participate in the photocatalytic reaction. The TPR is measured by several switching cycles of intermittent illumination, the result being shown in fig. 4 b. All photocatalytic materials exhibit a photocurrent response to varying degrees at the instant of lamp turn-on. 15D/R (2.21. Mu.A cm) -2 ) The photocurrent density was DUT-67 (0.37 μA cm) -2 ) Indicating that the presence of RGO and aerogel structures improves the photo-generated charge separation efficiency of DUT-67. Similarly, EIS was used to evaluate interfacial charge transfer (fig. 4 c). The semicircle in the Gao Pinnai nyquist plot is characteristic of the charge transfer process, and the diameter of the semicircle represents the charge transfer resistance. As expected, the composite material exhibited a smaller semi-circular radius. This is due to the good electron conductivity of three-dimensional RGOs, reducing the interfacial charge transfer resistance from DUT-67 to RGOs, thus improving charge transfer with the help of RGOs. The minimum semi-circular radius of 15D/R also corresponds to its maximum photocurrent density. Furthermore, the LSV curve also demonstrates that at the same current density, the overpotential required for 15D/R is minimal (FIG. 4D). Thus, charge transfer in 15D/R is easier.
The photocatalytic performance of the prepared material is realized by self-made photocatalytic CO 2 And (5) evaluating by a detection system. The photocatalyst was placed in the center of a closed quartz reactor, and after passing saturated water vapor of carbon dioxide through the reactor for 30min, the reactor was closed. The light source is provided by a 300W xenon lamp. After illumination for a fixed time, detecting the gas product by gas chromatography, and bringing the result into a standard curve to obtain the corresponding COYield.
Claims (6)
1. A preparation method of a three-dimensional DUT-67/RGO aerogel photocatalyst is characterized by comprising the following steps:
(1) Preparation of DUT-67:
dissolving zirconium chloride in a mixed solution of N, N-dimethylformamide and N-methylpyrrolidone, then adding 2, 5-thiophenedicarboxylic acid into the solution, adding acetic acid after ultrasonic treatment, transferring the mixture into an autoclave lined with Teflon, and obtaining white powder, namely DUT-67 through solvothermal reaction;
(2) Preparation of graphene oxide GO suspension:
uniformly dispersing graphene oxide GO in deionized water to obtain GO suspension;
(3) Preparation of DUT-67/RGO:
adding DUT-67 prepared in the step (1) and ascorbic acid into the GO suspension prepared in the step (2), performing hydrothermal reaction to obtain a 3D DUT-67/RGO hydrogel material, and performing freeze drying to obtain the 3D DUT-67/RGO aerogel photocatalyst
Wherein the dosage ratio of DUT-67, ascorbic acid and GO suspension is 25-125 mg:30mg:5mL;
the temperature of the hydrothermal reaction is 180 ℃, the reaction time is 3 hours, and the freeze drying time is 24 hours.
2. The method according to claim 1, wherein in the step (1), the ratio of zirconium chloride, 2, 5-thiophenedicarboxylic acid and acetic acid is 0.1165g:0.0585g:3.5mL.
3. The method according to claim 1, wherein in the step (1), the volume ratio of N, N-dimethylformamide to N-methylpyrrolidone is 1:1.
4. the process of claim 1, wherein in step (1), the solvothermal reaction is carried out at a temperature of 120℃for a period of 48 hours.
5. The method of claim 1, wherein in step (2), the GO suspension has a concentration of 3mg/mL.
6. Use of the three-dimensional DUT-67/RGO aerogel photocatalyst prepared by the preparation method of any of claims 1-5 for photocatalytic reduction of CO 2 Is provided.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210036106.1A CN114471722B (en) | 2022-01-13 | 2022-01-13 | Preparation method and application of three-dimensional DUT-67/RGO aerogel photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210036106.1A CN114471722B (en) | 2022-01-13 | 2022-01-13 | Preparation method and application of three-dimensional DUT-67/RGO aerogel photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114471722A CN114471722A (en) | 2022-05-13 |
| CN114471722B true CN114471722B (en) | 2023-08-22 |
Family
ID=81511338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210036106.1A Active CN114471722B (en) | 2022-01-13 | 2022-01-13 | Preparation method and application of three-dimensional DUT-67/RGO aerogel photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114471722B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN113318794A (en) * | 2021-05-12 | 2021-08-31 | 江苏大学 | Preparation method and application of plasmon composite photocatalyst Pd/DUT-67 |
| CN113649074A (en) * | 2021-08-30 | 2021-11-16 | 江苏大学 | UiO-66-NH2Preparation method and application of photocatalyst modified by RGO interface covalent bond |
| CN113828296A (en) * | 2021-09-24 | 2021-12-24 | 中广核环保产业有限公司 | Preparation method of 3D graphene oxide composite photocatalytic aerogel based on solid-phase reduction |
-
2022
- 2022-01-13 CN CN202210036106.1A patent/CN114471722B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN113318794A (en) * | 2021-05-12 | 2021-08-31 | 江苏大学 | Preparation method and application of plasmon composite photocatalyst Pd/DUT-67 |
| CN113649074A (en) * | 2021-08-30 | 2021-11-16 | 江苏大学 | UiO-66-NH2Preparation method and application of photocatalyst modified by RGO interface covalent bond |
| CN113828296A (en) * | 2021-09-24 | 2021-12-24 | 中广核环保产业有限公司 | Preparation method of 3D graphene oxide composite photocatalytic aerogel based on solid-phase reduction |
Non-Patent Citations (1)
| Title |
|---|
| 郑思辉."二氧化钛/石墨烯复合材料的制备及其光催化性能研究".《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》.2016,(第undefined期),摘要和第40-41页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114471722A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Synergy effect between adsorption and heterogeneous photo-Fenton-like catalysis on LaFeO3/lignin-biochar composites for high efficiency degradation of ofloxacin under visible light | |
| Xu et al. | Fabrication of 2D/2D Z-scheme highly crystalline carbon nitride/δ-Bi2O3 heterojunction photocatalyst with enhanced photocatalytic degradation of tetracycline | |
| Luo et al. | Trimetallic metal–organic frameworks and derived materials for environmental remediation and electrochemical energy storage and conversion | |
| Hu et al. | One-pot synthesis of step-scheme Bi2S3/porous g-C3N4 heterostructure for enhanced photocatalytic performance | |
| CN110180548B (en) | One-dimensional indium oxide hollow nanotube/two-dimensional zinc ferrite nanosheet heterojunction composite material and application thereof in removing water pollutants | |
| CN103922289B (en) | A kind of two dimensional crystal compound complex metal oxides nano-powder and preparation thereof, application | |
| CN111389442B (en) | P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof | |
| Chen et al. | Construction of novel 2D/1D g-C3N4/CaTiO3 heterojunction with face-to-face contact for boosting photodegradation of triphenylmethane dyes under simulated sunlight | |
| Zheng et al. | ZnCdS/NiAl hydrotalcite S-scheme heterojunction for efficient photocatalytic hydrogen evolution | |
| Wang et al. | Synergistic interface phenomena between MOFs, NiPx for efficient hydrogen production | |
| He et al. | NH2-MIL-125 (Ti) encapsulated with in situ-formed carbon nanodots with up-conversion effect for improving photocatalytic NO removal and H2 evolution | |
| CN106964339B (en) | Carbon-doped ultrathin bismuth tungstate nanosheet photocatalytic material and preparation method thereof | |
| CN105289498B (en) | A kind of preparation method of biomass carbon carbon nanomaterial compound | |
| CN106268869A (en) | A kind of preparation method and application of carbon quantum dot/flower-shaped indium sulfide calcium composite photo-catalyst | |
| Zhong et al. | Preparation of a novel composite photocatalyst BiOBr/ZIF-67 for enhanced visible-light photocatalytic degradation of RhB | |
| CN112108150A (en) | Based on magnetic Fe3O4Modified corncob biomass carbon dot composite Bi2WO6Preparation method and application of photocatalyst | |
| CN111151285B (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| Zhao et al. | Integration of 3D macroscopic reduced graphene oxide aerogel with DUT-67 for selective CO2 photoreduction to CO in Gas-Solid reaction | |
| Wu et al. | Highly selective conversion of CO 2 to C 2 H 6 on graphene modified chlorophyll Cu through multi-electron process for artificial photosynthesis | |
| CN108339544B (en) | Photocatalyst/super-hydrophobic membrane composite material modified by fullerene carboxyl derivative | |
| CN111729682A (en) | Photocatalyst g-C3N4/RGO/Bi2O3And method for preparing the same | |
| CN102000548A (en) | Method for preparing modified active carbon adsorbent of low-concentration organic waste gas | |
| CN109999917B (en) | Covalent organic framework-based composite photocatalyst for degrading organic pollutants in water and preparation method thereof | |
| CN113318794A (en) | Preparation method and application of plasmon composite photocatalyst Pd/DUT-67 | |
| Zhou et al. | In situ growth of CdIn2S4 on NH2-MIL-125 as efficient photocatalysts for H2 production under visible-light irradiation |
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 |