CN110013880B - MIL-101 composite photocatalytic material, preparation method and application - Google Patents
MIL-101 composite photocatalytic material, preparation method and application Download PDFInfo
- Publication number
- CN110013880B CN110013880B CN201910420801.6A CN201910420801A CN110013880B CN 110013880 B CN110013880 B CN 110013880B CN 201910420801 A CN201910420801 A CN 201910420801A CN 110013880 B CN110013880 B CN 110013880B
- Authority
- CN
- China
- Prior art keywords
- mil
- cds
- solution
- preparation
- stirring
- 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
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 92
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000004448 titration Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 82
- 239000011259 mixed solution Substances 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 63
- 238000001035 drying Methods 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 19
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000012456 homogeneous solution Substances 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 5
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 107
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052793 cadmium Inorganic materials 0.000 description 16
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000003638 chemical reducing agent Substances 0.000 description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004098 Tetracycline Substances 0.000 description 5
- 235000019364 tetracycline Nutrition 0.000 description 5
- 150000003522 tetracyclines Chemical class 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 230000032900 absorption of visible light Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/39—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides an MIL-101 composite photocatalytic material, a preparation method and an application, and the preparation method comprises the following three steps: preparing and activating a metal organic framework MIL-101 (Cr); preparing Ag/MIL-101, namely introducing MIL-101(Cr) with large surface area as a substrate for good dispersion growth of Ag nano particles to obtain Ag/MIL-101; ag @ CdS/MIL-101 is prepared by doping CdS particles on MIL-101(Cr) by a solution titration method, selectively coating CdS on Ag nanoparticles, loading CdS into an MIL-101(Cr) channel, and using a limited space provided by the channel as a microreactor to limit the growth and agglomeration of the CdS particles. The three-component heterogeneous structure composite photocatalytic material is applied to photocatalytic water hydrogen evolution, and the photocatalytic activity and the hydrogen evolution quantity are greatly improved.
Description
Technical Field
The invention belongs to the technical field of MOFs composite photocatalytic materials, and particularly relates to an MIL-101 composite photocatalytic material, a preparation method and application.
Background
The increasing energy crisis, environmental pollution caused by the combustion of fossil fuels, has led to an active search for renewable energy and environmentally friendly alternative energy resources. Hydrogen, as a next-generation energy source, has attracted research and development and utilization of countless scientists due to its characteristics of high energy efficiency, environmental friendliness, recyclability, and the like. In the early days, people usually obtained hydrogen from non-renewable resources, but this method inevitably resulted in environmental pollution and combustion of fossil fuels, which violated our original intention. Inspired by photosynthesis in the nature, people pursue to utilize sunlight as an energy source and then convert the solar energy into hydrogen energy by water decomposition reaction of a photocatalyst, and most of the existing photocatalytic materials are semiconductor photocatalytic materials.
The metal sulfide is a powerful candidate material and is widely researched. In particular, cadmium sulfide (CdS) has received much attention because of its narrow band gap (2.4eV) and suitable conduction band potential. However, pure CdS particles tend to aggregate, forming large particles, reducing the surface area and resulting in a high rate of recombination of photo-generated electrons and holes. In order to solve these problems, it is desirable to limit the growth and agglomeration of CdS particles, thereby increasing the photocatalytic activity of the CdS particles. Metal organic framework Materials (MOFs) are a new type of zeolite-like materials with a network-like structure formed by self-assembly of metal ions and organic ligands. Currently, MOFs have been used in many different fields, such as gas separation and storage, catalysis, drug release, chemical sensing, and fluorescent materials. The MOFs as a carrier has many advantages, such as a high specific surface area and a graded pore structure, which are beneficial to the high dispersion of guest particles, and MIL-101(Cr) is considered to be a very promising carrier. MIL-101(Cr) possesses two different types of inner cages with extremely high specific surface area (BET specific surface area up to 4000 m) in diameter and pore size window diameter2In terms of/g). MIL-101(Cr) has terminal water molecules attached to the octahedral Cr (III) building block, and this water molecule is removable under high vacuum, thus creating a potential Lewis acid site. MIL-101(Cr) and its ligand-modified derivatives exhibit significant stability to water, which makes it most suitable for use in humid or aqueous environments.
However, because the synthesis conditions of the metal organic framework material and the cadmium sulfide are not matched, the traditional combination mode has the problems that the cadmium sulfide particles are loaded on the metal organic framework unevenly, the particle size and the loading quantity cannot be controlled, and the like.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide an Ag @ CdS/MIL-101 composite photocatalytic material compounded by three components, a preparation method and application, a metal organic framework-cadmium sulfide composite material with a good interface effect is constructed, cadmium sulfide is selectively coated on silver nanoparticles, the advantages of the three components are fully exerted, and the composite material is used for photocatalytic selective organic synthesis and has a good hydrogen evolution effect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of an MIL-101 composite photocatalytic material comprises the following steps:
step S1, preparation and activation of Metal organic framework MIL-101(Cr)
Step s11, dissolving chromium nitrate nonahydrate and terephthalic acid into deionized water, dropwise adding hydrofluoric acid while stirring, and fully reacting to obtain a first mixed solution;
step s12, transferring the first mixed solution into a reaction kettle, preserving heat, naturally cooling to obtain a second mixed solution, and drying the second mixed solution to obtain a pure metal organic framework MIL-101 (Cr);
step s13, dispersing the MIL-101(Cr) prepared in the step s12 in absolute ethyl alcohol, transferring the mixture into a reaction kettle, and keeping the temperature; after natural cooling, washing and drying the MIL-101(Cr) to obtain activated MIL-101 (Cr);
step S2, preparation of Ag/MIL-101
Step s21, dispersing activated MIL-101(Cr) in n-hexane, performing ultrasonic treatment to obtain a homogeneous solution, intensively stirring the homogeneous solution, dropwise adding an inorganic silver solution while stirring, continuously stirring, and drying to obtain Ag+MIL-101 powder;
step s22, mixing the obtained Ag+Adding a reducing agent solution into the MIL-101 powder, continuously stirring and drying to obtain Ag/MIL-101;
step S3, preparation of Ag @ CdS/MIL-101
Step s31, adding Ag/MIL-101 into a sodium sulfide solution, stirring to obtain a mixed solution, and then adding a cadmium solution into the mixed solution to obtain a mixture;
and step s32, placing the mixture in a centrifuge for high-speed centrifugal separation to obtain Ag @ CdS/MIL-101, finally washing to remove impurities, and drying to obtain pure Ag @ CdS/MIL-101.
In the preparation method of the MIL-101 composite photocatalytic material, preferably, the molar ratio of the chromium nitrate nonahydrate to the terephthalic acid in the step s11 is 1: 1.
In the preparation method of the MIL-101 composite photocatalytic material, preferably, the inorganic silver solution in the step s21 is silver nitrate;
preferably, the concentration of silver nitrate is 0.019-0.076 mol/L.
In the method for preparing the MIL-101 composite photocatalytic material, preferably, the cadmium solution is added to the mixed solution in a titration manner when the cadmium solution is added in the step s 31;
preferably, when the cadmium solution is added, the cadmium solution is transferred to a burette and titrated into the mixed solution at a rate of 8-10 s/drop.
In the preparation method of the MIL-101 composite photocatalytic material, preferably, the cadmium solution is Cd (CH)3CO2)2And Cd (NO)3)2One kind of (1).
In the preparation method of the MIL-101 composite photocatalytic material, preferably, the molar ratio of the sodium sulfide solution to the cadmium solution added in the step s31 is 1: 1;
preferably, the concentration of the sodium sulfide solution is 0.005-0.01mol/L, and the concentration of the cadmium solution is 0.005-0.01 mol/L.
In the preparation method of the MIL-101 composite photocatalytic material, preferably, in the step s12, the first mixed solution is transferred to a reaction kettle, and is subjected to heat preservation at the temperature of 200-220 ℃ for 6-10 hours, and then is naturally cooled to obtain a second mixed solution.
In the preparation method of the MIL-101 composite photocatalytic material, preferably, the reducing agent solution added in the step s22 is NaBH4Continuously stirring the solution for 0.8-1.2h, and drying at 80-120 ℃ to obtain Ag/MIL-101;
preferably, the concentration of the reducing agent solution is 0.2-0.6 mol/L.
An MIL-101 composite photocatalytic material prepared by the preparation method.
An application of an MIL-101 composite photocatalytic material prepared by a preparation method of the MIL-101 composite photocatalytic material is disclosed, and the MIL-101 composite photocatalytic material is applied to photocatalytic water hydrogen evolution.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the invention discloses a Ag @ CdS/MIL-101 composite photocatalytic material compounded by three components, which is prepared by introducing MIL-101(Cr) with a large surface area as a substrate for the good dispersion growth of Ag nanoparticles, doping CdS particles on the MIL-101(Cr) by adopting a solution titration method instead of a hydrothermal method, selectively coating CdS on the Ag nanoparticles, and enabling a three-component Ag @ CdS/MIL-101 heterostructure to have a better hydrogen evolution rate than pure CdS/MIL-101 and Ag/MIL-101 composite materials under the irradiation of visible light.
According to the invention, the absorption of visible light is increased by utilizing the plasma resonance effect of Ag, the separation of electron-hole pairs is accelerated, the catalytic activity is improved, CdS is loaded into an MIL-101(Cr) pore channel, and the limited space provided by MOFs pore channels is used as a microreactor to limit the growth and aggregation of CdS particles, so that the photocatalytic activity of the CdS particles is improved.
The MIL-101(Cr) and Ag/MIL-101 in the preparation process have obvious effect of photocatalytic tetracycline degradation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 shows the X-ray diffraction measurements of MIL-101(Cr), Ag/MIL-101, CdS/MIL-101 and Ag @ CdS/MIL-101 prepared in example 1 of the present invention;
FIG. 2 shows UV-VIS absorption spectrum test results of MIL-101(Cr), Ag/MIL-101, CdS/MIL-101 and Ag @ CdS/MIL-101 prepared in example 2 of the present invention;
FIG. 3 shows the hydrogen evolution amounts of MIL-101(Cr), Ag/MIL-101, CdS/MIL-101 and Ag @ CdS/MIL-101 prepared in example 1 applied to different time points of the catalytic hydrogen production reaction;
FIG. 4 shows the results of the application of MIL-101(Cr), Ag/MIL-101 and CdS/MIL-101 prepared in example 4 of the present invention to the catalytic degradation of tetracycline.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
According to the MIL-101 composite photocatalytic material and the preparation method and application thereof, the absorption of visible light is increased by utilizing the plasma resonance effect of Ag, the separation of electron hole pairs is accelerated, and the catalytic activity is improved.
According to the novel efficient three-component Ag @ CdS/MIL-101 heterostructure prepared in the invention, a hydrothermal method is replaced by a solution titration method to dope CdS particles on MIL-101(Cr), so that the experimental steps are simplified, cadmium sulfide particles are uniformly loaded on a metal organic framework, the particle size and the loading amount are effectively controlled, the metal organic framework MIL-101(Cr) material prepared in the invention is in an octahedral structure, the particle size is 300-500nm, the metal organic framework MIL-101(Cr) material has a microporous structure, the particle size during CdS particle growth is limited, and CdS is loaded on Ag nanoparticles to avoid agglomeration of CdS particles, so that the catalytic efficiency and the activity of the three-component heterogeneous structure composite photocatalyst which can be excited by visible light and takes MIL-101(Cr) as a matrix material are greatly improved.
The invention provides a preparation method of an MIL-101 composite photocatalytic material, which comprises the following steps:
a preparation method of an MIL-101 composite photocatalytic material comprises the following steps:
step S1, preparation and activation of Metal organic framework MIL-101(Cr)
Step s11, dissolving chromium nitrate nonahydrate and terephthalic acid into deionized water, dropwise adding hydrofluoric acid while stirring, and fully reacting to obtain a first mixed solution;
step s12, transferring the first mixed solution into a reaction kettle, preserving heat, naturally cooling to obtain a second mixed solution, and drying the second mixed solution to obtain a pure metal organic framework MIL-101 (Cr);
step s13, dispersing the MIL-101(Cr) prepared in the step s12 in absolute ethyl alcohol, transferring the mixture into a reaction kettle, and keeping the temperature; after natural cooling, washing and drying the MIL-101(Cr) to obtain activated MIL-101 (Cr);
preferably, the molar ratio of chromium nitrate nonahydrate to terephthalic acid in step s11 is 1: 1.
Preferably, in step s12, the first mixed solution is transferred to a high pressure reactor, and is kept at 200-; preferably, the first mixed solution is transferred into a reaction kettle, and after the temperature is kept at 220 ℃ for 8 hours, the second mixed solution is obtained after natural cooling.
Preferably, the concentration of hydrofluoric acid is 40%.
Step S2, preparation of Ag/MIL-101
Step s21, dispersing activated MIL-101(Cr) in n-hexane, performing ultrasonic treatment to obtain a homogeneous solution, intensively stirring the homogeneous solution, dropwise adding an inorganic silver solution while stirring, continuously stirring, and drying to obtain Ag+MIL-101 powder;
step s22, mixing the obtained Ag+Adding a reducing agent solution into the MIL-101 powder, continuously stirring and drying to obtain Ag/MIL-101;
preferably, the inorganic silver solution in step s21 is silver nitrate; the concentration of silver nitrate is 0.019-0.076mol/L (such as 0.019mol/L, 0.02mol/L, 0.025mol/L, 0.03mol/L, 0.035mol/L, 0.04mol/L, 0.045mol/L, 0.05mol/L, 0.055mol/L, 0.06mol/L, 0.065mol/L, 0.07mol/L, 0.075 mol/L); still more preferably, the concentration of silver nitrate is 0.038 mol/L.
Preferably, the reducing agent solution added in step s22 is NaBH4Continuously stirring the solution for 0.8-1.2h (such as 0.85h, 0.9h, 0.95h, 1h, 1.05h, 1.1h, 1.15h), and drying at 80-120 deg.C (such as 82 deg.C, 84 deg.C, 86 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 94 deg.C, 96 deg.C, 98 deg.C, 100 deg.C, 102 deg.C, 104 deg.C, 106 deg.C, 108 deg.C, 110 deg.C, 112 deg.C, 114 deg.C, 116 deg.C, 118 deg.C; still preferably, the concentration of the reducing agent solution is 0.2 to 0.6mol/L (e.g., 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55 mol/L).
Step S3, preparation of Ag @ CdS/MIL-101
Step s31, adding Ag/MIL-101 into a sodium sulfide solution, stirring to obtain a mixed solution, and then adding a cadmium solution into the mixed solution to obtain a mixture;
and step s32, placing the mixture in a centrifuge for high-speed centrifugal separation to obtain Ag @ CdS/MIL-101, finally washing to remove impurities, and drying to obtain pure Ag @ CdS/MIL-101.
Preferably, the cadmium solution is added to the mixed solution in a titration manner when added in step s 31; preferably, when the cadmium solution is added, the cadmium solution is transferred to a burette and titrated into the mixed solution at a rate of 8-10 s/drop.
According to the invention, the titration speed of 8-10 s/drop reacts, the titration speed is relatively slow, the reaction can be slowly and uniformly carried out, CdS particles are uniformly formed and grow on Ag nano particles, and the Ag nano particles are loaded in MOFs pore channels to limit the growth of the CdS particles.
More preferably, the cadmium solution is Cd (CH)3CO2)2And Cd (NO)3)2One kind of (1).
Preferably, the molar ratio of sodium sulfide to cadmium solution added in step s31 is 1: 1; the concentration of the sodium sulfide solution is 0.005-0.01mol/L (such as 0.006mol/L, 0.007mol/L, 0.008mol/L, 0.009mol/L, 0.01mol/L), and the concentration of the cadmium solution is 0.005-0.01mol/L (such as 0.006mol/L, 0.007mol/L, 0.008mol/L, 0.009mol/L, 0.01 mol/L).
Preferably, the mixture is centrifuged at 5000-.
Preferably, the obtained Ag @ CdS/MIL-101 is washed by absolute ethyl alcohol to remove impurities and is dried at 50 ℃ to obtain pure Ag @ CdS/MIL-101.
The invention also protects the MIL-101 composite photocatalytic material prepared by the preparation method of the MIL-101 composite photocatalytic material.
The MIL-101 composite photocatalytic material prepared by the preparation method of the MIL-101 composite photocatalytic material is applied to photocatalytic water evolution hydrogen reaction.
Example 1
The preparation method of the MIL-101 composite photocatalytic material provided by the embodiment of the invention comprises the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 1.6g of chromium nitrate nonahydrate and 0.656g of terephthalic acid according to the stoichiometric ratio, dissolving into 20mL of deionized water, dropwise adding 452 mu L of hydrofluoric acid with the concentration of 40% while stirring, fully reacting, and stirring for 30min to obtain a mixed solution.
s12, transferring the mixed solution into a 100mL high-pressure reaction kettle, preserving the heat for 8 hours at 220 ℃, and naturally cooling to obtain a mixed solution; and drying the obtained mixed solution at 80 ℃ for 12h to obtain pure metal organic framework MIL-101 (Cr).
s13, dispersing the obtained pure MIL-101(Cr) in 40mL of absolute ethyl alcohol, transferring to a 100mL high-pressure reaction kettle, and preserving the heat at 100 ℃ for 20 h; naturally cooling, washing the obtained pure MIL-101(Cr) with anhydrous ethanol for several times, and drying at 150 deg.C to obtain activated MIL-101 (Cr).
S2, preparation of Ag/MIL-101:
s21, weighing 0.1g of activated MIL-101(Cr) in the step s13, dispersing in 40mL of n-hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; intensively stirring the homogeneous solution under a magnetic stirrer, dropwise adding 100 mu L of silver nitrate solution with the concentration of 0.038mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101。
s22 Ag obtained+Adding 10mL of reducing agent NaBH with the concentration of 0.3mol/L into MIL-101 powder4The solution was continuously stirred for 1h and dried at 100 ℃ to obtain Ag/MIL-101.
S3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 20mL of sodium sulfide solution with the concentration of 0.005mol/L, stirring for 10min under a magnetic stirrer, then weighing 20mL of cadmium acetate solution with the concentration of 0.005mol/L, transferring the cadmium acetate solution into a titration tube, titrating into a mixed solution at the speed of 8-10 s/drop, and stirring for 20min after titration is finished to obtain a mixture.
s32, centrifuging the obtained mixture at 6000r/min for 10min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and the pure Ag @ CdS/MIL-101 is obtained after drying at 50 ℃.
In order to analyze the structure and performance of the prepared Ag @ CdS/MIL-101, CdS/MIL-101 is also prepared in the embodiment, and the specific preparation method comprises the following steps:
0.04g of MIL-101(Cr) prepared in the step s13 is weighed and added into 20mL of 0.1mol/L sodium sulfide solution, stirring is carried out for 10min under a magnetic stirrer, then 20mL of 0.1mol/L cadmium acetate solution is weighed and transferred into a burette, the solution is titrated into the mixed solution at the speed of 8-10 s/drop, and stirring is carried out for 20min after titration is finished.
And centrifuging the obtained mixture at 6000r/min for 10min by using a concentration method in a high-speed centrifuge, and separating powder to obtain CdS/MIL-101. And washing the product with absolute ethyl alcohol for 2-3 times to remove impurities, and drying at 50 ℃ to obtain pure CdS/MIL-101.
X-ray powder diffraction measurements were performed on the MIL-101(Cr), Ag/MIL-101, CdS/MIL-101 and Ag @ CdS/MIL-101 materials obtained in example 1, as shown in FIG. 1:1 is the diffraction peak of MIL-101(Cr), which is consistent with the diffraction peak of the standard spectrum; 2 is an Ag/MIL-101 diffraction peak, and the diffraction peak contains an Ag nano particle diffraction peak, which shows that Ag and MIL-101(Cr) form a good composite structure; 3 is a CdS/MIL-101 composite structure, and the diffraction peak of the CdS/MIL-101 composite structure consists of CdS and MIL-101 (Cr); 4 is the diffraction peak of the ternary composite Ag @ CdS/MIL-101 photocatalyst material, the diffraction pattern of MIL-101 is consistent with the diffraction peak of a standard spectrum, which shows that the obtained samples have typical MIL-101(Cr) crystal structures, the obtained samples show that the MIL-101(Cr) XRD peak is not changed after the introduction of CdS, the MIL-101(Cr) crystal forms are not changed, the MIL-101(Cr) structures are kept complete, and the peaks at 26.5 degrees, 43.9 degrees and 52.0 degrees correspond to the CdS peaks, which are related to (111), (220) and (311) crystal faces of cubic CdS, because the content of the CdS is too low, the CdS particles are small enough to cause an unobvious X-ray diffraction signal, and the results show that the MIL-101(Cr) has good stability and good confinement effect on CdS nanoparticles.
The photocatalytic material prepared in the embodiment is subjected to hydrogen production test, and the specific method comprises the following steps: respectively preparing Na with the concentration of 0.2mol/L2S and Na2SO3Solution, then mixing10mg of the photocatalytic material to be detected was dispersed in a solution containing 20mmol of Na2S and Na2SO3100mL of aqueous solution. A LED with white light is used as the visible light source. Measurement of the H evolved by means of a Gas Chromatograph (GC) equipped with a Thermal Conductivity Detector (TCD)2The amount of (c).
In addition, the MIL-101(Cr), Ag/MIL-101 and CdS/MIL-101 prepared by the method have obvious effect of photocatalytic tetracycline degradation.
Example 2
The preparation method of the MIL-101 composite photocatalytic material provided by the embodiment of the invention comprises the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 0.4g of chromium nitrate nonahydrate and 0.164g of terephthalic acid according to the stoichiometric ratio, dissolving into 10mL of deionized water, dropwise adding 113 mu L of 40% hydrofluoric acid while stirring, fully reacting, and stirring for 30min to obtain a mixed solution.
s12, transferring the mixed solution into a 50mL high-pressure reaction kettle, preserving the heat for 8 hours at 200 ℃, and naturally cooling to obtain a mixed solution; drying the obtained mixed solution at 100 ℃ for 12h to obtain pure metal organic framework MIL-101 (Cr).
s13, dispersing the obtained pure MIL-101(Cr) in 20mL of absolute ethyl alcohol, transferring to a 50mL high-pressure reaction kettle, and preserving the heat at 100 ℃ for 20 h; naturally cooling, washing the obtained pure MIL-101(Cr) with anhydrous ethanol for several times, and drying at 150 deg.C to obtain activated MIL-101 (Cr).
S2, preparation of Ag/MIL-101:
s21, weighing 0.1g of activated MIL-101(Cr) in the step s13, dispersing in 40mL of n-hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; intensively stirring the homogeneous solution under a magnetic stirrer, dropwise adding 100 mu L of silver nitrate solution with the concentration of 0.02mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101。
s22 Ag obtained+Adding 10mL of reducing agent NaBH with the concentration of 0.2mol/L into MIL-101 powder4The solution was continuously stirred for 1h and dried at 120 ℃ to obtain Ag/MIL-101.
S3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 20mL of sodium sulfide solution with the concentration of 0.006mol/L, stirring for 10min under a magnetic stirrer, then weighing 20mL of cadmium acetate solution with the concentration of 0.006mol/L, transferring the solution into a titration tube, titrating into the mixed solution at the speed of 8-10 s/drop, and stirring for 20min after titration is finished to obtain a mixture.
s32, centrifuging the obtained mixture for 10min at the speed of 5000r/min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and the pure Ag @ CdS/MIL-101 is obtained after drying at 50 ℃.
In order to analyze the performance of the prepared Ag @ CdS/MIL-101, CdS/MIL-101 is also prepared in the embodiment, and the specific preparation method comprises the following steps:
0.04g of MIL-101(Cr) prepared in the step s13 is weighed and added into 20mL of 0.01mol/L sodium sulfide solution, stirring is carried out for 10min under a magnetic stirrer, then 20mL of 0.01mol/L cadmium acetate solution is weighed and transferred into a burette, the solution is titrated into the mixed solution at the speed of 8-10 s/drop, and stirring is carried out for 20min after titration is finished.
And centrifuging the obtained mixture at a speed of 5000r/min for 10min by using a concentration method in a high-speed centrifuge, and separating powder to obtain CdS/MIL-101. And washing the product with absolute ethyl alcohol for 2-3 times to remove impurities, and drying at 50 ℃ to obtain pure CdS/MIL-101.
FIG. 2 is a graph of UV-VIS absorption spectra obtained by testing the MIL-101(Cr), Ag/MIL-101, CdS/MIL-101 and Ag @ CdS/MIL-101 materials prepared in this example.
Example 3
The preparation method of the MIL-101 composite photocatalytic material provided by the embodiment of the invention comprises the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 0.8g of chromium nitrate nonahydrate and 0.328g of terephthalic acid according to the stoichiometric ratio, dissolving into 10mL of deionized water, dropwise adding 226 mu L of 40% hydrofluoric acid while stirring, fully reacting, and stirring for 30min to obtain a mixed solution.
s12, transferring the mixed solution into a 50mL high-pressure reaction kettle, preserving the heat for 10h at 200 ℃, and naturally cooling to obtain a mixed solution; and drying the obtained mixed solution at 70 ℃ for 14h to obtain pure metal organic framework MIL-101 (Cr).
s13, dispersing the obtained pure MIL-101(Cr) in 20mL of absolute ethyl alcohol, transferring to a 50mL high-pressure reaction kettle, and preserving heat at 120 ℃ for 18 h; naturally cooling, washing the obtained pure MIL-101(Cr) with anhydrous ethanol for multiple times, and drying at 180 deg.C to obtain activated MIL-101 (Cr).
S2, preparation of Ag/MIL-101:
s21, weighing 0.1g of activated MIL-101(Cr) in the step s13, dispersing in 50mL of n-hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; intensively stirring the homogeneous solution under a magnetic stirrer, dropwise adding 100 mu L of silver nitrate solution with the concentration of 0.06mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101。
s22 Ag obtained+Adding 10mL of reducing agent NaBH with the concentration of 0.6mol/L into MIL-101 powder4The solution was continuously stirred for 1h and dried at 120 ℃ to obtain Ag/MIL-101.
S3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 20mL of sodium sulfide solution with the concentration of 0.01mol/L, stirring for 10min under a magnetic stirrer, then weighing 20mL of cadmium nitrate solution with the concentration of 0.01mol/L, transferring the solution into a titration tube, titrating the solution into a mixed solution at the speed of 8-10 s/drop, and stirring for 20min after the titration is finished to obtain a mixture.
s32, centrifuging the obtained mixture for 10min at a speed of 5500r/min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and drying is carried out at 70 ℃ to obtain pure Ag @ CdS/MIL-101.
In order to perform performance comparison analysis on the prepared Ag @ CdS/MIL-101, CdS/MIL-101 is also prepared in the embodiment, and the specific preparation method comprises the following steps:
0.04g of MIL-101(Cr) prepared in the step s13 is weighed and added into 20mL of 0.01mol/L sodium sulfide solution, stirring is carried out for 10min under a magnetic stirrer, then 20mL of 0.01mol/L cadmium acetate solution is weighed and transferred into a burette, the solution is titrated into the mixed solution at the speed of 8-10 s/drop, and stirring is carried out for 20min after titration is finished.
And centrifuging the obtained mixture at 5500r/min for 10min by a high-speed centrifuge by using a concentration method, and separating powder to obtain CdS/MIL-101. And washing the product with absolute ethyl alcohol for 2-3 times to remove impurities, and drying at 50 ℃ to obtain pure CdS/MIL-101.
The material prepared in this example was subjected to a hydrogen production test according to the hydrogen production test method in example 1, and fig. 3 is a graph of the test results obtained by performing the hydrogen production performance test on the materials MIL-101(Cr), Ag/MIL-101, CdS/MIL-101, and Ag @ CdS/MIL-101 prepared in this example.
As can be seen from FIG. 3, in the same time, the hydrogen yield Ag @ CdS/MIL-101> CdS/MIL-101> MIL-101(Cr) is Ag/MIL-101, the three-component heterogeneous structure composite photocatalytic material Ag @ CdS/MIL-101 prepared in the embodiment of the invention has excellent hydrogen production performance which is higher than that of the two-component composite photocatalytic material CdS/MIL-101, and the Ag/MIL-101 and MIL-101(Cr) have no effect when applied to catalytic hydrogen evolution, have no catalytic activity and cannot produce hydrogen.
Example 4
The preparation method of the MIL-101 composite photocatalytic material provided by the embodiment of the invention comprises the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 1.6g of chromium nitrate nonahydrate and 0.656g of terephthalic acid according to the stoichiometric ratio, dissolving into 20mL of deionized water, dropwise adding 452 mu L of hydrofluoric acid with the concentration of 40% while stirring, fully reacting, and stirring for 30min to obtain a mixed solution.
s12, transferring the mixed solution into a 100mL high-pressure reaction kettle, preserving the heat for 6h at 220 ℃, and naturally cooling to obtain a mixed solution; and drying the obtained mixed solution at 80 ℃ for 14h to obtain pure metal organic framework MIL-101 (Cr).
s13, dispersing the obtained pure MIL-101(Cr) in 40mL of absolute ethyl alcohol, transferring to a 100mL high-pressure reaction kettle, and preserving heat at 100 ℃ for 18 h; naturally cooling, washing the obtained pure MIL-101(Cr) with anhydrous ethanol for multiple times, and drying at 130 deg.C to obtain activated MIL-101 (Cr).
S2, preparation of Ag/MIL-101:
s21, weighing 0.1g of activated MIL-101(Cr) in the step s13, dispersing in 40mL of n-hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; intensively stirring the homogeneous solution under a magnetic stirrer, dropwise adding 100 mu L of silver nitrate solution with the concentration of 0.076mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101。
s22 Ag obtained+Adding 10mL of reducing agent NaBH with the concentration of 0.5mol/L into MIL-101 powder4The solution was continuously stirred for 1h and dried at 100 ℃ to obtain Ag/MIL-101.
S3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 20mL of sodium sulfide solution with the concentration of 0.008mol/L, stirring for 10min under a magnetic stirrer, then weighing 20mL of cadmium acetate solution with the concentration of 0.008mol/L, transferring the cadmium acetate solution into a titration tube, titrating into a mixed solution at the speed of 8-10 s/drop, and stirring for 20min after titration is finished to obtain a mixture.
s32, centrifuging the obtained mixture at 7000r/min for 10min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and the pure Ag @ CdS/MIL-101 is obtained after drying at 50 ℃.
FIG. 4 shows the results of the test of example 4 for the catalytic degradation of organic tetracyclines.
From FIG. 4, it is known that the applications of MIL-101(Cr), Ag/MIL-101 and CdS/MIL-101 in catalyzing and degrading tetracycline have good effects.
Example 5
The preparation method of the MIL-101 composite photocatalytic material provided by the embodiment of the invention comprises the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 0.8g of chromium nitrate nonahydrate and 0.328g of terephthalic acid according to the stoichiometric ratio, dissolving into 10mL of deionized water, dropwise adding 226 mu L of 40% hydrofluoric acid while stirring, fully reacting, and stirring for 30min to obtain a mixed solution.
s12, transferring the mixed solution into a 50mL high-pressure reaction kettle, preserving the heat for 10h at 200 ℃, and naturally cooling to obtain a mixed solution; and drying the obtained mixed solution at 60 ℃ for 14h to obtain pure metal organic framework MIL-101 (Cr).
s13, dispersing the obtained pure MIL-101(Cr) in 20mL of absolute ethyl alcohol, transferring to a 50mL high-pressure reaction kettle, and preserving the heat at 80 ℃ for 20 h; naturally cooling, washing the obtained pure MIL-101(Cr) with anhydrous ethanol for multiple times, and drying at 170 deg.C to obtain activated MIL-101 (Cr).
S2, preparation of Ag/MIL-101:
s21, weighing 0.1g of activated MIL-101(Cr) in the step s13, dispersing in 50mL of n-hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; intensively stirring the homogeneous solution under a magnetic stirrer, dropwise adding 300 mu L of silver nitrate solution with the concentration of 0.01mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101。
s22 Ag obtained+Adding 10mL of reducing agent NaBH with the concentration of 0.5mol/L into MIL-101 powder4The solution was continuously stirred for 1h and dried at 100 ℃ to obtain Ag/MIL-101.
S3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 50mL of sodium sulfide solution with the concentration of 0.005mol/L, stirring for 10min under a magnetic stirrer, then weighing 50mL of cadmium nitrate solution with the concentration of 0.005mol/L, transferring the cadmium nitrate solution into a titration tube, titrating into a mixed solution at the speed of 8-10 s/drop, and stirring for 20min after titration is finished to obtain a mixture.
s32, centrifuging the obtained mixture at 7000r/min for 10min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and the pure Ag @ CdS/MIL-101 is obtained after drying at 50 ℃.
Comparative example 1
The difference between comparative example 1 and example 1 is that the concentration of silver nitrate in step s21 is 0.09mol/L, and the other steps are the same as example 1 and will not be described again.
The hydrogen yield of the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the comparative example is shown in the following table 1.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the concentration of the sodium sulfide solution in the step s31 is 0.02mol/L, the concentration of the cadmium solution is 0.02mol/L, and the other steps are the same as the example 1 and are not repeated herein.
The hydrogen yield of the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the comparative example is shown in the following table 1.
Comparative example 3
The difference between the comparative example 3 and the example 1 is that cadmium acetate is directly and rapidly added to the mixed solution in step s31 without adopting a titration method, and other steps are the same as those in the example 1 and are not repeated herein.
The hydrogen yield of the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the comparative example is shown in the following table 1.
Comparative example 4
Comparative example 4 differs from example 1 in that Ag was obtained in step s22+Adding 0.1mol/L reducer NaBH into MIL-101 powder4The solution was continuously stirred for 0.5h and then dried at 100 ℃ to obtain Ag/MIL-101, and the other steps were the same as in example 1 and will not be repeated herein.
The hydrogen yield of the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the comparative example is shown in the following table 1.
Comparative example 5
The difference between the comparative example 5 and the example 1 is that the mixed solution is transferred into a reaction kettle in the step s12, the temperature is kept for 4 hours at 100 ℃, and a mixed solution is obtained after natural cooling; other steps are the same as embodiment 1 and are not described herein again.
The hydrogen yield of the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the comparative example is shown in the following table 1.
The hydrogen production performance tests were performed on the composite photocatalytic materials Ag @ CdS/MIL-101 prepared in examples 1 to 5 and comparative examples 1 to 5, respectively, according to the photocatalytic material hydrogen production test method in example 1, and the hydrogen evolution amounts in different catalytic reaction times are shown in table 1 below:
TABLE 1 Effect of Ag @ CdS/MIL-101 preparation in examples and comparative examples on hydrogen production
In summary, the following steps: the three-component composite photocatalytic material Ag @ CdS/MIL-101 prepared in the examples 1-5 is applied to photocatalytic hydrogen evolution, the hydrogen evolution amount in different time is superior to that in the comparative examples 1-5, and the maximum hydrogen evolution amount in the example 1 is 1861.7 mu mol/mg at 80 min; in contrast example 3, the hydrogen yield is lowest when the product obtained by directly mixing cadmium acetate and sodium sulfide in step s31 is applied to photocatalytic hydrogen evolution, which indicates that in the process of producing CdS particles, the product obtained by mixing cadmium acetate and sodium sulfide in a titration mode can be selectively coated on Ag nanoparticles and uniformly loaded in the pore channel of MIL-101(Cr), and the pore channel limits the growth of CdS particles, thereby being beneficial to improving the photocatalytic performance of the composite photocatalytic material Ag @ CdS/MIL-101.
In the invention, MIL-101(Cr) with large surface area is introduced as a substrate for the good dispersion growth of Ag nanoparticles, a solution titration method is adopted to replace a hydrothermal method to dope CdS particles on the MIL-101(Cr), CdS is selectively coated on the Ag nanoparticles, the agglomeration of the CdS particles is avoided, and the Ag @ CdS/MIL-101 heterostructure composite material has better hydrogen evolution rate under the irradiation of visible light.
According to the invention, the absorption of visible light is increased by utilizing the plasma resonance effect of Ag, the separation of electron hole pairs is accelerated, the catalytic activity is improved, CdS is loaded into an MIL-101(Cr) channel, and the limited space provided by an MOFs channel is used as a microreactor to limit the growth and agglomeration of CdS particles.
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 (3)
1. A preparation method of an MIL-101 composite photocatalytic material is characterized by comprising the following steps:
s1, preparation and activation of metal organic framework MIL-101 (Cr):
s11, weighing 0.8g of chromium nitrate nonahydrate and 0.328g of terephthalic acid according to the stoichiometric ratio, dissolving into 10mL of deionized water, dropwise adding 226 mu L of 40% hydrofluoric acid while stirring, fully reacting, and stirring for 30min to obtain a mixed solution;
s12, transferring the mixed solution into a 50mL reaction kettle, preserving the heat for 10h at 200 ℃, and naturally cooling to obtain a mixed solution; drying the obtained mixed solution at 70 ℃ for 14h to obtain pure metal organic framework MIL-101 (Cr); the metal organic framework MIL-101(Cr) material is in an octahedral structure, the particle size is 300-500nm, and the metal organic framework MIL-101(Cr) material has a microporous structure;
s13, dispersing the obtained pure MIL-101(Cr) in 20mL of absolute ethyl alcohol, transferring to a 50mL reaction kettle, and preserving heat at 120 ℃ for 18 h; naturally cooling, washing the obtained pure MIL-101(Cr) with absolute ethyl alcohol, and drying at 180 ℃ to obtain activated MIL-101 (Cr);
s2, preparation of Ag/MIL-101:
s21, weighing 0.1g in step s13Dispersing the activated MIL-101(Cr) in 50mL of normal hexane, and carrying out ultrasonic treatment for 20min to obtain a homogeneous solution; stirring the homogeneous solution under a magnetic stirrer, dropwise adding 100 mu L of silver nitrate solution with the concentration of 0.06mol/L while stirring, continuously stirring for 3h to form a mixed solution, and drying the mixed solution at 100 ℃ to obtain Ag+/MIL-101；
s22 Ag obtained+Adding 10mL of NaBH with the concentration of 0.6mol/L into MIL-101 powder4Continuously stirring the solution for 1h, and drying at 120 ℃ to obtain Ag/MIL-101;
s3, preparation of Ag @ CdS/MIL-101:
s31, weighing 0.05g of Ag/MIL-101, adding the Ag/MIL-101 into 20mL of sodium sulfide solution with the concentration of 0.01mol/L, stirring for 10min under a magnetic stirrer, then weighing 20mL of cadmium nitrate solution with the concentration of 0.01mol/L, transferring the cadmium nitrate solution into a burette, titrating into a mixed solution at the speed of 8-10 s/drop, and stirring for 20min after titration is finished to obtain a mixture;
s32, centrifuging the obtained mixture for 10min at a speed of 5500r/min under a high-speed centrifuge, and separating powder to obtain Ag @ CdS/MIL-101; and then absolute ethyl alcohol is used for cleaning for 3-4 times to remove impurities, and drying is carried out at 70 ℃ to obtain the pure composite photocatalytic material Ag @ CdS/MIL-101.
2. The MIL-101 composite photocatalytic material prepared by the preparation method of the MIL-101 composite photocatalytic material as set forth in claim 1.
3. The application of the MIL-101 composite photocatalytic material prepared by the preparation method of the MIL-101 composite photocatalytic material as claimed in claim 1, wherein the MIL-101 composite photocatalytic material is applied to photocatalytic water hydrogen evolution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910420801.6A CN110013880B (en) | 2019-05-20 | 2019-05-20 | MIL-101 composite photocatalytic material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910420801.6A CN110013880B (en) | 2019-05-20 | 2019-05-20 | MIL-101 composite photocatalytic material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110013880A CN110013880A (en) | 2019-07-16 |
| CN110013880B true CN110013880B (en) | 2021-03-16 |
Family
ID=67194109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910420801.6A Active CN110013880B (en) | 2019-05-20 | 2019-05-20 | MIL-101 composite photocatalytic material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110013880B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686768B (en) * | 2020-06-30 | 2023-04-25 | 大连民族大学 | Photocatalytic reduction of Cr 6+ MIL-125/Ag/BiOBr composite catalyst, preparation method and application thereof |
| CN112473737A (en) * | 2020-09-25 | 2021-03-12 | 盐城工学院 | Ag @ MOF material, and preparation method and application thereof |
| CN112798571A (en) * | 2020-12-29 | 2021-05-14 | 中国检验检疫科学研究院 | Preparation method of SERS substrate, SERS substrate and application of SERS substrate |
| CN115518690B (en) * | 2022-07-28 | 2023-11-10 | 广东工业大学 | Cu (copper) alloy 7 S 4 -MOF composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107362830A (en) * | 2017-06-27 | 2017-11-21 | 哈尔滨理工大学 | A kind of preparation method of the CdS-loaded hydrogen production photocatalyst of MIL 101 (Cr) |
| CN108855216A (en) * | 2018-06-11 | 2018-11-23 | 福州大学 | Metal organic frame MIL-101 (Cr) optic catalytic composite material and the preparation method and application thereof of cadmium sulfide package |
| CN109201102A (en) * | 2018-09-28 | 2019-01-15 | 商丘师范学院 | A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst |
| CN109331883A (en) * | 2018-11-26 | 2019-02-15 | 中南大学 | A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application |
-
2019
- 2019-05-20 CN CN201910420801.6A patent/CN110013880B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107362830A (en) * | 2017-06-27 | 2017-11-21 | 哈尔滨理工大学 | A kind of preparation method of the CdS-loaded hydrogen production photocatalyst of MIL 101 (Cr) |
| CN108855216A (en) * | 2018-06-11 | 2018-11-23 | 福州大学 | Metal organic frame MIL-101 (Cr) optic catalytic composite material and the preparation method and application thereof of cadmium sulfide package |
| CN109201102A (en) * | 2018-09-28 | 2019-01-15 | 商丘师范学院 | A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst |
| CN109331883A (en) * | 2018-11-26 | 2019-02-15 | 中南大学 | A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Metal-induced Z-scheme CdS/Ag/g-C3N4 photocatalyst for enhanced hydrogen evolution under visible light: The synergy of MIP effect and electron mediator of Ag;Lun Qian, et al.;《Molecular Catalysis》;20180822;第458卷;第43-51页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110013880A (en) | 2019-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110013880B (en) | MIL-101 composite photocatalytic material, preparation method and application | |
| Jin et al. | Graphdiyne formed a novel CuI-GD/gC 3 N 4 S-scheme heterojunction composite for efficient photocatalytic hydrogen evolution | |
| CN104525238B (en) | A kind of carbonitride/sulfur-indium-zinc composite nano materials and its production and use | |
| CN104959158B (en) | Mo2C/CdS composite photocatalyst and preparation and application thereof | |
| CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
| CN108786849B (en) | Preparation and application of tin sulfide/titanium dioxide composite material | |
| CN108878903B (en) | Loaded Co2Macro preparation method of P nano-particle nitrogen-doped hollow carbon rod oxygen reduction electrocatalyst | |
| Zhu et al. | Efficient photocatalytic water splitting through titanium silicalite stabilized CoO nanodots | |
| CN110721698B (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN112791730B (en) | Z-type nano-copper vanadate-based composite photocatalyst and preparation method and application thereof | |
| CN108686658B (en) | C-QDs-Fe2O3/TiO2Composite photocatalyst and preparation method thereof | |
| CN109201090A (en) | The modified BiOCl of bismuth telluride forms the preparation method of the flower-shaped catalyst of photoresponse type and its application of reduction fixed nitrogen production ammonia | |
| CN103990472A (en) | Stable and efficient hydrogen production co-catalyst and preparation method thereof | |
| Chen et al. | A direct Z-scheme Bi2WO6/La2Ti2O7 photocatalyst for selective reduction of CO2 to CO | |
| CN113368876A (en) | Carbon dot-assisted Zn-AgIn5S8/Co9S8Preparation method of quantum dots and application of quantum dots in photohydrolysis hydrogen production | |
| An et al. | Enhancement of Ti 3 C 2 MXene on Au@ Ag/TiO 2 for the visible-light-driven photoreduction of nitroaromatics | |
| CN112354559A (en) | Two-dimensional receptor molecule/hierarchical pore TiO2Composite photocatalyst, preparation method and photocatalytic application thereof | |
| CN109078644B (en) | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof | |
| Li et al. | Chemical etching and phase transformation of Nickel-Cobalt Prussian blue analogs for improved solar-driven water-splitting applications | |
| CN106964380A (en) | A kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst and preparation method and applications | |
| CN115463667B (en) | Preparation method of composite photocatalytic nitrogen fixation material with iridium loaded by cuprous oxide of different crystal planes | |
| CN116371447A (en) | double-Z heterojunction photocatalyst and preparation method and application thereof | |
| Zhang et al. | Assembling CeO 2 nanoparticles on ZIF-8 via the hydrothermal method to promote the CO 2 photoreduction performance | |
| Gao et al. | In situ synthesis of p–n LaFeO3/ZnIn2S4 heterojunctions for enhanced photocatalytic activity | |
| CN113976127A (en) | 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 |