CN114177923A - Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application - Google Patents
Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application Download PDFInfo
- Publication number
- CN114177923A CN114177923A CN202111305681.9A CN202111305681A CN114177923A CN 114177923 A CN114177923 A CN 114177923A CN 202111305681 A CN202111305681 A CN 202111305681A CN 114177923 A CN114177923 A CN 114177923A
- Authority
- CN
- China
- Prior art keywords
- uio
- mos
- acetic acid
- nano material
- composite
- 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.)
- Withdrawn
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013207 UiO-66 Substances 0.000 claims abstract description 94
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002131 composite material Substances 0.000 claims abstract description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 16
- 239000012621 metal-organic framework Substances 0.000 claims description 16
- 239000004677 Nylon Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 229920001778 nylon Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000013032 photocatalytic reaction Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000002135 nanosheet Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000012924 metal-organic framework composite Substances 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000002149 hierarchical pore Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004577 artificial photosynthesis Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Abstract
The invention discloses a method for preparing CO2UiO-66/MoS for preparing acetic acid2A composite nano material, a preparation method and application belong to the technical field of photocatalytic energy conversion. According to the invention, the UiO-66 with a multistage pore channel structure is prepared by a simple pyrolysis method, and then molybdenum disulfide is injected into the pore channel of the UiO-66 by a solvothermal synthesis method to prepare the metal organic framework composite nanomaterial embedded with molybdenum disulfide nanosheets. The acetic acid is prepared by photocatalytic carbon dioxide reduction with water as the only hydrogen source in the absence of any electron sacrificial agent. The results show that: UiO-66 with multi-level pore structure is favorable for MoS2The nano-sheets enter the pore canal to form rich Zr-O-Mo interface structure which is not only beneficial toThe migration of the photon-generated carriers is more beneficial to C-C coupling in the reduction process of carbon dioxide to form C2 product acetic acid.
Description
Technical Field
The invention belongs toThe technical field of composite nano material synthesis and photocatalytic carbon dioxide conversion, and relates to UiO-66/MoS for preparing acetic acid by artificial photosynthesis2Preparation and application of composite nano material.
Background
With the development of industry, the use of large quantities of fossil fuels (petroleum, coal and natural gas) results in large quantities of carbon dioxide (CO)2) And is discharged to the atmosphere. Continuous consumption of non-renewable fossil fuels and greenhouse gas CO2Resulting in energy shortage and greenhouse effect. Introducing CO2The conversion to carbon monoxide (CO) and other value-added chemicals (methane, methanol, formic acid, ethanol, etc.) has become a research hotspot in the field of energy catalysis. The global photocatalytic reduction of carbon dioxide, mimicking natural photosynthesis in plants, into value-added products has attracted considerable research interest in the past few years. Photocatalytic reduction of CO2Is considered to be a green development scheme with great potential. On the one hand, the solar energy is used as a high-efficiency clean renewable energy source to carry out photocatalytic reduction on CO2Can be carried out at normal temperature and normal pressure, directly utilizes sunlight without consuming other auxiliary energy sources, and can really realize the recycling of carbon resources. Solar driven CO2The conversion of the carbon dioxide into high-value chemicals is one of feasible technical means for realizing the aim of carbon neutralization, and becomes a hotspot for researching the current research.
In recent years, Metal-Organic frameworks (MOFs) formed by self-assembling Metal ions or Metal clusters and Organic ligands are a novel class of porous crystalline solid materials, generally have the advantages of high porosity, high specific surface area, structure cuttability, easy functionalization, multiple active sites and the like, and have shown important application prospects in the fields of gas storage and separation, molecular sensing, photoelectric materials, drug carriers, catalysis and the like. The hot trends in the research using MOF materials as photocatalysts are mainly due to the fact that MOFs have several excellent properties, including: (1) energy band structure engineering, which effectively utilizes solar energy by adjusting the band gap distance; (2) the appearance structure is functionalized, the appearance structure of the material is designed, unsaturated sites are introduced, and a narrow window is designedAnd the method such as gap increases the absorption to the reactant, provides more active sites; (3) and the catalyst is coordinated and catalyzed to promote the separation and migration of photon-generated carriers and improve the catalytic activity. But currently, MOFs are used for photocatalytic CO2The reduction is mostly carried out in the presence of a sacrificial agent, and since the MOFs contain an organic ligand in the structure, the oxidation of the organic ligand can be realized in the oxidation process of water, and CO is difficult to realize2And H2The photocatalytic conversion of O does not follow the principle of green chemistry. In addition, most of the current MOFs catalyze the conversion of carbon dioxide to C1 product (CO, HCOOH, CH)4MeOH), it is difficult to achieve carbon chain growth, and conversion to high value-added chemicals is difficult.
The invention aims to overcome the defects of the prior art and is favorable for MoS of water decomposition2The carbon chain is loaded in the UiO-66 pore channel to form a rich interface structure, so that the conversion of carbon dioxide and water is realized, and the growth of the carbon chain is realized and the carbon chain is converted into a C2 product with high added value.
Disclosure of Invention
In order to solve the problems, the invention provides an effective synthesis method, the UiO-66 with a multistage pore channel structure is prepared by a simple pyrolysis method, and then molybdenum disulfide is injected into the pore channel of the UiO-66 by a solvothermal synthesis method to form an abundant Zr-O-Mo interface structure, wherein the interface structure is not only beneficial to the migration of a photon-generated carrier, but also more beneficial to C-C coupling in the reduction process of carbon dioxide to form C2 product acetic acid. The method is simple and easy to implement, the reaction condition is mild, and the prepared UiO-66/MoS2The nano composite material has higher capacity of converting carbon dioxide and water into acetic acid and oxygen by photocatalysis, realizes 'artificial photosynthesis' in a real sense and obtains high selectivity of a C2 product.
The technical scheme of the invention is as follows:
can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nanomaterial of UiO-66/MoS2The composite nano material is MoS2And a UiO-66 metal organic framework, wherein the UiO-66 metal organic framework has a multi-level pore canal structure, and the M is a porous materialoS2Embedded in the multilevel pore canal of the UiO-66 metal organic framework.
The MoS embedded in the multilevel pore canal of the UiO-66 metal organic framework2Forms an abundant Zr-O-Mo interface structure with the UiO-66.
Can be used for CO2UiO-66/MoS for preparing acetic acid2The preparation method of the composite nano material comprises the following specific steps:
the method comprises the following steps: preparation of metal organic framework structure UiO-66 with multilevel pore channels
And (3) putting the UiO-66 in a tube furnace, and calcining for a plurality of hours at high temperature under the protection of Ar.
Step two: mosaic MoS2In the UiO-66 pore canal
Ultrasonically dispersing the UiO-66 with the multistage pore structure and the ammonium tetrathiomolybdate prepared in the step one into an N, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, carrying out a solvothermal reaction for a plurality of hours, cooling to room temperature, centrifuging, washing and drying to obtain the UiO-66/MoS2A composite nanomaterial.
In the first step, the temperature of the high-temperature calcination is 400-450 ℃, and the time of the high-temperature calcination is 12-48 h.
In the second step, the mass ratio of UiO-66 to ammonium tetrathiomolybdate is 40-2: 1; the temperature of the solvothermal reaction is 120-200 ℃, and the reaction time is 6-24 h.
The UiO-66/MoS2Application of composite nano material, UiO-66/MoS2The composite nano material is used as a photocatalyst and applied to photocatalysis of carbon dioxide and water to be converted into acetic acid and oxygen. The concrete application is as follows:
mixing UiO-66/MoS2Loading the composite nano material on a nylon filter membrane, placing the nylon filter membrane in a gas-solid photocatalytic reaction system of water and carbon dioxide, and allowing visible light to reach lambda>Photocatalysis is carried out under the illumination of 420 nm.
The invention has the beneficial effects that:
(1) the invention prepares the UiO-66 with the multi-stage pore canal structure by a simple pyrolysis method, which is beneficial to MoS2Growing in the pore canal, is more beneficial to the material transmission in the photocatalysis process。
(2) According to the invention, through solvothermal reaction, MoS generated by pyrolysis of ammonium thiomolybdate under the conditions of high temperature and high pressure2The material can be uniformly embedded in a pore channel of the UiO-66 to form a rich Zr-O-Mo interface structure, and is more favorable for the transmission of current carriers generated under the excitation of illumination.
(3) The UiO-66/MoS provided by the invention2The composite nano material can rapidly separate and transfer photogenerated electrons and holes under the condition of optical excitation, and the holes are transferred to MoS2Oxygen is generated by oxidation of water, and electrons are transferred to Zr-O cluster metal nodes of UiO-66 to reduce carbon dioxide and convert the carbon dioxide into acetic acid. Under the synergistic effect of bimetal on Zr-O-Mo interface, the growth of C-C coupled carbon chain is realized.
Drawings
FIG. 1 is a hierarchical pore structure characterization plot of UiO-66 prepared in step (1) of example 1. Wherein (a) is a comparison of XRD patterns of the multi-stage channel structure synthesized in step (1) of example 1 and the complete UiO-66, which shows that the UiO-66 has obvious channel defect structure by pyrolysis. (b) Is a comparison graph of nitrogen absorption and desorption curves and pore distribution of the UiO-66 with the hierarchical pore structure prepared in the step (1) of the example 1 and the complete UiO-66, and shows that the UiO-66 has the hierarchical pore structure of micropores and mesopores through high-temperature pyrolysis, and the pore is obviously enlarged.
FIG. 2(a) shows the hierarchical cell structure of UiO-66 prepared in step (1) of example 1 and UiO-66/MoS prepared in step (2) of example 12Comparing the composite nanometer material with a real object; FIG. 2(b) is UiO-66/MoS prepared in step (2) of example 12Scanning electron microscope images of the composite nanomaterials; FIG. 2(c) is UiO-66/MoS prepared in step (2) of example 12Transmission electron microscopy images of composite nanomaterials. The structure shows that MoS can be converted by means of the heat of solution2The nano-particles are well embedded into UiO-66 to form a binary composite material with MoS2 nano-sheets uniformly dispersed in the UiO-66.
FIG. 3(a) is a photo-catalytic gas-solid reaction apparatus as mentioned in step (3) of example 1; FIG. 3(b) is CH as described in step (3) of example 13COOH and O2Time reaction yield diagram; FIG. 3(c) is the generation described in step (3) of example 1CH (A) of3COOH isotopically labelled13A CNMR map. The results show that the UiO-66/MoS prepared in example 12Has good capability of photocatalysis carbon dioxide and water to be converted into acetic acid and oxygen.
FIG. 4(a) is UiO-66/MoS prepared in step (2) of example 22Scanning electron microscope images of the composite nanomaterials; FIG. 4(b) is UiO-66/MoS prepared in step (2) of example 32Scanning electron microscope images of the composite nanomaterials; FIG. 4(c) is UiO-66/MoS prepared in step (2) of example 42Scanning electron microscope images of the composite nanomaterials; FIG. 4(d) is UiO-66/MoS prepared in step (2) of example 52Scanning electron microscope images of the composite nanomaterials. The results show that the MoS inlaid can be obtained under the limited conditions of the invention2UiO-66/MoS of nanosheets2A composite nanomaterial.
FIG. 5 shows UiO-66/MoS prepared in step (2) of examples 2-52Yield graph of photocatalytic product. The results show that the MoS inlaid can be obtained under the limited conditions of the invention2UiO-66/MoS of nanosheets2The composite nano material has good capability of photocatalysis carbon dioxide and water to be converted into acetic acid and oxygen.
FIG. 6 is a graph of the results of the product of the present invention.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1:
(1) 100mgUiO-66 is put into a tube furnace and calcined for 48 hours at the high temperature of 400 ℃ under the protection of Ar.
(2) 100mg UiO-66 with a hierarchical pore structure and 10mg ammonium tetrathiomolybdate which are prepared in the step (1) are mixed according to the mass ratio of 10: 1, ultrasonically dispersing into 10mLN, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 120 ℃, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66/MoS2Composite nanomaterial
(3) The UiO-66/MoS prepared in the step (2)2Dispersing 5mg of composite nano material in 10ml of water by ultrasonic wave, and loading the composite nano material to the nylon by suction filtrationAnd (5) drying the mixture on a nanofiltration membrane in vacuum to remove water. Placing the nylon filter membrane with catalyst in a gas-solid photocatalytic reaction system of water and carbon dioxide, and exposing to visible light (lambda)>420nm) for 8 h. Gas and liquid phase products were detected using a GC7900 type chromatograph and a Bruker AC-400FT spectrometer (500MHz), respectively. The detection structure shows that the product UiO-66/MoS prepared by the embodiment2Photocatalytic CO of catalyst2And H2The rates of O conversion to acetic acid and oxygen were 32.5. mu. mol/g/h and 65. mu. mol/g/h, respectively, with product selectivity to acetic acid as high as 94%.
Example 2:
(1) 100mg of UiO-66 was calcined at 450 ℃ for 12 hours in a tube furnace under the protection of Ar.
(2) 100mg of UiO-66 and 5mg of ammonium tetrathiomolybdate with a hierarchical pore structure, which are prepared in the step (1), wherein the mass ratio of the ammonium tetrathiomolybdate to the ammonium tetrathiomolybdate is 20: 1, ultrasonically dispersing into 10mLN, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, reacting for 6 hours at 200 ℃, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66/MoS2Composite nanomaterial
(3) The UiO-66/MoS prepared in the step (2)2Ultrasonically dispersing 5mg of the composite nano material in 10ml of water, carrying the composite nano material on a nylon filter membrane through suction filtration, and drying the composite nano material in vacuum to remove water. Placing the nylon filter membrane with catalyst in a gas-solid photocatalytic reaction system of water and carbon dioxide, and exposing to visible light (lambda)>420nm) for 8 h. Gas and liquid phase products were detected using a GC7900 type chromatograph and a Bruker AC-400FT spectrometer (500MHz), respectively. The detection structure shows that the product UiO-66/MoS prepared by the embodiment2Photocatalytic CO of catalyst2And H2The rates of O conversion to acetic acid and oxygen were 30.5. mu. mol/g/h and 62. mu. mol/g/h, respectively, with product selectivity to acetic acid as high as 92.6%.
Example 3:
(1) 100mg of UiO-66 was calcined in a tube furnace at a high temperature of 420 ℃ for 24 hours under the protection of Ar.
(2) 100mg of UiO-66 with a hierarchical pore structure and 20mg of ammonium tetrathiomolybdate, which are prepared in the step (1), are mixed according to the mass ratio of 5: ultrasonic dispersion of 1 to 10mLN, N-dimethylTransferring the formamide solution into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66/MoS2Composite nanomaterial
(3) The UiO-66/MoS prepared in the step (2)2Ultrasonically dispersing 5mg of the composite nano material in 10ml of water, carrying the composite nano material on a nylon filter membrane through suction filtration, and drying the composite nano material in vacuum to remove water. Placing the nylon filter membrane with catalyst in a gas-solid photocatalytic reaction system of water and carbon dioxide, and exposing to visible light (lambda)>420nm) for 8 h. Gas and liquid phase products were detected using a GC7900 type chromatograph and a Bruker AC-400FT spectrometer (500MHz), respectively. The detection structure shows that the product UiO-66/MoS prepared by the embodiment2Photocatalytic CO of catalyst2And H2The rates of O conversion to acetic acid and oxygen were 31.2. mu. mol/g/h and 63.2. mu. mol/g/h, respectively, with a product selectivity to acetic acid as high as 93.1%.
Example 4:
step (1) same as example 1;
(2) 100mg of UiO-66 and 5mg of ammonium tetrathiomolybdate with a hierarchical pore structure, which are prepared in the step (1), wherein the mass ratio of the ammonium tetrathiomolybdate to the ammonium tetrathiomolybdate is 20: 1, ultrasonically dispersing into 10mLN, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, reacting for 6 hours at 200 ℃, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66/MoS2Composite nanomaterial
(3) The UiO-66/MoS prepared in the step (2)2Ultrasonically dispersing 5mg of the composite nano material in 10ml of water, carrying the composite nano material on a nylon filter membrane through suction filtration, and drying the composite nano material in vacuum to remove water. Placing the nylon filter membrane with catalyst in a gas-solid photocatalytic reaction system of water and carbon dioxide, and exposing to visible light (lambda)>420nm) for 8 h. Gas and liquid phase products were detected using a GC7900 type chromatograph and a Bruker AC-400FT spectrometer (500MHz), respectively. The detection structure shows that the product UiO-66/MoS prepared by the embodiment2Photocatalytic CO of catalyst2And H2The rates of O conversion to acetic acid and oxygen were 32.1. mu. mol/g/h and 64.3. mu. mol/g/h, respectively, with a product selectivity for acetic acid as high as 93%.
Example 5:
step (1) same as example 1;
(2) 100mg of UiO-66 and 5mg of ammonium tetrathiomolybdate with a hierarchical pore structure, which are prepared in the step (1), wherein the mass ratio of the ammonium tetrathiomolybdate to the ammonium tetrathiomolybdate is 20: 1, ultrasonically dispersing into 10mLN, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, cooling to room temperature, centrifuging, washing and drying to obtain UiO-66/MoS2Composite nanomaterial
(3) The UiO-66/MoS prepared in the step (2)2Ultrasonically dispersing 5mg of the composite nano material in 10ml of water, carrying the composite nano material on a nylon filter membrane through suction filtration, and drying the composite nano material in vacuum to remove water. Placing the nylon filter membrane with catalyst in a gas-solid photocatalytic reaction system of water and carbon dioxide, and exposing to visible light (lambda)>420nm) for 8 h. Gas and liquid phase products were detected using a GC7900 type chromatograph and a Bruker AC-400FT spectrometer (500MHz), respectively. The detection structure shows that the product UiO-66/MoS prepared by the embodiment2Photocatalytic CO of catalyst2And H2The rates of O conversion to acetic acid and oxygen were 30.7. mu. mol/g/h and 62.8. mu. mol/g/h, respectively, with product selectivity to acetic acid as high as 92.6%.
In conclusion, the preparation example can be obtained;
(1) under a wider temperature range and pyrolysis time, the UiO-66 with the multi-level pore channel structure can be prepared by a high-temperature pyrolysis method.
(2) Under a wider mass ratio range, the MoS inlaid can be obtained by controlling the mass ratio of the UiO-66 with the multi-stage pore structure and the ammonium tetrathiomolybdate2Nanosheet UO-66/MoS 2 composite nanomaterial.
(3) The catalyst prepared by the invention can catalyze CO by photocatalysis under the condition of visible light2And H2O is converted to acetic acid and oxygen and high acetic acid yields and selectivities are obtained.
Claims (7)
1. Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nanomaterial characterised in that: the UiO-66/MoS2The composite nano material is MoS2And a UiO-66 metal organic frameworkThe composite material comprises a UiO-66 metal organic framework with a multi-stage pore canal structure, and the MoS2Embedded in the multilevel pore canal of the UiO-66 metal organic framework.
2. The composition of claim 1 useful for CO2UiO-66/MoS for preparing acetic acid2Composite nanomaterial characterised in that: the MoS embedded in the multilevel pore canal of the UiO-66 metal organic framework2Forms an abundant Zr-O-Mo interface structure with the UiO-66.
3. Use according to any of claims 1-2 for CO2UiO-66/MoS for preparing acetic acid2The preparation method of the composite nano material is characterized by comprising the following specific steps of:
the method comprises the following steps: preparation of metal organic framework structure UiO-66 with multilevel pore channels
Placing the UiO-66 in a tubular furnace, and calcining for a plurality of hours at high temperature under the protection of Ar;
step two: mosaic MoS2In the UiO-66 pore canal
Ultrasonically dispersing the UiO-66 with the multistage pore structure and the ammonium tetrathiomolybdate prepared in the step one into an N, N-dimethylformamide solution, transferring into a polytetrafluoroethylene reaction kettle, carrying out a solvothermal reaction for a plurality of hours, cooling to room temperature, centrifuging, washing and drying to obtain the UiO-66/MoS2A composite nanomaterial.
4. The catalyst of claim 3 useful for CO2UiO-66/MoS for preparing acetic acid2The preparation method of the composite nano material is characterized by comprising the following steps: in the first step, the temperature of the high-temperature calcination is 400-450 ℃, and the time of the high-temperature calcination is 12-48 h.
5. The composition of claim 3 or 4 for use in CO2UiO-66/MoS for preparing acetic acid2The preparation method of the composite nano material is characterized by comprising the following steps: in the second step, the mass ratio of the UiO-66 to the ammonium tetrathiomolybdate is 40-2: 1; the temperature of the solvothermal reaction is 120-200 ℃, and the reaction time is 6-one24h。
6. UiO-66/MoS according to any of claims 1 to 52The application of the composite nano material is characterized in that: the UiO-66/MoS2The composite nano material is used as a photocatalyst and applied to photocatalysis of carbon dioxide and water to be converted into acetic acid and oxygen.
7. Use according to claim 6, characterized in that: mixing UiO-66/MoS2Loading the composite nano material on a nylon filter membrane, placing the nylon filter membrane in a gas-solid photocatalytic reaction system of water and carbon dioxide, and allowing visible light to reach lambda>Photocatalysis is carried out under the illumination of 420 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111305681.9A CN114177923A (en) | 2021-11-05 | 2021-11-05 | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111305681.9A CN114177923A (en) | 2021-11-05 | 2021-11-05 | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114177923A true CN114177923A (en) | 2022-03-15 |
Family
ID=80540791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111305681.9A Withdrawn CN114177923A (en) | 2021-11-05 | 2021-11-05 | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114177923A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950563A (en) * | 2022-06-01 | 2022-08-30 | 中国科学院海洋研究所 | Photocatalyst capable of degrading organic dye and/or heavy metal ions and preparation method thereof |
| CN115463690A (en) * | 2022-09-20 | 2022-12-13 | 东南大学 | Two-dimensional hierarchical porous bimetallic MOF photocatalyst and preparation method thereof |
| WO2023173683A1 (en) * | 2022-03-16 | 2023-09-21 | 苏州大学 | Application of metal sulfide piezoelectric material in piezoelectric catalytic reduction of co2 |
| CN116791112B (en) * | 2022-03-16 | 2024-05-14 | 苏州大学 | Piezoelectric material of metal sulfide for piezocatalysis reduction of CO2Application in (a) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201706805D0 (en) * | 2017-04-28 | 2017-06-14 | Cambridge Entpr Ltd | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN110918126A (en) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst |
| CN113058659A (en) * | 2021-03-19 | 2021-07-02 | 东南大学 | Nano TiO (titanium dioxide)2Preparation method and application of/UiO-66 composite material |
| CN113318792A (en) * | 2021-06-22 | 2021-08-31 | 哈尔滨理工大学 | Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof |
-
2021
- 2021-11-05 CN CN202111305681.9A patent/CN114177923A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201706805D0 (en) * | 2017-04-28 | 2017-06-14 | Cambridge Entpr Ltd | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN110918126A (en) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst |
| CN113058659A (en) * | 2021-03-19 | 2021-07-02 | 东南大学 | Nano TiO (titanium dioxide)2Preparation method and application of/UiO-66 composite material |
| CN113318792A (en) * | 2021-06-22 | 2021-08-31 | 哈尔滨理工大学 | Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| YU FENGYANG 等: "Hierarchically Porous Metal-Organic Framework/MoS2 Interface for Selective Photocatalytic Conversion of CO2 with H2O into CH3COOH", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| ZHANG LE 等: "Facile synthesis of amorphous MoSx-Fe anchored on Zr-MOFs towards efficient and stable electrocatalytic hydrogen evolution", 《CHEMICAL COMMUNICATIONS》 * |
| 刘慧锦 等: "UiO-66-NH2/MoS2复合材料的形貌调控及光催化制氢", 《中国科技信息》 * |
| 独彪: "UiO-66、ZIF-8基异质结构可见光催化材料的设计与性能的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023173683A1 (en) * | 2022-03-16 | 2023-09-21 | 苏州大学 | Application of metal sulfide piezoelectric material in piezoelectric catalytic reduction of co2 |
| CN116791112A (en) * | 2022-03-16 | 2023-09-22 | 苏州大学 | Piezoelectric material of metal sulfide for piezocatalysis reduction of CO 2 Application in (a) |
| CN116791112B (en) * | 2022-03-16 | 2024-05-14 | 苏州大学 | Piezoelectric material of metal sulfide for piezocatalysis reduction of CO2Application in (a) |
| CN114950563A (en) * | 2022-06-01 | 2022-08-30 | 中国科学院海洋研究所 | Photocatalyst capable of degrading organic dye and/or heavy metal ions and preparation method thereof |
| CN114950563B (en) * | 2022-06-01 | 2023-05-12 | 中国科学院海洋研究所 | Photocatalyst capable of degrading organic dye and/or heavy metal ions and preparation thereof |
| CN115463690A (en) * | 2022-09-20 | 2022-12-13 | 东南大学 | Two-dimensional hierarchical porous bimetallic MOF photocatalyst and preparation method thereof |
| CN115463690B (en) * | 2022-09-20 | 2023-10-27 | 东南大学 | Two-dimensional hierarchical pore bimetallic MOF photocatalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114177923A (en) | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application | |
| CN110841622B (en) | Controllable In preparation based on MOF template2O3Method for preparing @ ZnO nano heterojunction photocatalytic material | |
| CN109331883A (en) | A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application | |
| CN108525677B (en) | Cerium dioxide/indium zinc sulfide nanosheet composite catalyst and application thereof in visible light catalysis of CO2Use in transformation | |
| CN114042471B (en) | Visible light response type Zn 2 TiO 4 /g-C 3 N 4 Heterojunction material and application thereof | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN111437846A (en) | Porous CoO/CoP nanotube and preparation method and application thereof | |
| CN112958096B (en) | Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst | |
| CN112844413A (en) | Preparation method and application of photocatalyst with sphalerite/wurtzite junction | |
| CN112354559A (en) | Two-dimensional receptor molecule/hierarchical pore TiO2Composite photocatalyst, preparation method and photocatalytic application thereof | |
| CN116726973A (en) | Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof | |
| CN111871463A (en) | Preparation method of electrocatalytic full-decomposition water material based on ZIF-67 and UiO-66 double MOFs | |
| CN112717958B (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
| CN116196944A (en) | Preparation method and application of biomass nitrogen-doped carbon quantum dot coupled ultrathin BiOBr nano-sheet composite photocatalyst | |
| CN115400792A (en) | Modified PDI photocatalyst and preparation method and application thereof | |
| CN112657516B (en) | Direct Z-type photocatalyst and preparation method and application thereof | |
| CN114192166A (en) | ZnOxSy photocatalyst with high visible light hydrogen production activity and preparation method thereof | |
| CN110252349B (en) | CdS @ MoS prepared by in-situ photo-deposition2Preparation method of composite photocatalyst | |
| CN112604705A (en) | NPC-MoS2/Bi4O5Br2Preparation method and application of composite material photocatalyst | |
| CN113751078A (en) | TiO under MOF confinement2Preparation method of nano composite photocatalyst | |
| CN112570030A (en) | Bi4O5Br2Preparation method and application of/Fe-MIL composite material photocatalyst | |
| CN106964384B (en) | A kind of nickel-base catalyst and preparation method thereof of nanometer silicon carbide load | |
| CN111871434A (en) | Bismuth oxyiodide/nano-diamond composite photocatalyst and preparation method thereof | |
| CN110721687A (en) | Self-supporting porous Fe2O3Nanorod array electrocatalyst and preparation method thereof | |
| CN110560099A (en) | Preparation method and application of BiOI nanoflower with three-dimensional layered structure |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220315 |
|
| WW01 | Invention patent application withdrawn after publication |