CN117019227B - Ni-MOF catalyst rich in oxygen vacancies and preparation method and application thereof - Google Patents
Ni-MOF catalyst rich in oxygen vacancies and preparation method and application thereof Download PDFInfo
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- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 238000009210 therapy by ultrasound Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000004577 artificial photosynthesis Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000005092 [Ru (Bpy)3]2+ Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of nano material photocatalysis, relates to a Ni-MOF catalyst rich in oxygen vacancies, and a preparation method and application thereof, and aims to solve the problem that a CO 2 product is difficult to regulate and control in solar photocatalytic reduction. Mainly comprises the following steps: NH 4 Cl is added into a precursor for synthesizing Ni-MOF by NiCl 2·6H2 O, terephthalic acid and the like, and the Ni-MOF series catalyst rich in oxygen vacancies is prepared through hydrothermal reaction. The method is simple and easy to operate; and the content of oxygen vacancies in the resulting Ni-MOF can be adjusted by simply controlling the content of NH 4 Cl, thereby affecting the selectivity of the Ni-MOF catalyst to the products CO and CH 4. The invention provides a new thought for preparing a catalyst for synthesizing a desired product by photocatalytic reduction of CO 2, and provides a preparation method of a photocatalyst with controllable product, which has very good prospect in the field of artificial photosynthesis.
Description
Technical Field
The invention belongs to the technical field of nano material photocatalysis, and relates to a Ni-MOF catalyst rich in oxygen vacancies, a preparation method and application thereof.
Background
The rapid development of industry has led to a dramatic increase in the CO 2 content in the atmosphere, an increasingly serious problem of greenhouse effect, and an urgent need to alleviate global warming and energy crisis. The photocatalytic reduction of CO 2 can generate energy fuels such as CO, CH 4、CH3 OH and the like, can effectively promote the development of green low carbon, and accords with the sustainable development concept. Therefore, the development of novel high-efficiency visible light photocatalysts is a research hotspot for photocatalytic reduction of CO 2.
Metal-organic frameworks (MOFs) are highly crystalline porous materials built by coordinating metal ions and organic ligands. MOFs materials have a range of unique properties, with great potential for gas capture and heterogeneous catalysis due to their permanent microporosity and large specific surface area, one of which is the catalysis of CO 2 capture and conversion reactions. The CO 2 reduction process is a multiprotocol coupled electron transfer process, and the final product formation is generally determined by the kinetic and thermodynamic parameters of the CO 2 reduction pathway. Taking CH 4 and CO as examples, CH 4 formation is thermodynamically favored over CO formation because the reaction of the former occurs at a lower potential. However, from a kinetic point of view, the formation of CH 4, which requires eight electrons, is more difficult than the two electron reduction of CO 2 to CO. Equations (1) and (2) for the reaction to generate CH 4 and CO are as follows (at ph=7):
In the chemical industry, CO is an important raw material for synthesizing a series of basic organic chemical products and intermediates as a main component of synthesis gas and various types of gas. Starting from CO, almost all of the basic chemicals present, such as ammonia, phosgene, and alcohols, acids, anhydrides, esters, ethers, amines, alkanes, alkenes, etc., can be produced. Methane is a high quality gaseous fuel with relatively high combustion values and is also an important feedstock for the production of synthesis gas and many chemical products. Patent CN114832830A discloses a MOF-derived B/A/B structure oxide heterojunction, a preparation method and application thereof, the invention prepares the B/A/B structure MOF heterojunction by reacting MnCo-MOF and absolute ethyl alcohol solution of first metal acetate in a closed reaction vessel at 70-100 ℃, then calcines the MOF-derived B/A/B structure oxide heterojunction at 400-550 ℃ to obtain the MOF-derived B/A/B structure oxide heterojunction, and the obtained B/A/B structure oxide heterojunction shows excellent product (CO and H 2) selectivity in the photo-reduction carbon dioxide reaction, but the preparation process requires further high-temperature calcination, the process is complex, and the regulation of the selectivity of the photo-catalytic product is difficult; CN116154199A discloses an ORR-OER catalyst with a nitrogen-doped carbon-supported cobalt-nickel double site and a preparation method thereof, and the preparation method is characterized in that a precursor CoPINi-MOF@ACW prepared through a series of processes is embedded by NH 4 Cl and pyrolyzed to obtain the ORR-OER catalyst with the nitrogen-doped carbon-supported cobalt-nickel double site of a target catalyst, wherein the preparation process is complex and the catalyst is mainly used for electrocatalysts. Therefore, regulating and controlling the product of photocatalytic reduction of CO 2 according to the requirements of practical application is a difficulty in the artificial light synthesis process.
Disclosure of Invention
Aiming at the difficulty that the photocatalytic reduction of carbon dioxide products is uncontrollable in the artificial photosynthesis field, the invention provides an oxygen vacancy-enriched Ni-MOF catalyst, and a preparation method and application thereof. The Ni-MOF catalyst rich in oxygen vacancies prepared by the method can regulate and control the photocatalytic reduction of CO 2 products, and the preparation mode of the catalyst is simple and the cost is low.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
A method for preparing a Ni-MOF catalyst rich in oxygen vacancies, comprising the steps of:
(1) Placing N, N-Dimethylformamide (DMF), ethanol (CH 3CH2 OH) and water in a container, stirring to uniformly mix them, and obtaining a colorless solution I;
(2) Adding terephthalic acid into the colorless solution I in the step (1), and performing ultrasonic dissolution to obtain colorless solution II;
(3) Adding nickel chloride hexahydrate (NiCl 2·6H2 O) into the colorless solution II obtained in the step (2), and performing ultrasonic dissolution to obtain a light green solution;
(4) Adding ammonium chloride (NH 4 Cl) into the light green solution in the step (3), carrying out ultrasonic treatment, stirring and dissolving, then placing the solution into a reaction kettle for hydrothermal reaction, respectively washing and centrifuging by using ethanol and water after the reaction is finished, pouring out supernatant, and drying the obtained product to obtain the Ni-MOF catalyst rich in oxygen vacancies.
In the step (1), the volume ratio of DMF, CH 3CH2 OH and water is (14-16) 1:1, and the stirring time is 5-10min.
The molar ratio of terephthalic acid to NiCl 2·6H2 O in the steps (2) and (3) is 1:1, and the dissolution is carried out by ultrasonic treatment for 10-15 min.
The molar concentration of NiCl 2·6H2 O in the step (3) is 0.021mol/L.
The molar concentration of NH 4 Cl in the step (4) is 0.026-0.093mol/L, ultrasonic is carried out for 15-20min, and stirring is carried out for 20min.
The reaction temperature in the step (4) is 150-200 ℃, and the reaction time is 20-24h.
The drying temperature in the step (4) is 50-90 ℃.
The Ni-MOF catalyst rich in oxygen vacancies is prepared by the preparation method.
The application of the Ni-MOF catalyst rich in oxygen vacancies in photocatalytic reduction of CO 2.
The invention has the beneficial effects that:
(1) The preparation method adopts a hydrothermal method, prepares the Ni-MOF catalyst containing oxygen vacancies with different concentrations through one-step reaction, and has simple preparation process.
(2) According to the Ni-MOF catalyst prepared by the preparation method, the amount of ammonia generated by decomposition in the synthesis process is gradually increased along with the increase of the addition amount of NH 4 Cl in the synthesis process, and ammonia is a reducing gas, so that the Ni-MOF cluster balls can be gradually enlarged on the one hand, and more oxygen vacancies can be promoted to be generated on the other hand, thereby being beneficial to improving the photocatalytic activity.
(3) According to the Ni-MOF catalyst obtained by the preparation method, the concentration of oxygen vacancies in the catalyst Ni-MOF can be influenced by adjusting the addition amount of NH 4 Cl, so that the transmission resistance of photo-generated electrons in the photo-catalytic reaction process is further influenced, and the selectivity of the obtained catalyst Ni-MOF for photo-catalytic reduction of reaction products (CO and CH 4) of CO 2 is further influenced. Therefore, the photocatalytic product can be regulated by simply controlling the addition amount of NH 4 Cl according to the requirements of practical application.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction (XRD) pattern of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3.
FIG. 2 is a scanning electron microscope image at the same magnification of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3: (A) pure Ni-MOF catalyst, (B) Ni-MOF-0.05 catalyst, (C) Ni-MOF-0.1 catalyst, and (D) Ni-MOF-0.18 catalyst.
FIG. 3 is an activity graph of photocatalytic reduction CO 2 for the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3: an activity map of (A) photocatalytic reduction of CO 2 to CO, (B) photocatalytic reduction of CO 2 to CH 4, and (C) photocatalytic reduction of CO 2 product regulation change histogram.
FIG. 4 is an ESR chart of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3.
FIG. 5 is an EIS diagram of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 32mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment for 5min for later use;
(2) Dissolving 0.75mmol of terephthalic acid in the solution obtained in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.75mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.05g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 15min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 24h at the temperature of 180 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 70 ℃ to obtain the Ni-MOF, and naming the Ni-MOF-0.05.
Example 2
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 32mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment of 5 min;
(2) Dissolving 0.75mmol of terephthalic acid in the solution obtained in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.75mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.1g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 15min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 24h at the temperature of 180 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 70 ℃ to obtain the Ni-MOF, and naming the Ni-MOF-0.1.
Example 3
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 32mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment for 5min for later use;
(2) Dissolving 0.75mmol of terephthalic acid in the solution obtained in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.75mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.18g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 17min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 24h at the temperature of 180 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 70 ℃ to obtain Ni-MOF, and naming the Ni-MOF-0.18.
Example 4
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 28mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment for 7min for later use;
(2) Dissolving 0.67mmol of terephthalic acid in the solution in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.67mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.09g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 20min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 24h at the temperature of 150 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 50 ℃ to obtain Ni-MOF, and naming the Ni-MOF-0.09.
Example 5
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 30mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment for 10min for later use;
(2) Dissolving 0.71mmol of terephthalic acid in the solution in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.71mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.12g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 15min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 20h at the temperature of 200 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 90 ℃ to obtain the Ni-MOF, and naming the Ni-MOF-0.12.
Example 6
The preparation method of the Ni-MOF catalyst rich in oxygen vacancies comprises the following steps:
(1) Placing 30mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment for 10min for later use;
(2) Dissolving 0.71mmol of terephthalic acid in the solution in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.71mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and performing ultrasonic treatment for 10min to obtain a light green solution for later use;
(4) Adding 0.06g of NH 4 Cl into the light green solution obtained in the step (3), carrying out ultrasonic treatment for 15min, stirring for 20min, after the solid is completely dissolved, transferring into a reaction kettle, placing the reaction kettle into an oven to react for 22h at the temperature of 170 ℃, respectively washing with ethanol and water, centrifuging, pouring out the supernatant, drying the obtained product at the temperature of 80 ℃ to obtain Ni-MOF, and naming the Ni-MOF-0.06.
Comparative example 1
The preparation method of the Ni-MOF catalyst of the comparative example comprises the following steps:
(1) Placing 32mL of DMF, 2mL of ethanol and 2mL of water into a 50mL small beaker for mixing, and uniformly mixing to form a colorless solution I after ultrasonic treatment of 5 min;
(2) Dissolving 0.75 mmol terephthalic acid in the solution in the step (1), and performing ultrasonic treatment for 10min to obtain a colorless solution II for later use;
(3) Adding 0.75 mmol of nickel chloride hexahydrate into the solution II obtained in the step (2), and carrying out ultrasonic treatment on the solution II to obtain a light green solution for later use, wherein the solution is obtained by ultrasonic treatment of 10 min;
(4) Transferring the light green solution obtained in the step (3) into a reaction kettle, placing the reaction kettle in an oven to react for 24 hours at the temperature of 180 ℃, then respectively washing and centrifuging by using ethanol and water, pouring out supernatant, and drying the obtained product at the temperature of 70 ℃ to obtain the pure Ni-MOF catalyst which is named as Ni-MOF-0.
Implementation effect analysis
(1) Characterization of the catalyst Crystal Structure
FIG. 1 shows XRD patterns of the pure Ni-MOF prepared in comparative example 1 and the Ni-MOF prepared in examples 1-3, which contain more oxygen vacancies. The characteristic diffraction peaks for all samples (Ni-MOF and Ni-MOF-NH 4 Cl) in FIG. 1 were evident as absorption peaks at2 theta values of 8.3, 15.0, 15.9, 17.0, 25.8, 30, consistent with the Ni-MOF (CCDC No. 985792) standard card, without any impurity peaks, indicating successful preparation of Ni-MOF. In addition, the shape of each diffraction absorption peak is relatively sharp in the figure, which shows that the prepared sample has relatively good crystallinity.
(2) Analysis of catalyst surface topography
FIG. 2 shows SEM images of pure Ni-MOFs prepared in comparative example 1 and Ni-MOFs containing more oxygen vacancies prepared in examples 1-3 at the same magnification. Panel A in FIG. 2 shows that the pure Ni-MOF is a clustered spherical particle. However, as the addition amount of NH 4 Cl increases during synthesis, the amount of ammonia gas generated by decomposition during synthesis is gradually increased, and the ammonia gas is a gas with reducibility, so that on one hand, ni-MOF cluster balls gradually grow larger, as shown in a diagram B in FIG. 2, a diagram C in FIG. 2 and a diagram D in FIG. 2, and on the other hand, more oxygen vacancies can be promoted.
(3) Activity test and analysis of catalyst photocatalytic reduction CO 2 product
The photocatalytic reduction experiments of CO 2 were carried out in a quartz glass reactor (100 mL), the light source of visible light being a 300W xenon lamp (PLS-SXE 300) fitted with a 420nm cut-off filter. Prior to the reaction, 5mg of the catalyst and 15mg of [ Ru (bpy) 3]Cl2·6H2 O were dispersed in 6mL of a mixed solution of acetonitrile (CH 3CN;3mL) ,H2 O (2 mL) and triethanolamine (TEOA; 1 mL). The TEOA was used as a sacrificial agent and [ Ru (bpy) 3]2+ was used as an electron mediator. Then, the reactor was evacuated and a CO 2 gas of 99.9% purity was introduced and the reaction was illuminated for 6h. The gas product was detected by gas chromatography equipped with TCD and FID (GC 7900).
In addition, the selectivity of CO and CH 4 can be calculated according to equation (1) and equation (2).
Wherein, the selectivity (%) of S CO to CO, the selectivity (%) of S CH4 to CH 4, and the reaction rate of n (CO) to CO (mmol g -1h-1）,n（CH4) to CH 4 (mmol g -1h-1) are all shown in the specification.
FIG. 3 shows the regulation of the photocatalytic reduction of carbon dioxide by pure Ni-MOF prepared in comparative example 1 and Ni-MOF prepared in examples 1-3, which contain more oxygen vacancies. In FIG. 3, A is a graph showing the comparison of activities of photocatalytic reduction of CO 2 to CO of pure Ni-MOF and Ni-MOF products containing more oxygen vacancies, and the result shows that the yield of CO generated by catalytic reduction of CO 2 by the Ni-MOF catalyst without NH 4 Cl is highest and can reach 8.0561 mmol.g -1. With the increase of the addition amount of NH 4 Cl during synthesis, the yield of the novel Ni-MOF catalyst for catalyzing and reducing CO 2 to CO gradually decreases from 8.0561 mmol.g -1 to 1.9944 mmol.g -1. FIG. 3B is a graph showing the comparison of activities of pure Ni-MOF and Ni-MOF products containing more oxygen vacancies to produce CH 4 by photocatalytic reduction of CO 2, and shows that: with the increase of the addition amount of NH 4 Cl during synthesis, the content of CH 4 in the product of the catalytic reduction CO 2 of the novel Ni-MOF catalyst is gradually increased from 0.07402 mmol.g -1 to 1.8782 mmol.g -1. The catalyst obtained by adding NH 4 Cl during synthesis is beneficial to the generation of a Ni-MOF photocatalytic reduction product CH 4, and a graph C in FIG. 3 is a product column summary graph, so that it can be clearly seen that the product of the photocatalytic reduction of CO 2 of Ni-MOF can be effectively regulated and controlled by controlling the addition amount of NH 4 Cl during synthesis, and the CO 2 is mainly CO in catalytic reduction of the Ni-MOF catalyst obtained by not adding NH 4 Cl, and the CO selectivity can be up to 96.45%; when the adding amount of NH 4 Cl reaches 0.18g, the product of the photocatalytic reduction of CO 2 by the catalyst is mainly CH 4, and the CH 4 selectivity can reach 79.03%. This is because adjusting the amount of NH 4 Cl added can affect the concentration of oxygen vacancies in the resulting catalyst Ni-MOF. The greater the concentration of oxygen vacancies, the less the transport resistance of the photogenerated electrons during the photocatalytic reaction (see FIG. 5), and the greater the proportion of the product CH 4 produced by the 8-electron reaction.
(4) ESR analysis of catalysts
Electron paramagnetic resonance (ESR) is the detection of the presence of paramagnetic species in the catalyst by a Bruker ESR a300-10/12 spectrometer in the dark state at room temperature (298K). The signal peak of g=2.003 corresponds to the presence of oxygen vacancies with single electron tethering.
FIG. 4 is an ESR chart of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3. From the figure, it can be seen that at g=2.003, all samples have a significant signal peak of oxygen vacancies, which proves that the prepared Ni-MOF catalyst contains oxygen vacancies. It can be seen from the graph that as the addition amount of NH 4 Cl increases during synthesis, the signal peak of ESR gradually increases, which indicates that the concentration of oxygen vacancies contained in the prepared catalyst gradually increases, and the specific size relationship is as follows: c VO,Ni-MOF-0.18>CVO,Ni-MOF-0.1>CVO,Ni-MOF-0.05>CVO, ni-MOF.
(5) EIS analysis of catalysts
The electrochemical impedance spectrum of the catalyst was measured using an electrochemical workstation (CHI 630E, china) equipped with a standard three-electrode photoelectrochemical cell. The working electrode was prepared as follows: 20mg of the catalyst to be tested was dispersed in 0.5mL of ultrapure water, followed by addition of 50 mL Nafion solution (5 wt%) to form a uniform slurry. The obtained slurry was uniformly coated on indium tin oxide (2.0 cm. Times.1.5 cm) glass to obtain a working electrode. An Ag/AgCl electrode and Pt filament were used as reference and counter electrodes, respectively. Electrochemical Impedance Spectroscopy (EIS) was measured using Zennium pro electrochemical workstation (ZAHNER, germany) under visible light irradiation in the frequency range of 100 kHz-0.1Hz, using a solution of 5mM [ Fe (CN) 6]3-/[Fe（CN）6]4- and 0.5M KCl as electrode solution.
FIG. 5 is an EIS spectrum of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3. Under visible light irradiation, the arc radius of the electrochemical impedance diagram of Ni-MOF-NH 4 Cl is smaller than that of Ni-MOF, and the arc radius of Ni-MOF-0.18 is minimum, which shows that the Ni-MOF-0.18 catalyst has the smallest charge transfer resistance, which greatly promotes the rapid transmission of photo-generated carriers.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements falling within the spirit and principles of the invention.
Claims (5)
1. A method for preparing a Ni-MOF catalyst rich in oxygen vacancies, comprising the steps of:
(1) Placing N, N-dimethylformamide, ethanol and water in a container, and stirring until the N, N-dimethylformamide, ethanol and water are uniformly mixed to prepare a colorless solution I;
(2) Adding terephthalic acid into the colorless solution I in the step (1), and dissolving the terephthalic acid by ultrasonic to prepare colorless solution II;
(3) Adding nickel chloride hexahydrate into the colorless solution II obtained in the step (2), wherein the molar ratio of the added nickel chloride hexahydrate to terephthalic acid is 1:1, and carrying out ultrasonic dissolution to obtain a pale green solution with the molar concentration of the nickel chloride hexahydrate of 0.021 mol/L;
(4) Adding ammonium chloride into the light green solution in the step (3), carrying out ultrasonic treatment, stirring and dissolving to ensure that the molar concentration of the ammonium chloride is 0.026-0.093mol/L, and then carrying out hydrothermal reaction for 20-24h at 150-200 ℃, washing, centrifuging and drying to obtain the Ni-MOF catalyst rich in oxygen vacancies.
2. The method for preparing an oxygen vacancy-rich Ni-MOF catalyst according to claim 1, wherein the volume ratio of N, N-dimethylformamide, ethanol and water in step (1) is (14-16): 1:1.
3. The method for producing an oxygen vacancy-rich Ni-MOF catalyst according to claim 2, wherein in step (4), the washing refers to washing with ethanol and water, respectively; the drying temperature is 50-90 ℃.
4. An oxygen vacancy-rich Ni-MOF catalyst prepared by the preparation method of any one of claims 1to 3.
5. Use of the oxygen vacancy-rich Ni-MOF catalyst of claim 4 for photocatalytic reduction of CO 2.
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| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
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| CN115109264A (en) * | 2022-06-28 | 2022-09-27 | 四川师范大学 | MOF (metal organic framework) nano material with oxygen vacancy as well as preparation method and application thereof |
| CN115274308A (en) * | 2022-06-24 | 2022-11-01 | 浙江师范大学 | Oxygen vacancy-rich MXene @ Ce-MOF material, preparation method thereof and application thereof in supercapacitor |
| CN116422378A (en) * | 2023-03-24 | 2023-07-14 | 大连理工大学 | Cu (copper) alloy 2 O-CuXbpy composite material CO 2 Preparation method and application of photoreduction catalyst |
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| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
| CN113113604A (en) * | 2021-03-04 | 2021-07-13 | 华南师范大学 | Micron open-cell cage-shaped defect MnO @ Ni material and preparation method and application thereof |
| CN115274308A (en) * | 2022-06-24 | 2022-11-01 | 浙江师范大学 | Oxygen vacancy-rich MXene @ Ce-MOF material, preparation method thereof and application thereof in supercapacitor |
| CN115109264A (en) * | 2022-06-28 | 2022-09-27 | 四川师范大学 | MOF (metal organic framework) nano material with oxygen vacancy as well as preparation method and application thereof |
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