CN117019227A - 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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- CN117019227A CN117019227A CN202311053901.2A CN202311053901A CN117019227A CN 117019227 A CN117019227 A CN 117019227A CN 202311053901 A CN202311053901 A CN 202311053901A CN 117019227 A CN117019227 A CN 117019227A
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- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 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
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000009210 therapy by ultrasound Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 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 15
- 238000003756 stirring Methods 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000004577 artificial photosynthesis Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004458 analytical method Methods 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 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
- 238000001035 drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 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
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid 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
- 238000001566 impedance spectroscopy 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
- 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
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- 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, and relates to an oxygen vacancy-enriched Ni-MOF catalyst, a preparation method and application thereof, which are used for solving the problem of CO reduction by solar photocatalysis 2 The product is difficult to regulate and control. Mainly comprises the following steps: in NiCl 2 ·6H 2 NH is added into precursor of synthesizing Ni-MOF by O, terephthalic acid and the like 4 Cl, and preparing the Ni-MOF series catalyst rich in oxygen vacancies through hydrothermal reaction. The method is simple and easy to operate; and can be controlled by simply controlling NH 4 Cl content to adjust the resulting Ni-The content of oxygen vacancies in the MOF, thereby affecting the Ni-MOF catalyst to the products CO and CH 4 Is selected from the group consisting of (1). The invention relates to a method for preparing photocatalytic reduction CO 2 The catalyst for synthesizing the expected product provides a new thought and provides a preparation method of the 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 CO in the atmosphere 2 The content is increased sharply, the problem of greenhouse effect is increased seriously, and the global warming and energy crisis are relieved. Photocatalytic reduction of CO 2 Can generate CO and CH 4 、CH 3 The energy fuels such as OH and the like can effectively promote the development of green low carbon and accord with the sustainable development concept. Therefore, a novel high-efficiency visible light photocatalyst is developed to be used for photocatalytic reduction of CO 2 Is a research hotspot.
Metal-organic frameworks (MOFs) are highly crystalline porous materials built by coordinating metal ions and organic ligands. MOFs materials have a unique set of properties, with great potential for gas capture and heterogeneous catalysis, one of which is CO, due to their permanent microporosity and large specific surface area 2 Capturing and catalyzing of the conversion reaction. CO 2 The reduction process being a multiprotocol coupled electron transfer process, the final product being formed generally from CO 2 Kinetic and thermodynamic parameters of the reduction pathway. By CH 4 And CO as an example, CH 4 The formation is thermodynamically favored over the formation of CO, as the reaction of the former occurs at a lower potential. However, from a kinetic point of view, a CH of eight electrons is required 4 Formation ratio CO of (C) 2 Two electron reduction to CO is more difficult. CH generation 4 Equations (1) and (2) for reaction with CO are as follows (at ph=7):
in the chemical industry, CO is a major component of synthesis gas and various gases, and is a synthetic gasA series of important raw materials of basic organic chemical products and intermediates. 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 an absolute ethanol solution of MnCo-MOF and 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 products (CO and H) in a photo-reduction carbon dioxide reaction 2 ) But the preparation process needs further high-temperature calcination, the process is complex, and the selectivity of the photocatalytic product is difficult to regulate and control; CN116154199A discloses a nitrogen-doped carbon-supported cobalt-nickel double-site ORR-OER catalyst and a preparation method thereof, and the invention uses NH for a precursor CoPINi-MOF@ACW prepared by a series of processes 4 The Cl is embedded and pyrolyzed to obtain the target catalyst nitrogen-doped carbon-loaded cobalt-nickel double-site ORR-OER catalyst, the preparation process is complex, and the catalyst is mainly used for electrocatalysts. Therefore, the photocatalytic reduction of CO is regulated according to the requirements of practical application 2 The product of (2) 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 reduce CO by photocatalysis 2 The product is regulated and controlled, and the catalyst has simple preparation mode and low cost.
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) By N, N-twoMethyl Formamide (DMF), ethanol (CH) 3 CH 2 OH) and water are placed in a container and stirred to be uniformly mixed, so as to prepare 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) Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) adding the mixture into the colorless solution II obtained in the step (2), and performing ultrasonic dissolution to obtain a light green solution;
(4) Ammonium chloride (NH) 4 Cl) is added into the light green solution in the step (3), ultrasonic treatment is carried out, stirring is carried out for dissolution, then the solution is put into a reaction kettle for hydrothermal reaction, ethanol and water are used for washing and centrifuging respectively after the reaction is finished, supernatant fluid is poured out, and the obtained product is dried to obtain the Ni-MOF catalyst rich in oxygen vacancies.
DMF, CH in the step (1) 3 CH 2 The volume ratio of OH to water is (14-16) 1:1, and the stirring time is 5-10min.
Terephthalic acid and NiCl in the steps (2) and (3) 2 ·6H 2 The mol ratio of O is 1:1, and the O is dissolved by ultrasonic treatment for 10-15 min.
NiCl in the step (3) 2 ·6H 2 The molar concentration of O is 0.021mol/L.
NH in the step (4) 4 The molar concentration of Cl 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 Ni-MOF catalyst rich in oxygen vacancies reduces CO in photocatalysis 2 Is used in the field of applications.
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) The Ni-MOF catalyst obtained by the preparation method of the invention is synthesized with NH 4 The addition amount of Cl is increased, the amount of ammonia generated by decomposition in the synthesis process is gradually increased, and ammonia is a reducing gas, so that Ni-MOF cluster balls can be gradually enlarged on 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) The Ni-MOF catalyst obtained by the preparation method of the invention adjusts NH 4 The addition amount of Cl can influence the concentration of oxygen vacancies in the Ni-MOF catalyst, thereby influencing the transmission resistance of photo-generated electrons in the photo-catalytic reaction process, and further influencing the photo-catalytic reduction of CO by the Ni-MOF catalyst 2 Reaction products (CO and CH) 4 ) Is selected from the group consisting of (1). Therefore, according to the practical application, the NH can be simply controlled 4 The Cl addition was adjusted for the photocatalytic product.
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 a photocatalytic reduction CO of the pure Ni-MOF catalyst prepared in comparative example 1 and the Ni-MOF catalysts containing oxygen vacancies prepared in examples 1-3 2 Is a graph of activity: (A) Photocatalytic reduction of CO 2 An activity map of CO generation, (B) photocatalysisReduction of CO 2 CH generation 4 (C) photocatalytic reduction of CO 2 Histogram of product regulation changes.
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) 0.05g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 15min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 24h at the temperature of 180 ℃, ethanol and water are used for washing and centrifuging respectively, the supernatant liquid is removed, and the obtained product is dried at the temperature of 70 ℃ to obtain the Ni-MOF and is named as 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 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) 0.1g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 15min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 24h at the temperature of 180 ℃, ethanol and water are respectively used for washing and centrifuging, the supernatant liquid is removed, and the obtained product is dried at the temperature of 70 ℃ to obtain the Ni-MOF and is named as 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) 0.18g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 17min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 24h at the temperature of 180 ℃, ethanol and water are respectively used for washing and centrifuging, the supernatant liquid is removed, and the obtained product is dried at the temperature of 70 ℃ to obtain the Ni-MOF and is named as 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) Will 0.09g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 20min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 24h at the temperature of 150 ℃, ethanol and water are used for washing and centrifuging respectively, supernatant liquid is removed, and the obtained product is dried at the temperature of 50 ℃ to obtain Ni-MOF and is named as 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) 0.12g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 15min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 20h at the temperature of 200 ℃, ethanol and water are respectively used for washing and centrifuging, the supernatant liquid is removed, and the obtained product is dried at the temperature of 90 ℃ to obtain the Ni-MOF and is named as 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) Will be 0.06g NH 4 Cl is added into the light green solution obtained in the step (3), ultrasonic treatment is carried out for 15min, stirring is carried out for 20min, after the solid is completely dissolved, the solid is transferred into a reaction kettle, the reaction kettle is placed into an oven to react for 22h at the temperature of 170 ℃, ethanol and water are used for washing and centrifuging respectively, supernatant liquid is removed, and the obtained product is dried at the temperature of 80 ℃ to obtain Ni-MOF and is named as 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 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) 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. All samples in FIG. 1 (Ni-MOF and Ni-MOF-NH 4 Cl) has distinct absorption peaks at 2θ values of 8.3 °, 15.0 °, 15.9 °, and 17.0 °, 25.8 °, 30 °, which are consistent with Ni-MOF (CCDC No. 985792) standard cards, 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, with NH at the time of synthesis 4 The addition amount of Cl is increased, the amount of ammonia gas generated by decomposition in the synthesis process is gradually increased, and the ammonia gas is a gas with reducibility, so that Ni-MOF cluster balls can be gradually enlarged, as shown in a diagram B in fig. 2, a diagram C in fig. 2 and a diagram D in fig. 2, on the one hand, and more oxygen vacancies can be promoted on the other hand.
(3) Catalyst photocatalytic reduction of CO 2 Activity test and analysis of products
CO 2 The photocatalytic reduction experiment of (2) was performed in a quartz glass reactor (100 mL), and the light source of visible light was a 300W xenon lamp (PLS-SXE 300) equipped with a 420nm cutoff filter. 5mg of catalyst and 15mg of [ Ru (bpy) ] before the reaction 3 ]Cl 2 ·6H 2 O was dispersed in 6mL of acetonitrile (CH 3 CN；3mL) ，H 2 O (2 mL) and triethanolamine (TEOA; 1 mL). Here TEOA is used as sacrificial agent, [ Ru (bpy) 3 ] 2+ As an electronic medium. Then, the reactor was evacuated and CO with a purity of 99.9% was introduced 2 The reaction was carried out for 6h under light. The gaseous product was detected by gas chromatography with TCD and FID (GC 7900).
In addition, CO and CH 4 The selectivity of (C) can be calculated according to the formula (1) and the formula #2) And (5) calculating to obtain the product.
Wherein S is CO To produce CO selectivity (%), S CH4 To generate CH 4 Selectivity (%),n(CO) reaction rate for CO production (mmol g) -1 h -1 ），n（CH 4 ) To generate CH 4 Reaction Rate (mmol g) -1 h -1 ）。
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. FIG. 3A is a diagram showing photocatalytic reduction of CO by pure Ni-MOF and Ni-MOF products containing more oxygen vacancies 2 An activity comparison graph of CO is generated, and the result shows that NH is not added 4 Catalytic reduction of CO by Cl-derived Ni-MOF catalyst 2 The highest CO yield can reach 8.0561 mmol.g -1 . With NH at synthesis 4 The addition amount of Cl is increased, and the novel Ni-MOF catalyst is obtained for catalyzing and reducing CO 2 The yield of CO was gradually decreased from 8.0561 mmol.g -1 Reduced to 1.9944 mmol.g -1 . FIG. 3B is a diagram showing photocatalytic reduction of CO by pure Ni-MOF and Ni-MOF products containing more oxygen vacancies 2 CH generation 4 The results show that: with NH at synthesis 4 The addition amount of Cl is increased, and the novel Ni-MOF catalyst is obtained for catalyzing and reducing CO 2 CH in the product 4 The content of (C) is increased gradually from 0.07402 mmol.g -1 Increase to 1.8782 mmol.g -1 . This indicates NH at synthesis 4 The addition of Cl gives a catalyst which is favorable for the photocatalytic reduction of the product CH of Ni-MOF 4 In FIG. 3, C is a summary of product columns, as can be clearly seen by controlling NH during synthesis 4 Cl addition amount can reduce CO by Ni-MOF photocatalysis 2 Effectively regulate and control the product of (C) without adding NH 4 Catalytic reduction of CO by Cl-derived Ni-MOF catalyst 2 CO is taken as a main component, and the CO selectivity can reach 96.45%; with NH 4 When the addition amount of Cl reaches 0.18g, the catalyst is used for reducing CO by photocatalysis 2 Is a product of (2)By CH 4 Mainly, CH 4 The selectivity can be as high as 79.03 percent. This is because of the regulation of NH 4 The amount of 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), the product CH resulting from the 8-electron reaction 4 The greater the ratio of (2).
(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. And it can also be seen from the figure that as NH is synthesized 4 The increase of the Cl addition amount and the gradual increase of the signal peak of ESR show that the concentration of oxygen vacancies contained in the prepared catalyst is gradually increased, and the specific size relationship is as follows: c (C) VO ，Ni-MOF-0.18>C VO ，Ni-MOF-0.1>C VO ，Ni-MOF-0.05>C VO ，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 the addition of 50mL of 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 Spectrometry (EIS) was measured using a Zennium pro electrochemical workstation (ZANER, germany) under visible light irradiation in the frequency range of 100 kHz-0.1Hz, using 5mM [ Fe (CN) 6 ] 3- /[Fe（CN） 6 ] 4- And 0.A solution of 5M KCl was used as the 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 the irradiation of visible light, ni-MOF-NH 4 The electrochemical impedance plot of Cl has a smaller arc radius than Ni-MOF and Ni-MOF-0.18 has the smallest arc radius, indicating that the Ni-MOF-0.18 catalyst has the smallest charge transfer resistance, which greatly promotes fast transport of photogenerated 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 (10)
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), and dissolving the nickel chloride hexahydrate by ultrasonic to prepare a light green solution;
(4) Adding ammonium chloride into the light green solution obtained in the step (3), carrying out ultrasonic treatment, stirring and dissolving, carrying out hydrothermal reaction, and carrying out post-treatment 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 preparing an oxygen vacancy-rich Ni-MOF catalyst according to claim 1, wherein in the steps (2) and (3), the molar ratio of the nickel chloride hexahydrate to the terephthalic acid is 1:1.
4. The method for preparing an oxygen vacancy-rich Ni-MOF catalyst according to claim 3, wherein the molar concentration of the nickel chloride hexahydrate is 0.021mol/L.
5. The method for producing an oxygen vacancy-rich Ni-MOF catalyst according to claim 1, wherein in the step (4), the NH is 4 The molar concentration of Cl is 0.026-0.093mol/L.
6. The method for producing an oxygen vacancy-rich Ni-MOF catalyst according to claim 5, wherein the temperature of the reaction in step (4) is 150 to 200 ℃.
7. The method for preparing an oxygen vacancy-rich Ni-MOF catalyst according to claim 6, wherein the reaction time in step (4) is 20 to 24 hours.
8. The method for producing an oxygen vacancy-rich Ni-MOF catalyst according to claim 7, wherein in the step (4), the post-treatment step is: after the reaction is finished, ethanol and water are used for washing and centrifugal separation respectively, the supernatant is poured off, and the obtained product is dried at the temperature of 50-90 ℃.
9. An oxygen vacancy-rich Ni-MOF catalyst prepared by the method of any one of claims 1-8.
10. The oxygen vacancy-rich Ni-MOF catalyst of claim 9 for photocatalytic reduction of CO 2 Is used in the field of applications.
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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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| 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 |
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