CN117282470A - Composite material with palladium loaded on surface of MOF material modified by nickel, and preparation method and application thereof - Google Patents
Composite material with palladium loaded on surface of MOF material modified by nickel, and preparation method and application thereof Download PDFInfo
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- CN117282470A CN117282470A CN202311217608.5A CN202311217608A CN117282470A CN 117282470 A CN117282470 A CN 117282470A CN 202311217608 A CN202311217608 A CN 202311217608A CN 117282470 A CN117282470 A CN 117282470A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 28
- 229910052759 nickel Inorganic materials 0.000 title claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019253 formic acid Nutrition 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 15
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—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]
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of nano composite materials, and particularly relates to a composite material with palladium loaded on the surface of a nickel-modified MOF material, and a preparation method and application thereof. The nickel-modified MOF material UIO-66-NH 2 The preparation method of the composite material with palladium loaded on the surface comprises the steps of adding zirconium chloride, 2-amino terephthalic acid, nickel nitrate hexahydrate and sodium chloropalladate into a mixed solution of N, N-dimethylformamide, formic acid and acetic acid, stirring uniformly, then transferring the mixed solution into a high-pressure reaction kettle, heating the mixed solution at a high temperature, and centrifugally drying the obtained product. The nickel-modified MOF material of the inventionUIO‑66‑NH 2 The composite material with palladium loaded on the surface is a novel composite material with controllable structure, excellent performance and good thermal stability, and has better performance on thermocatalytic carbon dioxide hydrogenation reduction; the preparation method has the advantages of low cost of raw materials, easy acquisition, simple experimental operation, no expensive equipment and contribution to industrial production.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a composite material with palladium loaded on the surface of a nickel-modified MOF material, and a preparation method and application thereof.
Background
Energy is an important guarantee for promoting social development and scientific and technical progress, along with economic development and rapid industrialization, people face the increasingly serious problem of energy shortage, and the high-added-value liquid fuel prepared by thermocatalytic carbon dioxide hydrogenation has great potential in solving the energy development. Currently, CO is thermocatalytically 2 The hydrogenation reaction for preparing formic acid is mainly focused on the development of catalytic materials and the exploration stage of reaction mechanisms, so that the design of high-activity catalytic materials is a focus of attention.
Metal Organic Frameworks (MOFs) are distinguished by their unique semiconducting properties, porous structure, high specific surface area and extremely high carbon dioxide storage capacity, and have therefore been widely used in recent years for the development of carbon dioxide adsorption and conversion. In addition, since Metal Organic Frameworks (MOFs) supported metals have good thermal stability, catalytic performance and gas adsorption performance, applications in carbon dioxide hydrogenation catalytic reactions have also been widely studied.
Among the supported metal nanoparticles, au, pd, pt, etc. are relatively common, wherein the Pd-based catalyst exhibits good activity, since the Pd nano metal may be H 2 Dissociative adsorption provides metal sites for CO 2 Adsorption hydrogenation provides interfacial sites and is therefore widely used for CO 2 In the hydrogenation reaction. The metal nano particles are loaded on Metal Organic Frameworks (MOFs), so that the utilization cost of materials is reduced, and the separation of carriers and the transfer of electrons are promoted, thereby improving the efficiency of thermocatalysis.
Disclosure of Invention
In order to improve the activity of the catalytic material, the invention provides a composite material with palladium supported on the surface of a nickel-modified MOF material UIO-66-NH2, which can effectively promote the separation of carriers and the transfer of electrons and can be widely used in the field of thermocatalytic carbon dioxide hydrogenation.
The application provides the following technical scheme:
the invention provides a preparation method of a composite material with palladium loaded on the surface of a nickel-modified MOF material, which comprises the following steps:
s11: mixing zirconium chloride, 2-amino terephthalic acid, nickel nitrate and sodium chloropalladate in a mixed solution, and heating at a high temperature to obtain a reaction product; the mixed solution consists of N, N-dimethylformamide, formic acid and acetic acid;
s12: and centrifugally drying the reaction product to obtain the composite material with palladium loaded on the surface of the nickel-modified MOF material.
Preferably, in the step S11, the molar ratio of zirconium chloride to 2-amino terephthalic acid is 2-3:3-4.
Preferably, in the step S11, the molar ratio of zirconium chloride to 2-amino terephthalic acid is 2:3.
preferably, in the step 11, the nickel nitrate is used in an amount of 0.2 to 1.4mmol.
Preferably, in the step S11, the mass of the sodium chloropalladate is 1-3% of that of the zirconium chloride.
Further, in the step S11, the mass of the sodium chloropalladate is 2% of that of the zirconium chloride.
Further, the nickel nitrate hexahydrate in the step S11 is used in an amount of 0.2 to 1.4mmol, preferably 1.0mmol.
Preferably, the volume ratio of N, N-dimethylformamide, formic acid and acetic acid in the step is 10-50:2-5:2-5.
Further, the amount of N, N-dimethylformamide used in the step is 10 to 50mL, preferably 50mL.
Further, in the step, formic acid and acetic acid are used in an amount of 2 to 5mL, preferably 5mL.
Preferably, in the step S11, the high-temperature heating is performed at 120-140 ℃.
Further, in the step S11, the high-temperature heating temperature is 130 ℃.
Preferably, in the step S11, the time of heating at high temperature is 20-28h.
Preferably, in the step S11, the time of heating at high temperature is 24 hours.
Preferably, in the step S11, the reaction product obtained by heating at high temperature is washed with water and ethanol.
Preferably, in the step S12, the drying temperature is 50-80 ℃ and the drying time is 10-12 hours.
Further, in the step S12, the drying temperature is 60 ℃, and the drying time is 12 hours.
Specifically, the nickel-modified MOF material UIO-66-NH 2 The preparation method of the composite material with palladium supported on the surface can comprise the following steps,
the molar ratio was set to 2:3 zirconium chloride and 2-amino terephthalic acid, 0.2-1.4mmol of nickel nitrate hexahydrate and 1-3 percent of sodium chloropalladate with the dosage of zirconium chloride are added into 50mL of mixed solution of N, N-dimethylformamide, 5mL of formic acid and acetic acid, the mixture is stirred uniformly and then is moved into a high-pressure reaction kettle to be heated for 24 hours at the high temperature of 130 ℃, and the obtained product is centrifugally dried to obtain the nickel modified MOF material UIO-66-NH 2 Composite material with palladium supported on surface.
The invention also provides the composite material of the nickel modified MOF material surface load palladium prepared by the preparation method.
The invention also provides a method for preparing formate by hydrogenation reduction of thermocatalytic carbon dioxide, which adopts the composite material with palladium loaded on the surface of the nickel-modified MOF material and comprises the following steps:
adding the composite material of the nickel modified MOF material surface loaded with palladium into saturated sodium bicarbonate water solution under inert atmosphere, heating and mixing, adding mixed gas, and reacting at 40-100 ℃ for 0.5-1.5h to obtain formic acid; the mixed gas consists of carbon dioxide and hydrogen.
The invention takes zirconium chloride, 2-amino terephthalic acid as a precursor, and N, N-dimethylformamide, formic acid and acetic acid as solvents, throughThe simple hydrothermal method encapsulates the nickel nano particles and palladium monoatoms in the MOF material to prepare the nickel modified UIO-66-NH 2 The composite material with palladium supported on the surface has nickel nitrate and sodium chloropalladate as nickel source and palladium source, and acetic acid to regulate the pH value of the solution to make the solution slightly acidic. After modification, the separation of carriers and the transfer of electrons are promoted, and the thermocatalytic performance is greatly improved.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention discloses a nickel-modified MOF material UIO-66-NH 2 The raw materials used in the preparation method of the composite material with palladium loaded on the surface are low in cost, easy to obtain, simple and convenient in experimental operation, expensive equipment is not used in the whole process, and industrial production is facilitated;
2. the invention discloses a nickel-modified MOF material UIO-66-NH 2 The composite material with palladium supported on the surface is a novel composite material with controllable structure, excellent performance and good thermal stability, has excellent performance on thermocatalytic carbon dioxide hydrogenation reduction, and is beneficial to industrial application.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) of a palladium-supported nickel-modified UIO-66-NH2 (Pd@UIO-66-NH 2 (Ni)) composite material of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) of a palladium-supported nickel-modified UIO-66-NH2 (Pd@UIO-66-NH 2 (Ni)) composite material of example 1;
FIG. 3 is a graph showing the effect of the palladium-supported nickel modified UIO-66-NH2 (Pd@UIO-66-NH 2 (Ni)) composite material of example 1 on preparing formate by catalytic reduction of carbon dioxide.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Palladium-supported nickel-modified UIO-66-NH 2 (Pd@UIO-66-NH 2 (Ni)) is prepared by the following specific steps:
93.2mg of zirconium chloride were added,108.7mg of 2-amino terephthalic acid, 0.2 to 1.4mmol of nickel nitrate hexahydrate and 2.1mg of sodium chloropalladate are added into 50mL of mixed solution of N, N-dimethylformamide, 5mL of formic acid and acetic acid, the mixture is stirred vigorously at room temperature, the mixture is moved to a high-pressure reaction kettle after being stirred uniformly and heated for 24 hours at the high temperature of 130 ℃, the obtained product is washed by ethanol and distilled water, and then the mixture is put into a drying box for drying, thus obtaining the nickel-modified MOF material UIO-66-NH 2 Composite material with palladium supported on surface. The Pd@UIO-66-NH 2 A TEM image of (Ni) is shown in fig. 1, and an SEM image is shown in fig. 2, from which it can be seen that the octahedral structure was successfully prepared and uniform in size.
Example 2
Adding 33.4mg of zirconium chloride, 27.3mg of 2-amino terephthalic acid, 0.2-1.4mmol of nickel nitrate hexahydrate and 0.84mg of sodium chloropalladate into 10mL of mixed solution of N, N-dimethylformamide and 2mL of formic acid and acetic acid, stirring at room temperature, transferring into a high-pressure reaction kettle, heating at 130 ℃ for 24 hours after stirring uniformly, cleaning the obtained product with ethanol and distilled water, and then putting into a drying box for drying to obtain the nickel-modified MOF material UIO-66-NH 2 Composite material with palladium supported on surface.
Example 3
Adding 300mg of zirconium chloride, 235mg of 2-amino terephthalic acid, 0.2-1.4mmol of nickel nitrate hexahydrate and 7.58mg of sodium chloropalladate into 30mL of mixed solution of N, N-dimethylformamide, 2mL of formic acid and acetic acid, stirring at room temperature, transferring into a high-pressure reaction kettle after stirring uniformly, heating at 130 ℃ for 24 hours, cleaning the obtained product with ethanol and distilled water, and then drying in a drying box to obtain the nickel-modified MOF material UIO-66-NH 2 Composite material with palladium supported on surface.
Application example 1
The thermal catalytic carbon dioxide reduction performance test under the heating condition comprises the following specific steps:
evaluation of the Nickel-modified MOF Material UIO-66-NH obtained in example 1 by means of a magnetic heating stirrer 2 Thermocatalytic carbon dioxide reduction activity of the surface-supported palladium composite.
5mg of the palladium-supported nickel-modified UIO-66-NH obtained in example 1 2 (Pd@UIO-66-NH 2 (Ni)) composite catalyst was dispersed in 5mL of saturated sodium bicarbonate ultrapure water, dispersed by ultrasonic, then transferred to a magnetic heating stirrer and sealed, then the air in the system was removed with inert gas, and after the completion, a carbon dioxide/hydrogen gas mixture of 1-3 megapascals was injected into the reactor, heated to 40-100 ℃ and reacted for 1 hour, and the yield of formic acid was obtained by ion chromatography and analysis according to standards.
FIG. 3 is a palladium-supported nickel-modified UIO-66-NH of example 1 2 (Pd@UIO-66-NH 2 (Ni)) composite material thermal catalytic carbon dioxide reduction performance diagram. As can be seen from FIG. 3, the palladium-supported nickel-modified UIO-66-NH 2 (Pd@UIO-66-NH 2 The (Ni)) composite material has excellent thermocatalytic carbon dioxide reduction performance, wherein the formic acid production efficiency of the optimal catalyst can reach 60.7mol FAmolPd -1 h -1 The composite material has the advantages of excellent performance, good stability, simple preparation process, low raw material price and easy industrial production.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the composite material with palladium supported on the surface of the nickel-modified MOF material is characterized by comprising the following steps of:
s11: mixing zirconium chloride, 2-amino terephthalic acid, nickel nitrate and sodium chloropalladate in a mixed solution, and heating at a high temperature to obtain a reaction product; the mixed solution consists of N, N-dimethylformamide, formic acid and acetic acid;
s12: and centrifugally drying the reaction product to obtain the composite material with palladium loaded on the surface of the nickel-modified MOF material.
2. The method according to claim 1, wherein in the step S11, the molar ratio of zirconium chloride to 2-amino terephthalic acid is 2 to 3:3-4.
3. The method according to claim 1, wherein the mass of sodium chloropalladate in the step is 1 to 3% of that of zirconium chloride.
4. The method according to claim 1, wherein the volume ratio of N, N-dimethylformamide, formic acid and acetic acid in the step is 10 to 50:2-5:2-5.
5. The method according to claim 1, wherein the high-temperature heating is performed at 120 to 140 ℃ in the step S11.
6. The method according to claim 1, wherein the high temperature heating time in step S11 is 20 to 28 hours.
7. The method according to claim 1, wherein the reaction product obtained by heating at high temperature is washed with water and ethanol in step S11.
8. The method according to claim 1, wherein in the step S12, the drying temperature is 50 to 80 ℃ and the drying time is 10 to 12 hours.
9. The composite material of palladium supported on the surface of the nickel-modified MOF material prepared by the preparation method of any one of claims 1-8.
10. A method for preparing formate by thermocatalytic carbon dioxide hydrogenation reduction, which is characterized in that the composite material of palladium loaded on the surface of the nickel-modified MOF material according to claim 9 comprises the following steps:
adding the composite material of the nickel modified MOF material surface loaded with palladium into saturated sodium bicarbonate water solution under inert atmosphere, heating and mixing, adding mixed gas, and reacting at 40-100 ℃ for 0.5-1.5h to obtain formic acid; the mixed gas consists of carbon dioxide and hydrogen.
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