CN116371472A - MOFs composite catalyst implanted with multicomponent metal nano colloid particles in situ, preparation method and application thereof - Google Patents
MOFs composite catalyst implanted with multicomponent metal nano colloid particles in situ, preparation method and application thereof Download PDFInfo
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- 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]
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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
- B01J31/18—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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
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- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract
The invention relates to the technical field of preparation of thermocatalytic materials, in particular to a composite catalyst with MOFs implanted in situ by multicomponent metal nano colloid particles, a preparation method and application thereof. The preparation method comprises the steps of in-situ implanting multicomponent metal nano particles into a ZIF-8 bulk phase to obtain a composite catalyst with a rhombic dodecahedron structure, limiting the multicomponent metal nano particles in ZIF-8 pore channels, wherein the mass fraction of ligand-free metal nano crystals in the ZIF-8 is 1.53-1.83wt%; the ligand-free metal nanocrystalline is implanted into the bulk phase in situ in the ZIF-8 synthesis process, so that the problems of deactivation and the like caused by easy aggregation of active metals are solved, the host-guest effect of the composite catalyst is further enhanced, and the liquid-phase cinnamaldehyde hydrogenation catalytic material with high activity, selectivity and stability is obtained.
Description
Technical Field
The invention belongs to the technical field of preparation of thermocatalytic materials, and relates to a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ, a preparation method and application thereof.
Background
The selective hydrogenation of alpha, beta-unsaturated aldehydes has attracted considerable attention from researchers because of the wide application of their products in various industries. Among the various α, β -unsaturated aldehydes, cinnamaldehyde (CAL) is an important and representative model reactant. The main products cinnamyl alcohol (COL) and phenylpropionaldehyde (HCAL) have been used in various fields including the production of pharmaceutical intermediates, chemicals, perfumes and fragrances. In recent years, metal-based catalysts have achieved significant results in the study of thermocatalytic, photo-thermocatalytic liquid phase cinnamaldehyde hydrogenation.
Different catalysts (including Pt-, pd-, ru-, ni-, co-, and Cu-based catalysts) have been extensively studied in CAL selective hydrogenation reactions. Pt-based and Pd-based single-component metal catalysts have been widely studied in hydrogenation reactions of c=o and c=c unsaturated bonds, however, the selectivity of the metal catalysts prepared by the conventional wet chemical method to certain target products is difficult to reach 100%, the preparation cost of the catalysts is high, and the environmental pressure is high. How to synthesize and optimize the novel catalyst to obtain higher yields of the target product is a technical difficulty to be solved by the person skilled in the art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a MOFs composite catalyst implanted with multicomponent metal nano colloid particles in situ, a preparation method and application thereof, wherein the multicomponent metal nano particles are implanted in situ in a ZIF-8 bulk phase to obtain the composite catalyst with a rhombic dodecahedron structure, the multicomponent metal nano particles are limited in ZIF-8 pore channels, and the mass fraction of ligand-free metal nano crystals in the ZIF-8 is 1.53-1.83wt%; the ligand-free metal nanocrystalline is implanted into the bulk phase in situ in the ZIF-8 synthesis process, so that the problems of deactivation and the like caused by easy aggregation of active metals are solved, the host-guest effect of the composite catalyst is further enhanced, and the liquid-phase cinnamaldehyde hydrogenation catalytic material with high activity, selectivity and stability is obtained.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the MOFs composite catalyst by in-situ implantation of the multicomponent metal nano-colloid particles comprises the following steps:
(1) Preparation of Pt (MeOH), cu (MeOH), pd (MeOH) solutions containing Pd, cu, pt single-component nanocolloids:
after cleaning Pt, cu and Pd metal targets respectively, carrying out transient pulse laser irradiation treatment I in methanol to obtain Pt (MeOH), cu (MeOH) and Pd (MeOH) solutions;
(2) Preparation of ligand-free PdCu (MeOH), ptCu (MeOH) solutions containing PdCu, ptCu bimetallic nanocolloids:
uniformly mixing the Pd (MeOH) solution and the Pt (MeOH) solution in the step (1) with the Cu (MeOH) solution respectively to obtain two colloid mixed solutions, and then performing transient pulse laser irradiation treatment II on the two colloid mixed solutions under the assistance of ultrasound respectively to obtain ligand-free PdCu (MeOH) solution and PtCu (MeOH) solution respectively; the PdCu and PtCu bimetallic colloid particles in the step (2) are formed by introducing Cu nano colloid into Pd or Pt colloid and then utilizing a transient high-temperature melting-condensing mechanism of pulse laser, wherein the liquid phase medium is anhydrous methanol;
(3) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
mixing Pt (MeOH), cu (MeOH) and Pd (MeOH) solutions in the step (1) with ZIF-8 precursor solutions respectively, and stirring to react I to obtain Pt@ZIF-8, cu@ZIF-8 and Pd@ZIF-8 composite catalysts; and (3) mixing the ligand-free PdCu (MeOH) solution and PtCu (MeOH) solution in the step (2) with the ZIF-8 precursor solution respectively, and stirring to react II to obtain the PdCu@ZIF-8 and PtCu@ZIF-8 composite catalyst.
Preferably, the Pd, cu and Pt single-component nano colloid in the step (1) is prepared according to the following steps:
s11, performing ultrasonic cleaning treatment on Pt, cu and Pd targets with diameters of 1.0-2.0cm and thicknesses of 1mm by sequentially adopting deionized water, ethanol and methanol to remove a surface oxide layer, then placing the targets in anhydrous methanol, and adjusting the energy density of the pulsed laser to be 0.8-1.6J/cm 2 Laser beamIrradiating for 5-15min, and performing deep cleaning treatment with pulse laser under the assistance of ultrasound to obtain a clean target;
wherein, the purities of Pt, cu and Pd targets are 99.999 percent;
s12, after replacing fresh methanol, soaking the cleaning target material in the step S11 in a methanol solution, and then performing transient pulse laser irradiation treatment I to obtain Pd, cu and Pt single-component nano colloid;
wherein the concentration of the Pd, cu and Pt single-component nano colloid in the Pt (MeOH), cu (MeOH) and Pd (MeOH) solution is 0.06-0.16mg/mL;
transferring the Pt (MeOH), cu (MeOH) and Pd (MeOH) solution containing Pd, cu and Pt single-component nano-colloid in the step (1) into a clean volumetric flask with a cover by using a pipette, and then preserving the obtained solution at 25 ℃, wherein the size of the metal colloid particles is 2-10nm.
Preferably, in the step (2), the volume ratio of Pd (MeOH) solution to Cu (MeOH) solution is (1-3): (1-3) the volume ratio of Pt (MeOH) solution to Cu (MeOH) solution is (1-3): (1-3).
Preferably, the conditions of the transient pulse laser irradiation treatment I in the step (1) and the transient pulse laser irradiation treatment II in the step (2) are the same, and the conditions are: irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 6-10mm, and laser irradiation energy density of 800-1600mJ/cm 2 The irradiation time is 5-15min; and the ultrasonic frequency in the step (2) is 20-40kHz.
Preferably, the concentration of the PdCu and PtCu bimetallic nano-colloid in the step (2) in the ligand-free PdCu (MeOH) and PtCu (MeOH) solution is 0.06-0.18mg/mL.
Preferably, the ZIF-8 precursor solution of step (3) is prepared according to the following steps:
respectively dissolving zinc nitrate hexahydrate and dimethyl imidazole in methanol until the solution is colorless and transparent, and then mixing the two solutions;
wherein, the mol ratio of the zinc nitrate hexahydrate to the dimethyl imidazole is 1:3.
preferably, in the step (3), the volume ratio of the Pt (MeOH), cu (MeOH), pd (MeOH) solution to the ZIF-8 precursor solution is 1:1-2;
the volume ratio of ligand-free PdCu (MeOH), ptCu (MeOH) solution to ZIF-8 precursor solution was 1:1-2.
Preferably, the stirring reaction I and stirring reaction II in the step (3) are the same and are magnetically stirred at 500rpm for 3-5 hours.
The invention also protects the MOFs composite catalyst implanted in situ by the multicomponent metal nano-colloid particles prepared by the preparation method, wherein the MOFs composite catalyst implanted in situ by the multicomponent metal nano-colloid particles is Pt@ZIF-8, cu@ZIF-8, pd@ZIF-8, pdCu@ZIF-8 and PtCu@ZIF-8 respectively.
The invention also protects the application of the multi-component metal nano colloid particles in-situ implanted MOFs composite catalyst in preparing the thermal catalytic material and the photo-thermal catalytic material.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the invention comprises the following steps: utilizing a solvothermal synthesis method to implant multicomponent metal nano colloid particles in situ in ZIF-8; preparing Pt (MeOH), cu (MeOH), pd (MeOH) solution, ligand-free PdCu (MeOH) and PtCu (MeOH) solution containing Pd, cu and Pt single-component nano colloid by utilizing transient pulse laser irradiation technology, mixing the solution with ZIF-8 precursor solution to obtain mixed solution, performing solvothermal reaction on the mixed solution, and stirring at room temperature for 3-5h to form the multi-component metal nano colloid particle in-situ implantation MOFs composite catalyst.
2. According to the invention, a selective transient pulse laser irradiation technology is adopted in a liquid phase medium, pt (MeOH), cu (MeOH) and Pd (MeOH) solutions containing Pd, cu and Pt single-component nano-colloids with good dispersibility and ligand-free PdCu (MeOH) and PtCu (MeOH) solutions containing PdCu and PtCu double-metal nano-colloids are introduced into a ZIF-8 precursor solution, and the multi-component metal nano-colloid particle in-situ implantation MOFs composite catalyst is prepared.
3. Ligand-free multicomponent metallic nano-particles prepared by the inventionThe nano-crystal is implanted into ZIF-8 in situ, so that the electronic states of active main metals Pd and Pt are improved; the ligand-free multicomponent metal nanocrystalline is implanted into the ZIF-8 in situ, so that the problem of easy agglomeration of active metal caused by large surface energy is inhibited, and H is promoted 2 And adsorption and activation of substrate molecules, so as to remarkably improve the selectivity of target products of cinnamaldehyde hydrogenation, researches show that the selectivity of phenylpropionaldehyde is improved from 63.5% of monometal implanted ZIF-8 to 100%, the modification strategy has strong universality, and a simple and convenient universal alternative scheme with good environmental compatibility and relatively low cost is provided for chemical products to adopt hydrogenation catalytic upgrading and high-efficiency generation of targeted target products.
4. The application prepares the laser-derived Pt@ZIF-8, cu@ZIF-8, pd@ZIF-8 composite catalyst and PdCu@ZIF-8 and PtCu@ZIF-8 composite catalyst by utilizing a liquid phase transient pulse laser irradiation technology for the first time, but the specific performance exploration shows that the bimetallic PdCu@ZIF-8 and PtCu@ZIF-8 composite catalyst is more representative, so that the specific performance exploration is focused on in the embodiment.
Drawings
FIG. 1 is a schematic diagram of the preparation steps of MOFs composite catalyst (Pd@ZIF-8, pt@ZIF-8, cu@ZIF-8, pdCu@ZIF-8, ptCu@ZIF-8) implanted in situ with multicomponent metal nano-colloid particles;
FIG. 2 is a schematic diagram of the liquid phase laser produced single metal and double metal nano-colloids in examples 1-3 of the present invention, wherein FIG. a is a photograph of the single metal Pd, cu, pt nano-colloids, and FIG. b is a schematic diagram of the double metals PdCu and PtCu;
FIG. 3 is an XRD pattern and a TEM pattern of ligand-free multicomponent metallic nanocrystals after transient pulsed laser irradiation in examples 1-3 of the present invention, wherein pattern a is an XRD pattern of ligand-free single metal Pd, pt, cu and bimetallic PdCu and PtCu nanocrystals, and pattern b is a TEM pattern of ligand-free Pd, pdCu, ptCu nanoparticles in sequence;
FIG. 4 is an XRD pattern of the ZIF-8 implant and representative SEM and TEM patterns of the PdCu implant ZIF-8 implant of the multicomponent metallic nanoparticle of example 1 of the present invention, wherein pattern a is an XRD pattern, pattern b is an SEM pattern, and pattern c is a TEM pattern;
FIG. 5 is a TEM image and an elemental mapping image of PdCu@ZIF-8 of example 1 of the invention at different magnifications, wherein FIG. a is a High Angle Annular Dark Field Transmission Electron Microscope (HAADFTEM) image of PdCu@ZIF-8, FIG. b is an elemental mapping image thereof, and FIG. c is a high resolution TEM image of an implanted bimetallic PdCu particle;
fig. 6 is an XPS diagram of a bimetal PdCu in example 1 of the present invention, wherein fig. a is an XPS diagram of Pd 3d and fig. b is an XPS diagram of Cu 2 p;
fig. 7 is an XPS diagram of the bimetal PtCu in example 1 of the present invention, wherein fig. a is an XPS diagram of Pt 4f and fig. b is an XPS diagram of Cu 2 p;
FIG. 8 is H in example 1 of the present invention 2 A graph of the influence of pressure and temperature change on the hydrogenation performance of cinnamaldehyde of PdCu@ZIF-8, wherein a is the influence of hydrogen pressure on the hydrogenation performance of cinnamaldehyde, and b is the influence of temperature change on the hydrogenation performance of cinnamaldehyde;
FIG. 9 is a graph showing the effect of rotation speed and hydrogenation time on the cinnamaldehyde hydrogenation performance of PdCu@ZIF-8 in example 1 of the invention, wherein a is the effect of stirring speed on the cinnamaldehyde hydrogenation performance, and b is the effect of hydrogenation time on the cinnamaldehyde conversion rate;
FIG. 10 is a graph showing the effect of PdCu@ZIF-8 catalyst in example 1 on the life of cyclic hydrogenation of cinnamaldehyde;
FIG. 11 is a graph showing the effect of Pt@ZIF-8 in example 2 and PtCu@ZIF-8 in example 1 of the present invention on the hydrogenation performance of cinnamaldehyde, wherein a is the performance of Pt@ZIF-8 in catalyzing the hydrogenation of cinnamaldehyde, and b is the performance of PtCu@ZIF-8 in catalyzing the hydrogenation of cinnamaldehyde.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
A preparation method of a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ comprises the following steps:
(1) Preparation of Pt (MeOH), cu (MeOH), pd (MeOH) solutions containing Pd, cu, pt single-component nanocolloids:
s11, selecting Pd, pt and Cu target pieces with the diameter of 1.5cm, the thickness of 1mm and the purity of 99.999%, sequentially ultrasonically cleaning the target pieces for 20min by using water, ethanol and methanol before using the target pieces, and then drying the target pieces by using a nitrogen gun to obtain a pre-cleaned metal target piece;
throwing the pre-cleaned metal target material into target solvent methanol, and pretreating with pulse laser under 1.2J/cm for 5min 2 Further removing the oxide layer and the excessive impurities;
s12, placing the clean metal Pd target material in fresh 5mL of methanol (MeOH) solvent, carrying out transient pulse laser irradiation treatment I at an ultrasonic frequency of 20Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 8mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time was 5min, obtaining a Pd (MeOH) colloidal solution, as shown in fig. 2 a;
placing clean metal Pt target material in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I under ultrasonic frequency of 20Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 8mm, and laser irradiation energy density of 1200mJ/cm 2 The irradiation time was 5min, obtaining a Pt (MeOH) colloidal solution, as shown in fig. 2 a;
placing clean metal Cu target in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I under ultrasonic frequency of 20Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 8mm, and laser irradiation energy density of 1200mJ/cm 2 The irradiation time was 5min, yielding a Cu (MeOH) colloidal solution, as shown in fig. 2 a;
(2) Preparing PdCu and PtCu bimetallic nano colloid solution;
s21, uniformly mixing Pd (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at an ultrasonic frequency of 20Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 8mm, and the energy density of laser irradiation is 800mJ/cm 2 The irradiation time was 10min, resulting in ligand-free PdCu (MeOH) solution, as shown in fig. 2 b;
s22, uniformly mixing Pt (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at the frequency of 20Hz, irradiating by adopting pulse unfocused laser beams, wherein the output wavelength of the unfocused laser beams is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 8mm, and the energy density of laser irradiation is 800mJ/cm 2 The irradiation time was 10min, yielding ligand-free PtCu (MeOH) solution, as shown in fig. 2 b;
(3) Preparing ZIF-8 precursor solution:
0.532g of dimethylimidazole (2-MIM) and 0.476g of zinc nitrate hexahydrate (ZnNO) 3 ·6H 2 O) respectively dissolving in 20mL of methanol (MeOH) solvent, fully dissolving to make the solution in a transparent state, and then mixing the two solutions to implant the subsequent colloidal particles in situ;
(4) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
and (3) uniformly mixing 40mL of ligand-free PdCu (MeOH) solution in the step S21 and 40mL of ligand-free PtCu (MeOH) solution in the step S22 with the ZIF-8 precursor solution obtained in the step (3) respectively to obtain mixed solutions, performing ultrasonic dispersion for 15min, magnetically stirring at 500rpm at room temperature for 5h, centrifugally washing with methanol for three times, and drying in a 70 ℃ electrothermal blowing drying oven for 24h to obtain the PdCu@ZIF-8 and PtCu@ZIF-8 particle catalysts, wherein the cross-sectional SEM (SEM) picture of the catalyst is shown in fig. 4 b.
Example 2
A preparation method of a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ comprises the following steps:
(1) Preparation of Pt (MeOH), pd (MeOH) solution containing Pd, pt single-component nano-colloid:
s11, selecting Pd and Pt target pieces with the diameter of 1.5cm, the thickness of 1mm and the purity of 99.999%, sequentially carrying out ultrasonic cleaning on the Pd and Pt target pieces for 20min before use by using water, ethanol and methanol, and then drying by using a nitrogen gun to obtain a pre-cleaned metal target piece;
throwing the pre-cleaned metal target material into target solvent methanol, and pretreating with pulse laser under 1.2J/cm for 5min 2 Further removing the oxide layer and the excessive impurities;
s12, placing the clean metal Pd target material in fresh 5mL of methanol (MeOH) solvent, carrying out transient pulse laser irradiation treatment I at an ultrasonic frequency of 20Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 8mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time was 5min, obtaining a Pd (MeOH) colloidal solution, as shown in fig. 2 a;
placing clean metal Pt target material in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I under ultrasonic frequency of 20Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 8mm, and laser irradiation energy density of 1200mJ/cm 2 The irradiation time was 5min, obtaining a Pt (MeOH) colloidal solution, as shown in fig. 2 a;
(2) Preparing ZIF-8 precursor solution:
0.532g of dimethylimidazole (2-MIM) and 0.476g of zinc nitrate hexahydrate (ZnNO) 3 ·6H 2 O) respectively dissolving in 20mL of methanol (MeOH) solvent, fully dissolving to make the solution in a transparent state, and then mixing the two solutions to implant the subsequent colloidal particles in situ;
(3) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
uniformly mixing 40mL of the Pd (MeOH) colloidal solution and the Pt (MeOH) colloidal solution obtained in the step S12 with the ZIF-8 precursor solution obtained in the step (2) respectively to obtain a mixed solution; after the mixed solution is ultrasonically dispersed for 15min, magnetically stirring for 5h at room temperature at 500rpm, then centrifugally cleaning for three times by using methanol, and drying for 24h in an electrothermal blowing drying oven at 70 ℃ to obtain Pd@ZIF-8 and Pt@ZIF-8 particle catalysts.
Example 3
A preparation method of a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ comprises the following steps:
(1) Preparation of Cu (MeOH) solution containing Cu single-component nanocolloids:
s11, selecting a Cu target piece with the diameter of 1.5cm, the thickness of 1mm and the purity of 99.999%, sequentially carrying out ultrasonic cleaning on the Cu target piece for 20min by using water, ethanol and methanol before using, and then drying the Cu target piece by using a nitrogen gun to obtain a pre-cleaned metal target piece;
throwing the pre-cleaned metal target material into target solvent methanol, and pretreating with pulse laser under 1.2J/cm for 5min 2 Further removing the oxide layer and the excessive impurities;
s12, placing the clean metal Cu target in fresh 5mL of methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I at an ultrasonic frequency of 20Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 8mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time was 5min, yielding a Cu (MeOH) colloidal solution, as shown in fig. 2 a;
(2) Preparing ZIF-8 precursor solution:
0.532g of dimethylimidazole (2-MIM) and 0.476g of zinc nitrate hexahydrate (ZnNO) 3 ·6H 2 O) respectively dissolving in 20mL of methanol (MeOH) solvent, fully dissolving to make the solution in a transparent state, and then mixing the two solutions to implant the subsequent colloidal particles in situ;
(3) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
uniformly mixing 40mL of the Cu (MeOH) colloid solution obtained in the step S12 and the ZIF-8 precursor solution obtained in the step (2) to obtain a mixed solution;
and (3) after carrying out ultrasonic dispersion on the mixed solution obtained in the step (S41) for 15min, magnetically stirring at 500rpm for 5h at room temperature, then centrifugally cleaning with methanol for three times, and drying in an electrothermal blowing drying oven at 70 ℃ for 24h to obtain Cu@ZIF-8.
Example 4
A preparation method of a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ comprises the following steps:
(1) Preparation of Pt (MeOH), cu (MeOH), pd (MeOH) solutions containing Pd, cu, pt single-component nanocolloids:
s11, selecting Pd, pt and Cu target pieces with the diameter of 1cm, the thickness of 1mm and the purity of 99.999%, sequentially carrying out ultrasonic cleaning on the target pieces for 20min by using water, ethanol and methanol before using the target pieces, and then drying the target pieces by using a nitrogen gun to obtain a pre-cleaned metal target piece;
throwing the pre-cleaned metal target material into target solvent methanol, and pretreating with pulse laser under 1.2J/cm for 10min 2 Further removing the oxide layer and the excessive impurities;
s12, placing the clean metal Pd target material in fresh 5mL of methanol (MeOH) solvent, carrying out transient pulse laser irradiation treatment I at ultrasonic frequency of 30Hz, irradiating by adopting pulse unfocused laser beams, wherein the output wavelength of the unfocused laser beams is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 6mm, and the energy density of laser irradiation is 1600mJ/cm 2 The irradiation time is 10min, and Pd (MeOH) colloid solution is obtained;
placing clean metal Pt target material in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I under ultrasonic frequency of 30Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 6mm, and laser irradiation energy density of 1600mJ/cm 2 The irradiation time is 10min, and Pt (MeOH) colloid solution is obtained;
the clean metal Cu target is placed in fresh 5mL of methanol (MeOH) solvent and subjected to transient pulsed laser irradiation treatment at ultrasonic frequency of 30HzI, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 6mm, and the energy density of laser irradiation is 1600mJ/cm 2 The irradiation time is 10min, and Cu (MeOH) colloid solution is obtained;
(2) Preparing PdCu and PtCu bimetallic nano colloid solution;
s21, uniformly mixing Pd (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at an ultrasonic frequency of 20Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 10mm, and the energy density of laser irradiation is 1600mJ/cm 2 The irradiation time was 5min, yielding ligand-free PdCu (MeOH) solution, as shown in fig. 2 b;
s22, uniformly mixing Pt (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at the frequency of 30Hz, irradiating by adopting pulse unfocused laser beams, wherein the output wavelength of the unfocused laser beams is 1064nm, the pulse frequency is 20Hz, the diameter of an output light spot is 10mm, and the energy density of laser irradiation is 1600mJ/cm 2 The irradiation time was 5min, yielding ligand-free PtCu (MeOH) solution, as shown in fig. 2 b;
(3) Preparing ZIF-8 precursor solution:
0.532g of dimethylimidazole (2-MIM) and 0.476g of zinc nitrate hexahydrate (ZnNO) 3 ·6H 2 O) respectively dissolving in 20mL of methanol (MeOH) solvent, fully dissolving to make the solution in a transparent state, and then mixing the two solutions to implant the subsequent colloidal particles in situ;
(4) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
uniformly mixing 40mL of ligand-free PdCu (MeOH) solution in the step S21 and 40mL of ligand-free PtCu (MeOH) solution in the step S22 with 120mL of ZIF-8 precursor solution obtained in the step (3) respectively to obtain mixed solutions, performing ultrasonic dispersion for 15min, magnetically stirring at 500rpm at room temperature for 4h, centrifugally cleaning with methanol for three times, and drying in an electrothermal blowing drying oven at 70 ℃ for 24h to obtain PdCu@ZIF-8 and PtCu@ZIF-8 particle catalysts.
Example 5
A preparation method of a MOFs composite catalyst with multicomponent metal nano-colloid particles implanted in situ comprises the following steps:
(1) Preparation of Pt (MeOH), cu (MeOH), pd (MeOH) solutions containing Pd, cu, pt single-component nanocolloids:
s11, selecting Pd, pt and Cu target pieces with the diameter of 2cm, the thickness of 1mm and the purity of 99.999%, sequentially carrying out ultrasonic cleaning on the target pieces for 20min by using water, ethanol and methanol before using the target pieces, and then drying the target pieces by using a nitrogen gun to obtain a pre-cleaned metal target piece;
throwing the pre-cleaned metal target material into target solvent methanol, and pretreating with pulse laser for 15min under the laser treatment condition of 0.8J/cm 2 Further removing the oxide layer and the excessive impurities;
s12, placing the clean metal Pd target material in fresh 5mL of methanol (MeOH) solvent, carrying out transient pulse laser irradiation treatment I at an ultrasonic frequency of 40Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 10mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time is 15min, and Pd (MeOH) colloid solution is obtained;
placing clean metal Pt target material in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I under ultrasonic frequency of 40Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 10mm, and laser irradiation energy density of 1200mJ/cm 2 The irradiation time is 15min, and Pt (MeOH) colloid solution is obtained;
placing clean metal Cu target in fresh 5mL methanol (MeOH) solvent, performing transient pulse laser irradiation treatment I at ultrasonic frequency of 40Hz, irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 10mm, and laser irradiation energyDensity of 1200mJ/cm 2 The irradiation time is 15min, and Cu (MeOH) colloid solution is obtained;
(2) Preparing PdCu and PtCu bimetallic nano colloid solution;
s21, uniformly mixing Pd (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at an ultrasonic frequency of 40Hz, irradiating by adopting a pulse unfocused laser beam, wherein the output wavelength of the unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 6mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time was 15min, resulting in ligand-free PdCu (MeOH) solution, as shown in fig. 2 b;
s22, uniformly mixing Pt (MeOH) colloid and Cu (MeOH) colloid to obtain colloid mixed solution, carrying out transient pulse laser irradiation treatment II on the mixed solution at the frequency of 40Hz, irradiating by adopting pulse unfocused laser beams, wherein the output wavelength of the unfocused laser beams is 1064nm, the pulse frequency is 30Hz, the diameter of an output light spot is 6mm, and the energy density of laser irradiation is 1200mJ/cm 2 The irradiation time was 15min, yielding ligand-free PtCu (MeOH) solution, as shown in fig. 2 b;
(3) Preparing ZIF-8 precursor solution:
0.532g of dimethylimidazole (2-MIM) and 0.476g of zinc nitrate hexahydrate (ZnNO) 3 ·6H 2 O) respectively dissolving in 20mL of methanol (MeOH) solvent, fully dissolving to make the solution in a transparent state, and then mixing the two solutions to implant the subsequent colloidal particles in situ;
(4) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
uniformly mixing 120mL of ligand-free PdCu (MeOH) solution in the step S21 and 120mL of ligand-free PtCu (MeOH) solution in the step S22 with the ZIF-8 precursor solution obtained in the step (3) respectively to obtain mixed solutions, performing ultrasonic dispersion for 15min, magnetically stirring at 500rpm at room temperature for 3h, centrifugally cleaning with methanol for three times, and drying in an electrothermal blowing drying oven at 70 ℃ for 24h to obtain the PdCu@ZIF-8 and PtCu@ZIF-8 particle catalyst.
The foregoing disclosure is merely illustrative of specific embodiments of the invention, but the embodiments are not limited thereto and variations within the scope of the invention will be apparent to those skilled in the art.
The multicomponent metal nano-colloid particles prepared in examples 1-5 are implanted into MOFs composite catalyst in situ, the effects are basically the same, and the single-component Pd@ZIF-8, pt@ZIF-8 and Cu@ZIF-8 catalysts prepared in examples 1-3 are tested for cinnamaldehyde hydrogenation performance by taking samples of examples 1-3 as examples, and specific results are shown in Table 1.
Table 1 table for evaluating hydrogenation performance of cinnamaldehyde
As can be seen from Table 1, the bimetallic catalyst PdCu@ZIF-8 and PtCu@ZIF-8 prepared in example 1 exhibited the best cinnamaldehyde hydrogenation performance (1 MPaH) as compared with the Pd@ZIF-8, pt@ZIF-8 and Cu@ZIF-8 prepared in example 2-3 2 The conversion rate of cinnamaldehyde hydrogenation for 1h at 70 ℃ is 98.03%, the selectivity of phenylpropionaldehyde is 100%, the conversion rate of monometal Pd@ZIF-8 cinnamaldehyde is 34.49%, and meanwhile, the PtCu@ZIF-8 catalyst prepared in the example 1 loses activity due to electron transfer from Pd to Cu, so that the conversion rate of cinnamaldehyde hydrogenation is lower than that of Pt@ZIF-8 by 82.42%. In addition, the Cu@ZIF-8 catalyst has higher selectivity to the target product phenylpropionaldehyde obtained by hydrogenating cinnamaldehyde, which is also a main reason for regulating and controlling active centers and active site transfer of two active metals.
To illustrate the effect of the present invention, the present invention also tested the properties of the raw materials and the products prepared in examples 1-3, and the specific results are shown in FIGS. 2-11.
Fig. 2 is a single metal and double metal nano colloid physical diagram prepared by liquid phase laser in the embodiment 1-3 of the invention, wherein the diagram a is a physical photograph of single metal Pd, cu and Pt nano colloid, the diagram b is a physical photograph of double metal PdCu and PtCu, the concentration is about 0.06-0.16mg/mL, and the result of fig. 2 shows that the transient pulse laser irradiation treatment is adopted to bombard a metal target in liquid, so that series of target metal nano colloids can be accurately prepared, and technical support is provided for preparing a composite catalyst.
FIG. 3 is an XRD pattern and a TEM pattern of ligand-free multicomponent metallic nanocrystals after laser irradiation in examples 1 to 3 of the present invention, wherein pattern a is an XRD pattern of ligand-free single-metal Pd, pt, cu, and bimetallic PdCu and PtCu nanocrystals, and PdCu JCPDS No.48-1551 and PdCu JCPDS No.48-1549 are PDF standard cards; FIG. b is a TEM image of ligand-free monometal Pd, pdCu, ptCu bimetallic nanocrystals, and FIG. 3 shows that ultra-fine metal nanoparticles with particle diameters of 1-3nm have been successfully prepared using this technique;
FIG. 4 is an XRD pattern for the implantation of multicomponent metallic nanoparticles into ZIF-8 and a TEM pattern for the implantation of representative PdCu into ZIF-8 in example 1 of the present invention, and the results of FIG. 4 show that the present invention successfully implants ultrafine metallic particles into ZIF-8 without affecting the morphology of the ZIF-8 carrier;
FIG. 5 is a TEM image and an elemental mapping image at various magnifications of PdCu@ZIF-8 in example 1 of the present invention, wherein FIG. a is a High Angle Annular Dark Field Transmission Electron Microscope (HAADFTEM) image of PdCu@ZIF-8 and FIG. b is an elemental mapping image thereof; FIG. c is a high resolution TEM image of the implanted bimetallic PdCu particles, and the results of FIG. 5 show that the PdCu bimetallic particles are uniformly distributed inside ZIF-8, demonstrating the feasibility of the technique;
FIG. 6 is an XPS diagram of the bimetallic PdCu in the embodiment 1 of the invention, wherein the diagram a is a Pd 3d XPS diagram, the diagram b is a Cu 2p XPS diagram, and the result of FIG. 6 shows that the introduction of Cu element enriches electrons on the Pd surface, thereby being beneficial to the catalytic activity;
FIG. 7H in example 1 of the present invention 2 The effect of pressure and temperature changes on the cinnamaldehyde hydrogenation performance of PtCu@ZIF-8, and the result of FIG. 7 shows that electrons on active Pt are transferred to the Cu surface, so that the electron density of the Pt surface is reduced, and the activity of main metals is inhibited;
the experimental methods of fig. 8-11 are:
the selective hydrogenation of Cinnamaldehyde (CAL) was carried out in a 25mL lined tetrafluoroethylene stainless steel autoclave equipped with a mechanical stirrer, a pressure gauge and an automatic temperature control device (Yanzheng Experimental Instruments co., ltd). For a typical caseIn the reactor, 0.4mmol of CAL, 20mg of catalyst and 3mL of solvent were added, using H 2 The autoclave was washed 4 times and the final H of the autoclave was 2 The pressure is set to 0.0-3.5MPa, then heated to the desired temperature (25-90 ℃ C.) and maintained at the desired temperature for the desired reaction time. For all experiments in this study, the stirring speed was set at 300-700rpm; after the reaction was completed, the reaction solution was filtered through a membrane (0.22 μm) and quantitatively analyzed by GC (Agilent 8860), and the final result of the performance test was an average of three or more test results. The used catalyst can be easily collected by centrifugation, washed with ethanol, and dried in a vacuum oven at 60 ℃ for 24 hours.
FIG. 8 effect of rotation speed and hydrogenation time on cinnamaldehyde hydrogenation performance of PdCu@ZIF-8 in example 1 of the invention, the result of FIG. 8 shows that 1MPa H 2 The condition of 70 ℃ is the optimal condition of liquid phase catalytic hydrogenation of cinnamaldehyde;
FIG. 9 the effect of PdCu@ZIF-8 catalyst in example 1 of the invention on the life of cyclic hydrogenation of cinnamaldehyde, and the result of FIG. 9 shows that with increasing rotation speed, the hydrogenation activity of cinnamaldehyde increases until equilibrium is reached at 500 rpm; the conversion rate of cinnamaldehyde is improved by prolonging the hydrogenation time, but the selectivity of the target product is reduced by more than 1h, so that the reaction time of 1h is most suitable for obtaining the target product;
FIG. 10 is a graph showing the effect of the PdCu@ZIF-8 catalyst of example 1 of the invention on the life of cyclic hydrogenation of cinnamaldehyde, and the result of FIG. 10 shows that the catalyst prepared by the technology has excellent catalyst life and is gradually deactivated after 5 cycles;
FIG. 11 shows the effect of Pt@ZIF-8 in example 2 and PtCu@ZIF-8 in example 1 of the invention on the hydrogenation performance of cinnamaldehyde, and the result of FIG. 11 shows that the PtCu@ZIF-8 catalyst has reduced catalytic activity due to the introduction of Cu element compared with Pt@ZIF-8.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the MOFs composite catalyst by in-situ implantation of the multicomponent metal nano-colloid particles is characterized by comprising the following steps:
(1) Preparation of Pt (MeOH), cu (MeOH), pd (MeOH) solutions containing Pd, cu, pt single-component nanocolloids:
respectively cleaning Pt, cu and Pd metal targets, and respectively carrying out transient pulse laser irradiation treatment I under the assistance of ultrasonic waves in methanol to respectively obtain Pt (MeOH), cu (MeOH) and Pd (MeOH) solutions;
(2) Preparation of ligand-free PdCu (MeOH), ptCu (MeOH) solutions containing PdCu, ptCu bimetallic nanocolloids:
uniformly mixing the Pd (MeOH) solution and the Pt (MeOH) solution in the step (1) with the Cu (MeOH) solution respectively to obtain two colloid mixed solutions, and then performing transient pulse laser irradiation treatment II on the two colloid mixed solutions under the assistance of ultrasound respectively to obtain ligand-free PdCu (MeOH) solution and PtCu (MeOH) solution respectively;
(3) Preparation of MOFs composite catalyst by in-situ implantation of multicomponent metal nano colloid particles:
mixing Pt (MeOH), cu (MeOH) and Pd (MeOH) solutions in the step (1) with ZIF-8 precursor solutions respectively, and stirring to react I to obtain Pt@ZIF-8, cu@ZIF-8 and Pd@ZIF-8 composite catalysts; and (3) mixing the ligand-free PdCu (MeOH) solution and PtCu (MeOH) solution in the step (2) with the ZIF-8 precursor solution respectively, and stirring to react II to obtain the PdCu@ZIF-8 and PtCu@ZIF-8 composite catalyst.
2. The method for preparing the MOFs composite catalyst by in-situ implantation of multicomponent metallic nano-colloid particles according to claim 1, wherein the Pd, cu and Pt single-component nano-colloids in the step (1) are prepared according to the following steps:
s11, sequentially carrying out ultrasonic cleaning treatment on Pt, cu and Pd targets by adopting deionized water, ethanol and methanol, then placing the targets in the methanol, and carrying out deepening cleaning treatment by adopting pulse laser to obtain clean targets;
wherein, the purities of Pt, cu and Pd targets are 99.999 percent;
s12, soaking the cleaning target material in the step S11 in a methanol solution, and then performing transient pulse laser irradiation treatment I to obtain Pd, cu and Pt single-component nano colloid;
wherein the concentration of the Pd, cu and Pt single-component nano colloid in the Pt (MeOH), cu (MeOH) and Pd (MeOH) solution is 0.06-0.16mg/mL, and the size of the Pd, cu and Pt single-component nano colloid particles is 2-10nm.
3. The method for preparing the multi-component metal nano-colloid particles in-situ implanted MOFs composite catalyst according to claim 1, wherein in the step (2), the volume ratio of Pd (MeOH) solution to Cu (MeOH) solution is (1-3): (1-3) the volume ratio of Pt (MeOH) solution to Cu (MeOH) solution is (1-3): (1-3).
4. The method for preparing the MOFs composite catalyst by in-situ implantation of multicomponent metallic nano-colloid particles according to claim 1, wherein the transient pulse laser irradiation treatment I in the step (1) and the transient pulse laser irradiation treatment II in the step (2) are consistent in condition, and are: irradiating with pulse unfocused laser beam with output wavelength of 1064nm, pulse frequency of 30Hz, output spot diameter of 6-10mm, and laser irradiation energy density of 800-1600mJ/cm 2 The irradiation time is 5-15min; and the ultrasonic frequency in the step (2) is 20-40kHz.
5. The method for preparing the multi-component metal nano-colloid particles in-situ implanted MOFs composite catalyst according to claim 1, wherein the concentration of the PdCu and PtCu bimetallic nano-colloid in the step (2) in the ligand-free PdCu (MeOH) and PtCu (MeOH) solution is 0.06-0.18mg/mL.
6. The method for preparing the MOFs composite catalyst by in-situ implantation of multicomponent metallic nano-colloid particles according to claim 1, wherein the ZIF-8 precursor solution of the step (3) is prepared according to the following steps:
respectively dissolving zinc nitrate hexahydrate and dimethyl imidazole in methanol until the solution is colorless and transparent, and then mixing the two solutions;
wherein, the mol ratio of the zinc nitrate hexahydrate to the dimethyl imidazole is 1:3.
7. the method for preparing the multi-component metal nano-colloid particles in-situ implanted MOFs composite catalyst according to claim 1, wherein the volume ratio of Pt (MeOH), cu (MeOH), pd (MeOH) solution to ZIF-8 precursor solution in the step (3) is 1:1-2;
the volume ratio of ligand-free PdCu (MeOH), ptCu (MeOH) solution to ZIF-8 precursor solution was 1:1-2.
8. The method for preparing the MOFs composite catalyst by in-situ implantation of multicomponent metallic nano-colloid particles according to claim 1, wherein the stirring reaction I and the stirring reaction II in the step (3) are the same in condition and are magnetically stirred for 3-5h under the condition of 500 rpm.
9. The multi-component metal nano-colloid particle in-situ implantation MOFs composite catalyst prepared by the preparation method of any one of claims 1-8, wherein the multi-component metal nano-colloid particle in-situ implantation MOFs composite catalyst is Pt@ZIF-8, cu@ZIF-8, pd@ZIF-8, pdCu@ZIF-8 and PtCu@ZIF-8 respectively.
10. An application of the multicomponent metallic nano-colloid particles in-situ implanted MOFs composite catalyst in preparing thermocatalytic materials and photo-thermocatalytic materials.
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