CN111450893A - Preparation of palladium-loaded quasi-MOF photocatalyst with special morphology and one-pot multi-step hydrogenation N-alkylation reaction - Google Patents

Preparation of palladium-loaded quasi-MOF photocatalyst with special morphology and one-pot multi-step hydrogenation N-alkylation reaction Download PDF

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CN111450893A
CN111450893A CN202010362240.1A CN202010362240A CN111450893A CN 111450893 A CN111450893 A CN 111450893A CN 202010362240 A CN202010362240 A CN 202010362240A CN 111450893 A CN111450893 A CN 111450893A
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蒋和雁
成洪梅
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Chongqing Technology and Business University
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Abstract

The invention discloses a preparation method of a palladium-loaded quasi-MOF photocatalyst with a special morphology and a one-pot multi-step hydrogenation N-alkylation reaction, wherein the preparation method of the catalyst comprises the following steps: 2-methylimidazole is used as a coordinator to prepare MOFs materials by a solvothermal method, palladium is loaded by a double-solvent method, and then the materials are calcined for 30 minutes at 300 ℃ under nitrogen to prepare the palladium-loaded quasi-MOF photocatalyst with a special morphology. The reaction method of photocatalytic one-pot multi-step hydrogenation N-alkylation comprises the following steps: the method comprises four continuous steps of taking an aromatic nitro compound or an aromatic nitrile compound as a raw material, carrying out alcohol dehydrogenation to aldehyde and hydrogenation of the aromatic nitro compound or the aromatic nitrile compound to amine in a reactor with nitrogen or a hydrogen balloon under the action of a photocatalyst and alkali, and carrying out condensation of the aldehyde and the amine to form imine and hydrogenation of the imine to form N-alkylamine. The preparation method of the catalyst is simple and easy to operate, can be used for high-efficiency photocatalytic one-pot multi-step hydrogenation N-alkylation reaction, and has the advantages of mild reaction conditions, high chemical selectivity of N-alkylamine, good catalyst stability and easy recycling.

Description

Preparation of palladium-loaded quasi-MOF photocatalyst with special morphology and one-pot multi-step hydrogenation N-alkylation reaction
Technical Field
The invention relates to a reaction path of synthesis modification and N-alkylation of MOFs, in particular to preparation of a palladium-supported quasi-MOF photocatalyst with a special morphology and a one-pot multi-step hydrogenation N-alkylation reaction.
Background
N-alkylated products have wide application in many important fields such as pesticides, medicines and bioactive molecules. The N-alkylation reaction can be classified into the following according to the type of reaction and the alkylating agent used: substitution with alcohols, halogenated alkanes and lipids as alkylating agents; addition methods using acrylic acid derivatives, epoxy compounds, and the like as alkylating agents; condensation reduction method using aldehyde and ketone as alkylating agent. The N-alkylation of alcohols with amines over catalysts remains a current focus of research. However, the one-pot synthesis of N-alkylamines with high chemoselectivity using more challenging starting materials, such as nitrobenzene or benzonitrile, remains quite attractive and challenging.
In order to adapt to the development of environment-friendly economy, green and clean light energy resources are receiving wide attention. The visible light driven photocatalysis method as an environment-friendly green technology shows good application prospect in the aspect of pollutant treatment. The Metal Organic Frameworks (MOFs) have the advantages of various porous crystal structures, high degree of order, large specific surface area, easy synthesis and modification, good thermal stability and chemical stability and the like. Thus, MOFs are currently an important subject of research in the field of photocatalytic materials. At present, a great deal of research reports on MOFs as a photocatalyst in the fields of light-driven water decomposition for hydrogen production, oxygen production, photocatalytic reduction for carbon dioxide and the like are provided, but the research in the field of photocatalytic organic synthesis is relatively less.
Disclosure of Invention
The invention provides preparation of a palladium-loaded quasi-MOF photocatalyst with a special morphology and a one-pot multi-step hydrogenation N-alkylation reaction.
The method utilizes the prepared palladium-supported quasi-MOF photocatalyst with special morphology to prepare N-alkylamine through one-pot multi-step hydrogenation N-alkylation of visible nitrobenzene or benzonitrile, and has the advantages of mild reaction conditions and high conversion rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for the preparation of a palladium supported "quasi-MOF" photocatalyst having a specific morphology, said process comprising the steps of:
1) FeCl was added to a 60 m L N, N-dimethylformamide solution3·6H2O (2.704 g) and terephthalic acid (0.828 g), sonication of the mixture for 20 min, transfer of the resulting solution to a 100 m L Teflon lined stainless steel autoclave, incubation at 110 ℃ for 24 h, separation and washing of the synthesized MI L-101 (Fe), conversion of terephthalic acid to 2-aminoterephthalic acid (0.905 g), preparation of NH2-MIL-101(Fe)。
2) Adding 2-methylimidazole (0.328 g) in the synthesis process, and synthesizing MI L-101 (Fe) or NH with special morphology in the same way in other steps2-MIL-101 (Fe), abbreviated as MI L-101 (Fe) -2MI or NH2-MIL-101(Fe)-2MI.
3) 100 mg of the above-mentioned MI L-101 (Fe) -2MI or NH were added2-MI L-101 (Fe) -2MI was suspended in 20 m L n-hexane, and Pd (OAc) was added dropwise over 15 min with vigorous stirring2After stirring the aqueous solution for 2 hours, separating the solid from the supernatant, washing the solid with ethanol, and drying the solid in vacuum at 150 ℃ to obtain the MOF (metal organic framework) loaded with the negative palladium and having a special shape, namely Pd/MI L-101 (Fe) -2MI or Pd/NH2Preparation of Pd/NH from-MI L-101 (Fe) -2 MI.2-MIL-101(Fe)。
4) Pd/NH2heating-MI L-101 (Fe) -2MI to 300 ℃ at the heating rate of 5 ℃/min in nitrogen and keeping the temperature for 30 min to obtain the palladium-supported quasi-MOF material, Pd/NH for short2-MIL-101(Fe)-2MI（300）。
The mass fraction of palladium element in the obtained palladium-supported quasi-MOF catalyst with special morphology is 1 wt%. No additional reducing agent is required for all palladium reductions.
The preparation of palladium supported quasi-MOF photocatalyst with special morphology and one-pot multistep hydrogenation N-alkylation reaction includes the following steps:
Pd/NH of 'quasi-MOF' supported palladium catalyst with special morphology2MI L-101 (Fe) -2MI (300) and potassium phosphate were placed in a glass reactor equipped with a nitrogen balloon, nitrobenzene and benzyl alcohol solution were added, the reaction was carried out for 24 h under irradiation of a 100W blue L ED lamp and the nitrobenzene conversion and product selectivity were analyzed by GC and GC-MS.
Further, the aromatic nitro compound is: nitrobenzene, 2-chloronitrobenzene, 4-fluoronitrobenzene, 4-nitrobenzaldehyde, 2-nitroacetophenone, 3-nitroacetophenone, 2-methoxynitrobenzene, 4-methoxynitrobenzene, 2-methylnitrobenzene, 4-nitrophenol, etc.
Further, the alcohol includes: 4-methoxybenzyl alcohol, 4-methylbenzyl alcohol, 2-methylbenzyl alcohol, n-butanol, and the like.
Further, benzonitrile and benzyl alcohol were used to react under hydrogen.
Further, the aromatic nitrile compound is: benzonitrile, 4-trifluoromethylbenzonitrile, 2-methylbenzonitrile, 4-methylbenzonitrile, 3-methoxybenzonitrile, and the like.
In the above reaction, the alcohol is not only an aromatic nitro compound, an aromatic nitrile compound, a hydrogen donor for hydrogenation reduction of imine, but also an alkylating agent for N-alkylation. The palladium-loaded quasi-MOF photocatalyst with special morphology is a catalyst for preparing aldehyde by dehydrogenating alcohol, a catalyst for preparing amine by hydrogenating aromatic nitro compounds or aromatic nitrile compounds, and a catalyst for preparing N-alkylamine by condensing aldehyde and amine into imine and hydrogenating imine.
Compared with the prior art, the invention has the following advantages and effects:
1. the preparation method of the catalyst is simple, and the supported palladium is reduced without an additional reducing agent and is subjected to in-situ photoreduction in the reaction process.
2. The photocatalyst prepared by the method is used for the multi-step hydrogenation N-alkylation reaction in a photocatalytic one-pot process, so that the defects of harsh reaction conditions, separation and purification of intermediates and the like in the N-alkylation reaction process are overcome, and the atom economy is improved. An efficient process for obtaining N-alkylamines in nitrobenzene or benzonitrile and alcohols is provided.
Drawings
FIG. 1 shows the preparation of MI L-101 (Fe), NH in EXAMPLE 12MI L-101 (Fe) and MI L-101 (Fe) -2MI, NH2SEM picture of-MI L-101 (Fe) -2 MI.
FIG. 2 shows NH prepared in example 12-X-ray diffraction pattern (XRD) of MI L-101 (Fe) catalyst.
FIG. 3 is Pd/NH prepared in example 12SEM and Transmission Electron Microscopy (TEM) of MI L-101 (Fe) -2MI (300);
FIG. 4 is Pd/NH prepared in example 12-MI L-101 (Fe) -2MI and Pd/NH2X-ray photoelectron spectroscopy (XPS) of Fe and Pd for MI L-101 (Fe) -2MI (300).
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
the preparation method of the palladium-supported quasi-MOF with special morphology shown in the embodiment of the invention comprises the following steps
(1) FeCl was added to a 60 m L N, N-dimethylformamide solution3·6H2O (2.704 g) and terephthalic acid (0.828 g), sonication of the mixture for 20 min, transfer of the resulting solution to a 100 m L Teflon lined stainless steel autoclave, incubation at 110 ℃ for 24 h, separation and washing of the synthesized MI L-101 (Fe), conversion of terephthalic acid to 2-aminoterephthalic acid (0.905 g), preparation of NH2-MIL-101(Fe)。
(2) Adding 2-methylimidazole (0.328 g) in the synthesis process, and synthesizing MI L-101 (Fe) or NH with special morphology in the same way in other steps2MI L-101 (Fe), abbreviated MI L-101 (Fe) -2MI or NH2-MIL-101(Fe)-2MI。
(3) 100 mg of the above-mentioned MI L-101 (Fe) -2MI or NH were added2-MI L-101 (Fe) -2MI was suspended in 20 m L n-hexane, and Pd (OAc) was added dropwise over 15 min with vigorous stirring2After stirring the aqueous solution for 2 hours, separating the solid from the supernatant, washing the solid with ethanol, and drying the solid in vacuum at 150 ℃ to obtain the MOF (metal organic framework) loaded with the negative palladium and having a special shape, namely Pd/MI L-101 (Fe) -2MI or Pd/NH2Preparation of Pd/NH from-MI L-101 (Fe) -2 MI.2-MIL-101(Fe)。
(4) Pd/NH2heating-MI L-101 (Fe) -2MI to 300 ℃ at a heating rate of 5 ℃/min in nitrogen and keeping the temperature for 30 min to obtain a palladium-supported quasi-MOF material, dispersing the calcined material in an acetonitrile solution, adding benzyl alcohol under the condition of nitrogen, irradiating for 24 h with 100W blue L ED, simulating reaction conditions to reduce palladium, and preparing Pd/NH2-MIL-101(Fe)-2M(300)。
FIG. 1 shows MI L-101 (Fe), NH synthesized in steps (1) and (2) above2MI L-101 (Fe) and MI L-101 (Fe) -2MI, NH2SEM image of-MI L-101 (Fe) -2MI, from which it is evident that MI L-101 (Fe) and NH were coordinated with 2-methylimidazole2-MIL-101(Fe) The appearance of the alloy is obviously changed.
For NH prepared in this example2XRD analysis of the-MI L-101 (Fe) catalyst materials is shown in FIG. 2, in which NH is synthesized2-MI L-101 (Fe) with simulated NH2The MI L-101 (Fe) has higher goodness of fit from NH2MI L-101 (Fe) to NH2The intensity of characteristic peak of-MI L-101 (Fe) -2MI is increased due to the increase of crystallinity of the sample after loading palladium, no obvious palladium diffraction phenomenon is found, which may be related to small loading and high dispersion degree2-MI L-101 (Fe) -2MI (300) broadening at diffraction peak around 5-10 °, other diffraction peaks with NH2-MI L-101 (Fe) -2MI is essentially identical, obviously, NH2the-MI L-101 (Fe) -2MI has certain skeleton structure maintained during calcination, but the organic ligand is decomposed partially, and the decomposition is favorable for enhancing the interaction between the inorganic node and the Pd NPs.
FIG. 3 shows Pd/NH prepared in the above (4)2SEM image and TEM image of-MI L-101 (Fe) -2MI (300), from which it can be seen that after calcination, the morphology is associated with NH2Same as-MI L-101 (Fe) -2MI, from TEM image, it can be seen that Pd nanoparticles are uniformly dispersed in NH2On MI L-101 (Fe) -2MI (300), the (111) lattice fringes of Pd were clearly observed in the high-resolution TEM image.
FIG. 4 shows Pd/NH prepared in the above (3) and (4)2-MI L-101 (Fe) -2MI and Pd/NH2XPS of-MI L-101 (Fe) -2MI (300) from which the successful reduction of Pd to zero-valent Pd/NH2XPS of-MI L-101 (Fe) -2MI (300) showed Fe 2p and Pd03d has a higher binding energy due to NH2The partial decomposition of-MI L-101-2 MI changes the coordination environment of Fe and Pd, and enhances the interaction between inorganic nodes and Pd NPs.
MI L-101 (Fe), NH prepared for (1), (3) and (4) above2-MIL-101(Fe)、Pd/NH2-MIL-101(Fe)，Pd/NH2-MI L-101 (Fe) -2MI and Pd/NH2The characterization of MI L-101 (Fe) -2MI (300) by ultraviolet-visible diffuse reflectance (UV-VisDRS) shows that the absorption capacity of light in the ultraviolet-visible region is increased gradually, and the forbidden band width is reduced gradually.NH2-MIL-101(Fe)、Pd/NH2-MIL-101(Fe)，Pd/NH2-MI L-101 (Fe) -2MI and Pd/NH2MI L-101 (Fe) -2MI (300) was characterized by photocurrent and Electrochemical Impedance (EIS), Pd/NH2-MI L-101 (Fe) -2MI (300) has the highest charge separation efficiency and the lowest charge transfer resistance, and 2-methylimidazole and Pd nanoparticles are favorable for improving charge separation efficiency and electron transfer.
Example 2 (reaction reference Table 1, entry 1)
20 mg of prepared Pd/MI L-101 (Fe) -2MI and 0.2mmol of potassium phosphate were placed in a closed glass reactor, the air in the tube was replaced with nitrogen several times, a balloon filled with nitrogen was fitted, a solution of 0.1 mmol of nitrobenzene, 3mmol of benzyl alcohol and 2m L of acetonitrile was added, the reaction was carried out for 24 hours under irradiation of a 100W blue L ED lamp, and the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 100.0%, and the selectivity of N-benzylaniline (4 a) was 85%.
EXAMPLE 3 (Ref. Table 1, entry 4)
20 mg of prepared Pd/MI L-101 (Fe) -2MI and 0.2mmol of potassium phosphate were placed in a closed glass reactor, the air in the tube was replaced with nitrogen several times, a balloon filled with nitrogen was fitted, a solution of 0.1 mmol of nitrobenzene, 3mmol of benzyl alcohol and 2m L of acetonitrile was added, the reaction temperature was controlled by a water bath at 80 ℃, the reactor was wrapped with tinfoil paper, reacted for 24 hours, and the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS.
EXAMPLE 4 (Ref. Table 1, entry 6)
20 mg of prepared Pd/MI L-101 (Fe) and 0.2mmol of potassium phosphate were placed in a closed glass reactor, the air in the tube was replaced with nitrogen several times, a balloon filled with nitrogen was fitted, a solution of 0.1 mmol of nitrobenzene, 3mmol of benzyl alcohol and 2m L of acetonitrile was added, and the reaction was carried out for 24 hours under irradiation of a 100W blue L ED lamp, and the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 73%, and the selectivity of N-benzylaniline (4 a) was 51%.
EXAMPLE 5 (Ref. Table 1, entry 7)
20 mg of prepared Pd/MI L-101 (Fe), 0.02mmol of 2-methylimidazole and 0.2mmol of potassium phosphate were placed in a closed glass reactor, the air in the tube was replaced several times with nitrogen, a balloon filled with nitrogen was fitted, a solution of 0.1 mmol of nitrobenzene, 3mmol of benzyl alcohol and 2m L of acetonitrile was added, the reaction was carried out for 24 hours under irradiation of a 100W blue L ED lamp, and the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 72%, and the selectivity of N-benzylaniline (4 a) was 50%.
EXAMPLE 6 (Ref. Table 1, entry 9)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI and 0.2mmol potassium phosphate in a closed glass reactor, after displacing the air in the tube several times with nitrogen, equipped with a balloon filled with nitrogen, 0.1 mmol nitrobenzene, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 100% and the selectivity of N-benzylaniline (4 a) was 86%.
EXAMPLE 7 (Ref. Table 1, entry 10)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium phosphate in a closed glass reactor, after replacing the air in the tube with nitrogen several times, equipped with a balloon filled with nitrogen, 0.1 mmol nitrobenzene, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 100%, the selectivity of N-benzylaniline (4 a) was 96%.
Figure DEST_PATH_IMAGE001
Figure DEST_PATH_IMAGE002
Example 8 (reaction reference Table 2, entry 1)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) was placed multiple times in a closed glass reactor using nitrogen gasAfter changing the atmosphere in the tube, a balloon filled with nitrogen was fitted, a solution of 0.1 mmol of nitrobenzene, 3mmol of benzyl alcohol and 2m L of acetonitrile was added and the reaction was carried out for 24 h under irradiation of a 100W blue L ED lamp, and the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS.
Example 9 (reaction reference Table 3, entry 1)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium phosphate in a closed glass reactor, after replacing the air inside the tube with nitrogen several times, equipped with a balloon filled with nitrogen, 0.1 mmol 2-chloronitrobenzene, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of 2-chloronitrobenzene was 75% and the selectivity of the corresponding N-alkylamine (4) was 86%.
EXAMPLE 10 (Ref. Table 3, entry 7)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium phosphate in a closed glass reactor, after replacing the air in the tube with nitrogen several times, equipped with a balloon filled with nitrogen, 0.1 mmol 2-methoxynitrobenzene, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of 2-methoxynitrobenzene was 89% and the selectivity of the corresponding N-alkylamine (4) was 90%.
EXAMPLE 11 (Ref. Table 3, entry 8)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium phosphate in a closed glass reactor, after replacing the air in the tube with nitrogen several times, equipped with a balloon filled with nitrogen, 0.1 mmol 4-methoxynitrobenzene, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of 4-methoxynitrophenylbenzene was 96% and the selectivity of the corresponding N-alkylamine (4) was 92%.
EXAMPLE 12 (Ref. Table 3, entry 13)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium phosphate in a closed glass reactor, after displacing the air inside the tube several times with nitrogen, equipped with a balloon filled with nitrogen, 0.1 mmol nitrobenzene, 3mmol 4-methylbenzyl alcohol and 2m L acetonitrile solution were added and reacted for 24 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS, the conversion of nitrobenzene was 90% and the selectivity of the corresponding N-alkylamine (4) was 93%.
Figure DEST_PATH_IMAGE003
Example 13 (reaction reference Table 4, entry 3)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium carbonate in a closed glass reactor, after multiple displacement of the air in the tube with hydrogen, equipped with a balloon filled with hydrogen, 0.1 mmol benzonitrile, 3mmol benzyl alcohol and 2m L acetonitrile solution were added and reacted for 30 h under irradiation of a 100W blue L ED lamp, the conversion of nitrobenzene and the product selectivity were analyzed by GC and GC-MS-the conversion of benzonitrile was 91% and the selectivity of dibenzylamine (7 a) was 95%.
Figure DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE005
Example 14 (reaction reference Table 5, entry 1)
20 mg of prepared Pd/NH2-MI L-101 (Fe) -2MI (300) and 0.2mmol potassium carbonate in a closed glass reactor, after multiple replacement of the air in the tube with hydrogen, equipped with a balloon filled with hydrogen, 0.1 mmol 4-trifluoromethylbenzonitrile, 3mmol benzyl alcohol and 2m L acetonitrile solution, reacted for 24 h under irradiation of a 100W blue L ED lamp, analyzed by GC and GC-MS for nitrobenzene conversion and product selectivity 45% for 4-trifluoromethylbenzonitrile and 91% for the corresponding N-alkylamine (7) when irradiatedThe reaction time was extended to 48 h, the conversion of 4-trifluoromethylbenzonitrile was 85%, and the selectivity to the corresponding N-alkylamine (7) was 92%.

Claims (8)

1. A preparation method of a palladium-loaded quasi-MOF photocatalyst with a special morphology and a one-pot multi-step hydrogenation N-alkylation reaction comprises the following steps: 2-methylimidazole is used as a coordinator to prepare MOFs materials by a solvothermal method, and after palladium is loaded by a double-solvent method, the MOFs materials are calcined for 30 minutes at 300 ℃ under nitrogen to prepare a palladium-loaded quasi-MOF photocatalyst with a special morphology; the method for photocatalytic one-pot multistep hydrogenation N-alkylation reaction comprises the following steps: the method comprises four continuous steps of taking an aromatic nitro compound or an aromatic nitrile compound as a raw material, carrying out alcohol dehydrogenation to aldehyde and hydrogenation of the aromatic nitro compound or the aromatic nitrile compound to amine in a reactor with nitrogen or a hydrogen balloon under the action of a photocatalyst and alkali, and carrying out condensation of the aldehyde and the amine to form imine and hydrogenation of the imine to form N-alkylamine.
2. The method according to claim 1, wherein the supported metal is one or more selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, gold and silver, and the color of the light is one or more selected from red, orange, yellow, green, blue, indigo and violet.
3. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1, characterized in that: the catalyst has higher catalytic activity when no morphology regulation and 'quasi-MOF' structure is introduced; the catalytic activity of the reaction is greatly improved under the conditions of carrying out morphology regulation and forming a quasi-MOF structure.
4. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1, characterized in that: the catalytic system has no catalytic activity in the absence of illumination, and has high catalytic activity under light induction.
5. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1 is characterized in that: the catalytic reaction can be carried out in an alkali-free environment, the catalytic activity is greatly improved by introducing an alkali additive, and the alkali comprises one or more of potassium phosphate, sodium hydroxide, potassium carbonate, dipotassium hydrogen phosphate, potassium bicarbonate, triethylamine and the like.
6. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1, characterized in that: the aromatic nitro compound comprises: nitrobenzene, 2-chloronitrobenzene, 4-fluoronitrobenzene, 4-nitrobenzaldehyde, 2-nitroacetophenone, 3-nitroacetophenone, 2-methoxynitrobenzene, 4-methoxynitrobenzene, 2-methylnitrobenzene, 4-nitrophenol, etc.; the aromatic nitrile compound comprises: benzonitrile, 4-trifluoromethylbenzonitrile, 2-methylbenzonitrile, 4-methylbenzonitrile, 3-methoxybenzonitrile, and the like.
7. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1, characterized in that: the alcohol comprises: aromatic alcohol and alkyl alcohol such as 4-methoxybenzyl alcohol, 4-methylbenzyl alcohol, 2-methylbenzyl alcohol and n-butanol.
8. The preparation and one-pot multi-step hydrogenation N-alkylation reaction of the palladium-supported quasi-MOF photocatalyst with special morphology according to claim 1, characterized in that: the nitrogen or hydrogen pressure employed in the catalytic system is pressurized or 1 atm.
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