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CN-121991136-A - Preparation of nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand and application thereof in catalytic hydrogen production

CN121991136ACN 121991136 ACN121991136 ACN 121991136ACN-121991136-A

Abstract

The invention belongs to the technical field of chemical synthesis technology and hydrogen energy science, and particularly relates to preparation of a nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand and application thereof in catalytic hydrogen production. The nickel complex is dihydrate Acetate radical 2- (((2-Morpholinoethyl) imino) methyl) -4-nitrophenoxy nickel (II) having the chemical structure: . The nickel complex has the advantages of simple synthesis method, mild reaction conditions, short preparation period, high yield and the like, and can be suitable for preparing the nickel complex of Schiff base ligand by condensing other amino compounds with salicylaldehyde and derivatives thereof. The nickel complex of the invention has high-efficiency electrocatalytic and photocatalytic hydrogen production activities and has potential application value in the field of hydrogen energy.

Inventors

  • XIE BIN
  • Zheng Jixi
  • HUANG YUFENG
  • LI RENKUN
  • WANG YALI
  • QI JI
  • SUN RAN
  • Quan Zhipeng
  • ZHANG XIN

Assignees

  • 四川轻化工大学

Dates

Publication Date
20260508
Application Date
20260202

Claims (10)

  1. 1. A nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand is characterized in that the nickel complex is dihydrate Acetate radical 2- (((2-Morpholinoethyl) imino) methyl) -4-nitrophenoxy nickel (II) having the chemical structure: 。
  2. 2. Use of the nickel complex as defined in claim 1 for electrocatalytic hydrogen production.
  3. 3. Use of the nickel complex as defined in claim 1 for photocatalytic hydrogen production.
  4. 4. A process for the preparation of a nickel complex containing a 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol ligand according to claim 1, characterized in that it is prepared by the following route: 。
  5. 5. A process for the preparation of a nickel complex containing a 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol schiff base ligand according to claim 1, characterised in that it comprises the steps of: 1) Adding N-2-aminoethyl morpholine into methanol to obtain colorless transparent solution, adding methanol solution containing 5-nitro salicylaldehyde, heating, stirring and refluxing for a period of time at a certain temperature; 2) Carrying out reduced pressure filtration on the product obtained after the reaction in the step 1), and washing a filter cake for multiple times by using cold methanol and cold diethyl ether in sequence; 3) Drying the obtained solid in vacuum, heating and dissolving the solid by using ethanol to obtain a saturated solution, slowly cooling to room temperature, standing overnight, filtering under reduced pressure, washing a filter cake by using cold ethanol and cold diethyl ether in sequence, and drying in vacuum to obtain yellow flaky crystals of 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol; 4) Dissolving the obtained 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol in an organic solvent, and adding Ni (OAc) containing thereto 2 4H 2 O, heating, stirring, refluxing for a period of time, filtering under reduced pressure, washing filter cake with cold ethanol and cold diethyl ether sequentially, and vacuum drying to obtain dark green powder, i.e. dihydrate Acetate radical 2- (((2-Morpholinoethyl) imino) methyl) -4-nitrophenoxy nickel (II).
  6. 6. The process for preparing a nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand according to claim 5, wherein in step 1), the molar ratio of N-2-aminoethylmorpholine to 5-nitrosalicylaldehyde is 1-1.2:1, the heating reflux temperature is 85℃and the stirring time is 60-90 min.
  7. 7. The method for preparing a nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand according to claim 5, wherein in the step 4), the organic solvent is any one of ethanol, methanol or acetonitrile, and the heating and stirring reflux time is 60-90 min.
  8. 8. The process for preparing a nickel complex containing a 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand according to claim 7, wherein in step 4), 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol, ni (OAc) 2 The dosage ratio of 4H 2 O to organic solvent is 1 mmol:1 mmol:30-45 mL.
  9. 9. The method for preparing hydrogen by electrocatalytic hydrogen production using a nickel complex as set forth in claim 2, wherein the proton source is any one of acetic acid, trifluoroacetic acid and triethylammonium chloride.
  10. 10. The method of producing hydrogen by photocatalysis as claimed in claim 3, wherein the photocatalysis system comprises nickel complex, cdS NRs and electron sacrificial agent aqueous solution, wherein the electron sacrificial agent is any one of ascorbic acid, triethanolamine or lactic acid.

Description

Preparation of nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand and application thereof in catalytic hydrogen production Technical Field The invention belongs to the technical field of chemical synthesis technology and hydrogen energy science, and particularly relates to preparation of a nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand and application thereof in catalytic hydrogen production. Background With the continuous increase of global energy demand, environmental problems caused by the massive consumption of traditional fossil energy are increasingly prominent, and the development of clean, efficient and renewable new energy has become a great core direction of scientific research nowadays. The hydrogen energy is recognized as a new energy source with great potential in a future energy system by virtue of the extremely high quality energy density and the clean pollution-free characteristics, and has wide application prospect. In the existing hydrogen production technology path, the electrolytic water and the photolytic hydrogen production are not dependent on fossil energy, and are highly connected with renewable energy sources in nature such as solar energy, wind energy and the like, so that the hydrogen production technology path is widely paid attention to the industry. Especially, the light driving hydrogen production which can directly convert solar energy into chemical energy is an ideal way for realizing green energy conversion. However, in practical application, the photoelectric hydrogen production generally faces technical bottlenecks of slow reaction, low hydrogen production efficiency, high energy consumption and the like, and the large-scale development of hydrogen energy is severely restricted. Therefore, in order to reduce energy consumption and improve hydrogen production efficiency, developing a catalyst with high efficiency, stability and low cost becomes a hot problem in research of hydrogen production technology. Inspired by the efficient catalytic proton reduction of natural hydrogenase to generate hydrogen, the research of exploring artificial catalysts for simulating biological enzymes, in particular to transition metal complexes taking non-noble metals such as nickel, cobalt, iron and the like as cores, is in progress. Compared with natural hydrogenase, the artificial catalyst has obvious advantages in resource reserves, synthesis modes, structural diversity and stability under chemical environment. At present, a large number of transition metal complexes with different coordination numbers and different ligands have been designed and synthesized, and the application potential of the transition metal complexes in the field of electrocatalytic and photocatalytic hydrogen production is continuously mined. Disclosure of Invention The invention aims at providing a nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand, which is named as dihydrateAcetate radical2- (((2-Morpholinoethyl) imino) methyl) -4-nitrophenoxy nickel (II). The nickel complex is used as a catalyst for hydrogen production, and has important application value in the technical field of hydrogen energy science. The invention also aims to provide a preparation method of the nickel complex, which has the characteristics of simple synthetic route, mild reaction condition, simple operation, short preparation period, high yield and the like, and can be used for preparing derivatives of the complex. In order to achieve the above object, the present invention has the following specific technical scheme: Nickel complex containing 2- (((2-morpholinoethyl) imino) methyl) -4-nitrophenol Schiff base ligand and named as dihydrate Acetate radical2- (((2-Morpholinoethyl) imino) methyl) -4-nitrophenoxy nickel (II) having the molecular structure shown below: 。 The Schiff base adopted in the application has simple and convenient synthesis and easy regulation and control structure, and can form stable coordination bond with the metal center through imine nitrogen atoms. The Schiff base can introduce different substituents at two sides of an imine bond to regulate and control the electron cloud density and molecular configuration of the whole complex, and the addition of potential protonation sites in the ligand can effectively improve the electron transfer and protonation capacity of the complex catalyst, so that the hydrogen production efficiency of the catalyst is improved. The morpholine as saturated heterocycle containing nitrogen and oxygen atoms can improve the solubility of the complex in polar solvents, and meanwhile, the nitrogen and oxygen atoms on the group can be used as active sites for protonation due to the lone pair electrons, so that the metal-ligand synergistic catalysis effect is formed, and the catalytic hydrogen production efficiency of the complex is improved. Theref