Magnetic-nanoparticle-supported catalyst and method of making

Patent metadata

Field	Value
Publication number	US-12162001-B2
Application number	US-202418607097-A
Country	US
Kind code	B2
Filing date	Mar 15, 2024
Priority date	Aug 23, 2022
Publication date	Dec 10, 2024
Grant date	Dec 10, 2024

Abstract

A method for making a magnetic-nanoparticle-supported catalyst includes reacting a ferrocenyl phosphine compound with an amino alcohol compound to form a ligand having a phosphine group, an amine group and at least one hydroxyl group; anchoring the ligand to a surface of magnetic nanoparticles via an oxygen atom of the hydroxyl group to form a ligand complex; combining the ligand complex with a metal precursor comprising Rh to bind the metal precursor with the ligand complex and form the magnetic-particle-supported catalyst. The magnetic-particle-supported catalyst is a Rh complex of magnetic-Fe3O4-nanoparticle-supported ferrocenyl phosphine catalyst.

First claim

The invention claimed is:

1. A method for making a magnetic-nanoparticle-supported catalyst for hydrogen transfer and hydroformylation reactions, comprising:
reacting a ferrocenyl phosphine compound with an amino alcohol compound to form a ligand having a ferrocene unit comprising a central iron atom, an unsubstituted cyclopentadienyl (Cp) ring, a substituted Cp ring substituted with (i) an alkyl group having an amine group and a phenyl group having at least one hydroxyl group, and (ii) one phosphine group;
wherein the Cp ring and the alkyl substituted Cp ring are bound to the central iron atom;
wherein the phosphine group is attached to the alkyl substituted Cp ring;
anchoring the ligand to a surface of magnetic nanoparticles via an oxygen atom of the hydroxyl group to form a ligand complex;
collecting the ligand complex with a magnet;
combining the ligand complex with a metal precursor comprising Rh to bind the metal precursor with the ligand complex and form the magnetic-nanoparticle-supported catalyst.

2. The method of claim 1 , further comprising:
acylating a ferrocene and reductive aminating with an alkylamine to provide an alkylamine substituted ferrocene;
phosphorylating the alkylamine substituted ferrocene with an organophosphorus compound to provide an alkylamine substituted ferrocenyl phosphine;
wherein the alkylamine substituted ferrocenyl phosphine comprises the phosphine group and an alkylamine group, and wherein the phosphine group and the alkylamine group are on the same Cp ring;
acylating the alkylamine substituted ferrocenyl phosphine to provide the ferrocenyl phosphine compound.

3. The method of claim 2 , wherein:
the alkylamine is dimethylamine;
the organophosphorus compound is diphenylphosphine chloride;
the alkylamine substituted ferrocenyl phosphine is N,N-dimethyl-1-[-2-(diphenyl phospheno)ferrocenyl]ethylamine (PPFA);
the ferrocenyl phosphine compound is 1-[-2-(diphenyl phospheno)ferrocenyl]ethylacetate (PPFA-OAc);
the amino alcohol compound is dopamine hydrochloride (dop);
the ligand is dopamine ferrocenyl phosphine (dop-Fc);
the magnetic nanoparticles are superparamagnetic Fe 3 O 4 nanoparticles, in the form of spheres;
the ligand complex is a magnetic-Fe 3 O 4 -nanoparticle-supported dopamine ferrocenyl phosphine;
the metal precursor is bicyclo[2.2.1]hepta-2,5-diene-rhodium(I) chloride dimer; and
the magnetic-nanoparticle-supported catalyst is a Rh complex of the magnetic-Fe 3 O 4 -nanoparticle-supported dopamine ferrocenyl phosphine.

4. The method of claim 1 , further comprising:
sonicating the magnetic nanoparticles to form a first suspension;
mixing the ligand and the suspension, and sonicating to form a second suspension comprising ligand anchored magnetic nanoparticles; and
wherein the magnetic nanoparticles are Fe 3 O 4 nanoparticles;
wherein the ligand is dop-Fc; and
wherein the ligand anchored magnetic nanoparticles are magnetic-Fe 3 O 4 -nanoparticle-supported dopamine ferrocenyl phosphine nanoparticles.

5. The method of claim 1 , wherein the magnetic-nanoparticle-supported catalyst has 0.2 to 0.3 mmol of Rh per gram of the catalyst.

6. The method of claim 1 , wherein the magnetic-nanoparticle-supported catalyst has a particle size in a longest dimension of 5 nm to 10 nm.

7. The method of claim 1 , wherein individual crystals of magnetite (Fe 3 O 4 ) within the magnetic-nanoparticle-supported catalyst have an interplanar distance of 0.2 nm to 0.25 nm between the individual crystals.

8. The method of claim 7 , wherein the individual crystals of magnetite are uniformly distributed throughout the magnetic-nanoparticle-supported catalyst.

9. The method of claim 1 , wherein the magnetic-nanoparticle-supported catalyst has a crystalline morphology.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Shaikh M Nasiruzzaman
• Hussain S M Shakil
• Aziz Md Abdul

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J31/2414

  comprising aliphatic or saturated rings · CPC title