IP Library › Granted Patent US 12,246,968
Granted Patent B2
US 12,246,968 · App. 17/417,684 · Granted Mar 11, 2025

Oleophilic hydrophobic magnetic porous materials

Inventors: Vikas Nandwana (Evanston, IL); Vinayak P. Dravid (Glenview, IL)
Assignee: Northwestern University
C01B32/22B01J20/06B01J20/20B01J20/262B01J20/28007B01J20/28009B01J20/32B01J20/3212B01J20/3236B01J20/324B82Y30/00C01B32/20C02F1/281C02F1/283C02F1/288C09K3/32C10G25/003C10G25/006C11B13/04H01M4/583H01M4/667B82Y40/00C02F2101/32C02F2103/007C02F2303/16C10G2300/1003C10G2300/1014H01M2004/021
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,246,968
App. No.
17/417,684
Granted
Mar 11, 2025
Kind
B2
Abstract

Oleophilic-hydrophobic-magnetic (OHM) porous materials are provided. In embodiments, an OHM porous material comprises a porous substrate having a solid matrix defining a plurality of pores distributed through the solid matrix, the OHM porous material further comprising a coating of a nanocomposite on surfaces of the solid matrix. The nanocomposite comprises a multilayer stack of a plurality of layers of a two-dimensional, layered material having nucleation sites interleaved between a plurality of layers of magnetic nanoparticles, wherein individual layers of magnetic nanoparticles in the plurality of layers of magnetic nanoparticles are each directly anchored on a surface of a layer of the plurality of layers of the two-dimensional, layered material via the nucleation sites, and are each separated by multiple layers of the plurality of layers of the two-dimensional, layered material. Methods of making and using the OHM porous materials are also provided.

Claims (18)

1. An oleophilic-hydrophobic-magnetic (OHM) porous material for recovering a hydrophobic material from a mixture, the OHM porous material comprising a porous substrate having a solid matrix defining a plurality of pores distributed through the solid matrix, the OHM porous material further comprising a coating of a nanocomposite on surfaces of the solid matrix,

the nanocomposite comprising dimensional, layered material having nucleation sites interleaved between a plurality of layers of a multilayer stack of a plurality of layers of graphite, each graphite layer in the plurality of layers of graphite comprising multiple graphene layers and each graphite layer having nucleation sites thereon, the nanocomposite further comprising a plurality of layers of magnetic nanoparticles interleaved with the plurality of layers of graphite, wherein individual layers of magnetic nanoparticles in the plurality of layers of magnetic nanoparticles are each directly anchored on a surface of a graphite layer of the plurality of layers of graphite via the nucleation sites and individual layers of magnetic nanoparticles are each separated by a graphite layer of the plurality of layers of graphite,

further wherein neighboring layers in the multilayer stack are held together via van der Waals forces such that the nanocomposite is free of isolated graphene layers.

2. The OHM porous material of claim 1 , wherein the nanoparticles and the plurality of layers of graphite are unfunctionalized.

3. The OHM porous material of claim 1 , wherein the magnetic nanoparticles comprise iron, iron oxide, or an alloy of iron or iron oxide.

4. The OHM porous material of claim 1 , wherein the nanocomposite is free of aggregated magnetic nanoparticles.

5. The OHM porous material of claim 1 , wherein the magnetic nanoparticles have an average diameter such that the magnetic nanoparticles exhibit superparamagnetic behavior.

6. The OHM porous material of claim 1 , wherein the solid matrix is composed of polyurethane, cellulose, melamine, polyimide, acrylic, polyamide, polyester, polycarbonate, polyaramide, or combinations thereof.

7. The OHM porous material of claim 1 , wherein the nanocomposite forms a coating on the solid matrix having an average thickness in a range of from 300 nm to 3 μm.

8. A method of recovering a hydrophobic material from a mixture, the method comprising contacting the OHM porous material of claim 1 with a mixture comprising a hydrophobic material for a period of time to absorb at least a portion of the hydrophobic material from the mixture onto the OHM porous material and provide the mixture with a reduced amount of the hydrophobic material.

9. The method of claim 8 , wherein the hydrophobic material is an oil or a water insoluble organic compound or a water immiscible organic compound or combinations thereof.

10. The method of claim 8 , further comprising releasing the absorbed hydrophobic material from the OHM porous material.

11. The method of claim 10 , wherein the releasing is accomplished by exposing the OHM porous material to an external stimulus to generate heat.

12. The method of claim 11 , wherein the external stimulus is a radio-frequency (RF) field applied for a period of time.

13. A method of making the OHM porous material of claim 1 , the method comprising immersing the porous substrate in a formulation comprising the nanocomposite for a period of time to form the coating of the surfaces of the solid matrix, the method further comprising forming the nanocomposite by:

(a) combining a first input stream of flowing fluid provided by a flow reactor, the first input stream comprising the graphite, a second input stream of flowing fluid provided by the flow reactor, the second input stream comprising a magnetic nanoparticle precursor material, and a third input stream of flowing fluid provided by the flow reactor, the third input stream comprising a nanoparticle nucleation agent, to form an output stream of flowing fluid;

(b) sonicating the output stream for a period of time to induce exfoliation of the graphite into the graphite layers of the plurality of graphite layers and nucleation and growth of magnetic nanoparticles on the nucleation sites to form magnetic nanoparticle decorated graphite layers; and

(c) inducing reassembly of the magnetic nanoparticle decorated graphite layers and precipitation of the nanocomposite within the liquid of the output stream.

Assignments (2)
CONFIRMATORY LICENSE Recorded Feb 13, 2025
From: NORTHWESTERN UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 070206/0353 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 29, 2021
From: NANDWANA, VIKAS; DRAVID, VINAYAK P.
To: NORTHWESTERN UNIVERSITY
Reel/Frame 057018/0591 →
Continuity (3)
Provisional Application 62788347 · Jan 4, 2019
Provisional Application 62788321 · Jan 4, 2019
Related Publication 20220118422A1 · Apr 21, 2022
References Cited (76)
US 9911974B2 · de Guzman et al. · 2018 [cited by applicant]
US 20030224168A1 · Mack et al. · 2003 [cited by applicant]
US 20040108276A1 · Christodoulou · 2004 [cited by applicant]
US 20090198076A1 · Guckel · 2009 [cited by applicant]
US 20120018382A1 · Stein · 2012 [cited by applicant]
US 20130284968A1 · Azizov et al. · 2013 [cited by applicant]
US 20140183415A1 · Song · 2014 [cited by applicant]
US 20150217222A1 · Hedin et al. · 2015 [cited by applicant]
US 20160204416A1 · Wu et al. · 2016 [cited by applicant]
US 20160243523A1 · Saini et al. · 2016 [cited by applicant]
US 20170136062A1 · Alsharaeh et al. · 2017 [cited by applicant]
US 20180208734A1 · Ozkan et al. · 2018 [cited by applicant]
US 20180241032A1 · Pan et al. · 2018 [cited by applicant]
US 20180370801A1 · Patole et al. · 2018 [cited by applicant]
US 20190389744A1 · Biris · 2019 [cited by examiner]
US 20210107792A1 · Nandwana et al. · 2021 [cited by applicant]
US 20220059839A1 · Nandwana et al. · 2022 [cited by applicant]
US 20230084588A1 · Ribet et al. · 2023 [cited by applicant]
CN 103965835A · 2014 [cited by applicant]
KR 20140073720A · 2014 [cited by applicant]
KR 1020180037659A · 2018 [cited by applicant]
WO WO2012155196A1 · 2012 [cited by applicant]
WO WO2013022051 · 2013 [cited by examiner]
WO WO2017015648 · 2017 [cited by examiner]
WO WO2020142261 · 2020 [cited by applicant]
The extended European Search Report issued on Jan. 26, 2022 for EP Patent Application No. 19907789.2; pp. 1-11. [cited by applicant]
Bracamonte M. Victoria et al., “Lithium dual uptake anode materials: crystalline Fe3O4 nanoparticles supported over graphite for lithium-ion batteries,” [cited by applicant]
Xu Z. et al., “Dispersion of iron nano-particles on expanded graphite for the shielding of electromagnetic radiation,” [cited by applicant]
The extended European Search Report issued on Jan. 26, 2022 for EP Patent Application No. 19907115.0; pp. 1-13. [cited by applicant]
Hamed Hosseini Bay et al., “Scalable Multifunctional Ultra-Thin Graphite Sponge: Free-standing, Superporous, Superhydrophobic, Oleophilic Architecture with Ferromagnetic Properties for Environmental Cleaning,” [cited by applicant]
Wen Qi et al., “Sandwich-structured nanocomposites of N-doped graphene and nearly monodisperse Fe3O4 nanoparticles as high-performance Li-ion battery anodes,” [cited by applicant]
Lei Zhang et al., “Iron-Oxide-Based Advanced Anode Materials for Lithium-Ion Batteries,” [cited by applicant]
Guangmin Zhou et al., “Graphene-Wrapped Fe3O4 Anode Material with Improved Reversible Capacity and Cyclic Stability for Lithium Ion Batteries,” [cited by applicant]
Taegyune Yoon et al., “Electrostatic Self-Assembly of Fe3O4 Nanoparticles on Graphene Oxides for High Capacity Lithium-Ion Battery Anodes,” [cited by applicant]
Paul M. Winkler et al., “Heterogeneous Nucleation Experiments Bridging the Scale from Molecular Ion Clusters to Nanoparticles,” [cited by applicant]
Xiaoyang Pan et al., “Defect-Mediated Growth of Noble-Metal (Ag, Pt, and Pd) Nanoparticles on TiO2 with Oxygen Vacancies for Photocatalytic Redox Reactions under Visible Light,” [cited by applicant]
The International Search Report and the Written Opinion issued on Mar. 18, 2020 for International Patent Application No. PCT/US2019/067782; pp. 1-12. [cited by applicant]
Andrea C. Ferrari, “Raman Spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects,” [cited by applicant]
D. Morillo et al., Poster—“Fe3O4 Nanoparticles-Loaded Cellulose Sponge: Novel system for the Arsenic removal from aqueous solution,” TNT2009, Sep. 7-11, 2009, Barcelona-Spain; pp. 1-2. [cited by applicant]
Shanhu Liu et al., “Superhydrophobic/Superoleophilic magnetic polyurethane sponge for oil/water separationt,” [cited by applicant]
Xuemei Zhang et al., “Preparation of Superhydrophobic Magnetic Polyurethane Sponge for Removing Oil Pollutants from Water,” [cited by applicant]
Viet-Ha Thi Tran et al., “Novel fabrication of a robust superhydrophobic PU@ZnO@ Fe3O4@SA sponge and its application in oil-water separations,” [cited by applicant]
M. Anju et al., “Magnetically actuated graphene coated polyurethane foam as potential sorbent for oils and organics,” [cited by applicant]
Lei Wu et al., “Magnetic, Durable, and Superhydrophobic polyurethane@Fe3O4@SiO2@Fluoropolymer Sponges for Selective Oil Absorption and Oil/Water Separation,” [cited by applicant]
Huili Peng et al., “Preparation of Superhydrophobic Magnetic Cellulose Sponge for Removing Oil from Water,” [cited by applicant]
The International Search Report and Written Opinion issued in International Patent Application No. PCT/US18/46674 on Jan. 11, 2019, pp. 1-11. [cited by applicant]
Liu et al., “Iron Oxide Decorated MoS2 Nanosheets with Double PEGylation for Chelator-Free Radiolabeling and Multimodal Imaging Guided Photothermal Therapy,” [cited by applicant]
Nandwana et al., “One-Pot Green Synthesis of Fe3O4/ MoS2 0D/2D Nanocomposites and Their Application in Noninvasive Point-of-Care Glucose Diagnostics,” [cited by applicant]
Peng et al., “Ultrathin Two-Dimensional MnO2/Graphene Hybrid Nanostructures for High-Performance, Flexible Planar Supercapacitors,” [cited by applicant]
Peng et al., Supporting Information for “Ultrathin Two-Dimensional MnO2/Graphene Hybrid Nanostructures for High-Performance, Flexible Planar Supercapacitors,” 2013, pp. 1-11. [cited by applicant]
Wang et al., “Biosensor Based on Ultrasmall MoS2 Nanoparticles for Electrochemical Detection of H2O2 Released by Cells at the Nanomolar Level,” [cited by applicant]
Yu et al., “Smart MoS2/ Fe3O4 Nanotheranostic for Magnetically Targeted Photothermal Therapy Guided by Magnetic Resonance/Photoacoustic Imaging,” [cited by applicant]
Joensen et al., “Single-Layer MoS2,” [cited by applicant]
Zhu et al., “Fast Li Storage in MoS2-Graphene-Carbon Nanotube Nanocomposites: Advantageous Functional Integration of 0D, 1D, and 2D Nanostructures,” [cited by applicant]
V. Nicolosi et al., “Liquid Exfoliation of Layered Materials,” [cited by applicant]
D. Yang et al., “Li-Intercalation and Exfoliation of WS2,” [cited by applicant]
Kufer et al., “Hybrid 2D-0D MoS2-PbS Quantum Dot Photodetectors,” [cited by applicant]
Q. Qu et al., “2D Sandwich-like Sheets of Iron Oxide Grown on Graphene as High Energy Anode Material for Supercapacitors,” [cited by applicant]
Jonathan N. Coleman, “Liquid Exfoliation of Defect-Free Graphene,” [cited by applicant]
Ahmad et al., “Functionalized Molybdenum Disulfide Nanosheets for 0D-2D Hybrid Nanostructures: Photoinduced Charge Transfer and Enhanced Photo response,” [cited by applicant]
Sandoval et al., “Raman study and lattice dynamics of single molecular layers of MoS2,” [cited by applicant]
Smith et al., “Large-Scale Exfoliation of Inorganic Layered Compounds in Aqueous Surfactant Solutions,” [cited by applicant]
Chou et al., “Ligand Conjugation of Chemically Exfoliated MoS2,” [cited by applicant]
The International Search Report and the Written Opinion issued on Apr. 21, 2021 for International Patent Application No. PCT/US2021/019324; pp. 1-12. [cited by applicant]
Lei et al., “Simple fabrication of multi-functional melamine sponges,” Materials Letters, vol. 190, Dec. 28, 2016 [retrieved on Mar. 28, 2021]. Retrieved from the Internet: ,URL: https://www.sciencedirect.com/science/ar… [cited by applicant]
Calcagnile et al., “Magnetically Driven Floating Foams for the Removal of Oil Contaminants from Water,” ACS Nano, vol. 6, No. 6, May 11, 2012 [retrieved on Mar. 28, 2021]. Retrieved from the Internet: URL: https//pubs.a… [cited by applicant]
Guan et al., “Superwetting Polymeric Three Dimensional (3D) Porous Materials for Ol/Water Separation: A Review,” Polymers, vol. 11, No. 806, May 6, 2019 [retrieved on Mar. 28, 2021]. Retrieved from the Internet: URL: ht… [cited by applicant]
Zeeshan Ajmal et al., “Phosphate removal from aqueous solution using iron oxides: Adsorption, desorption and regeneration characteristics,” [cited by applicant]
Dema A. Almasri et al., Adsorption of phosphate on iron oxide doped halloysite nanotubes, [cited by applicant]
Jiang, D., Amano, Y. & Machida, M. Removal and Recovery of Phosphate from Water by a Magnetic Fe3O4@ASC Adsorbent. [cited by applicant]
Yoon, S. Y. et al. Kinetic, Equilibrium and Thermodynamic Studies for Phosphate Adsorption to Magnetic Iron Oxide Nanoparticles. [cited by applicant]
Choi, J., Chung, J., Lee, W. & Kim, J. O. Phosphorous Adsorption on Synthesized Magnetite in Wastewater. [cited by applicant]
Zach-Maor, A., Semiat, R. & Shemer, H. Synthesis, Performance, and Modeling of Immobilized Nano-Sized Magnetite Layer for Phosphate Removal. [cited by applicant]
Jung, K. W. & Ahn, K. H. Fabrication of Porosity-Enhanced MgO/biochar for Removal of Phosphate from Aqueous Solution: Application of a Novel Combined Electrochemical Modification Method. [cited by applicant]
Examination Report issued on Jan. 17, 2023 for Indian Patent Application No. 202137033787; pp. 1-6. [cited by applicant]
The International Search Report and Written Opinion issued on Mar. 11, 2020 for international patent application No. PCT/US19/67839; pp. 1-7. [cited by applicant]