# US 11,897,793 B2 · Catalysts for Fenton system containing metal oxide containing functional group on surface and Fenton system using the same

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- Number: US 11,897,793 B2
- Document ID: US11897793B2
- Status: Granted
- Kind: B2
- Application number: 17/115,468
- Filed: 2020-12-08
- Published: 2021-09-30
- Granted: 2024-02-13
- Earliest claimed: 2020-03-25
- Assignees: Korea Institute of Science and Technology
- Applicants: Korea Institute of Science and Technology
- Inventors: Jongsik Kim; Heon Phil Ha
- Web page: https://patentgrep.com/patent/US11897793B2

## CPC

- B01J 23/00: Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 (B01J21/16 takes precedence)
- C02F 1/46109: {Electrodes}
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 37/20: Sulfiding
- B01J 37/28: Phosphorising
- C02F 1/4672: {by electrooxydation}
- C02F 2001/46142: {Catalytic coating}
- C02F 2101/10: Inorganic compounds
- C02F 2101/345: {Phenols}
- C02F 2101/38: containing nitrogen
- C02F 2305/023: Reactive oxygen species, singlet oxygen, OH radical
- C02F 2305/026: Fenton's reagent
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)

## Abstract

Provided is a catalyst for a Fenton system, and a method of preparing the same. The catalyst includes one or more species of d0-orbital-based or non-d0-orbital-based catalyst including NO3−/SO42−/H2PO4−/HPO42−/PO43− functional groups on the surface thereof. The method includes preparing a d0-orbital-based or non-d0-orbital-based transition metal oxide; and preparing a transition metal oxide catalyst comprising a NO3−, SO42−, H2PO4−, HPO42−, or PO43− functional group on the surface of the catalyst via nitrification, sulfation, or phosphorylation of the transition metal oxide.

## Claims

### Claim 1

A catalyst for a Fenton system, the catalyst comprising one or more species of d0-orbital-based or non-d0-orbital-based transition metal oxide catalyst grains including a NO3−, H2PO4−, HPO42−, or PO43− functional group on the surface thereof.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein the catalyst grains have a porous structure, and optionally, wherein the catalyst grains have a diameter of 0.1 nm to 500 μm.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein a metal of the transition metal oxide catalyst grains comprises at least one selected from a 3d-block metal (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn), a 4d-block metal (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, or Cd), a 5d-block metal (La, Hf, Ta, W, Re, Os, Ir, Pt, Au, or Hg), and a 6d-block metal (Ac, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn) in the periodic table, or any combination thereof.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein the catalyst is supported by a carrier and coated on a substrate, and a binder is interposed between the carrier and the substrate to increase coating adhesion strength.

### Claim 5 (depends on 4)

The catalyst of claim 4, wherein the carrier is carbon (C), Al2O3, MgO, ZrO2, CeO2, TiO2, or SiO2.

### Claim 6 (depends on 4)

The catalyst of claim 4, wherein the catalyst is included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the carrier.

### Claim 7 (depends on 4)

The catalyst of claim 4, wherein the binder is a polymer that is insoluble in an aqueous solution or an inorganic binder.

### Claim 8 (depends on 4)

The catalyst of claim 4, wherein an electro-Fenton reaction occurs in an aqueous electrolytic solution.

### Claim 9 (depends on 8)

The catalyst of claim 8, wherein the aqueous electrolytic solution has a pH of 3 to 10, and electro-Fenton reaction occurs by inputting a power.

### Claim 10 (depends on 8)

The catalyst of claim 8, wherein the electro-Fenton reaction comprises:
(1) production of ·OH species by heterogeneous decomposition of H2O2;
(2) conversion of the NO3− functional group into NO3· species by the ·OH species, or conversion of the H2PO4−/HPO42−/PO43− functional groups into H2PO4·/HPO4·−/PO42·− species by the ·OH species; and
(3) decomposition of a non-degradable organic material by the NO3·, H2PO4·, HPO4·−, or PO42·− species.

### Claim 11

A method of preparing a catalyst for a Fenton system, the method comprising:
preparing a d0-orbital-based or non-d0-orbital-based transition metal oxide; and
preparing a transition metal oxide catalyst comprising a NO3−, H2PO4−, HPO42−, or PO43− functional group on the surface of the catalyst via nitrification, sulfation, or phosphorylation of the transition metal oxide.

### Claim 12 (depends on 11)

The method of claim 11, wherein the nitrification is performed with a reaction gas comprising NO and O2, the sulfation is performed with a reaction gas comprising SO2 and O2, and the phosphorylation is performed with a reaction solution comprising a phosphorylating precursor.

### Claim 13 (depends on 4)

The catalyst of claim 4, wherein hydrogen peroxide is supplied from a hydrogen peroxide supply unit, and a non-electro-Fenton reaction occurs in an aqueous electrolytic solution.

### Claim 14 (depends on 13)

The catalyst of claim 13, wherein the aqueous electrolytic solution has a pH of 5 to 10, and
the non-electro-Fenton reaction occurs by supplying hydrogen peroxide using a hydrogen peroxide supply unit at a rate of 10−5 mol/L to 105 mol/L.

### Claim 15 (depends on 13)

The catalyst of claim 13, wherein the non-electro-Fenton reaction comprises:
(1) production of ·OH species by heterogeneous decomposition of H2O2;
(2) conversion of the NO3− functional group into NO3· species by the ·OH species, or conversion of the H2PO4−/HPO42−/PO43− functional groups into H2PO4·/HPO4·−/PO42·− species by the ·OH species; and
(3) decomposition of a non-degradable organic material by the NO3·, H2PO4·, HPO4·−, or PO42·− species.