Single vessel solvent based method for making a Zn/Cu composite

Patent metadata

Field	Value
Publication number	US-12129381-B1
Application number	US-202418739388-A
Country	US
Kind code	B1
Filing date	Jun 11, 2024
Priority date	Sep 12, 2019
Publication date	Oct 29, 2024
Grant date	Oct 29, 2024

Abstract

A composite nanomaterial of ZnO impregnated by, e.g., a green copper phthalocyanine compound (CuPc) can be an efficient solar light photocatalyst for water remediation. The composite may include hollow shell microspheres and hollow nanospheres of CuPc-ZnO. CuPc may function as a templating and/or structure modifying agent, e.g., for forming hollow microspheres and/or nanospheres of ZnO particles. The composite can photocatalyze the degradation of organic pollutants such as crystal violet (CV) and 2,4-dichlorophenoxyacetic acid as well as microbes in water under solar light irradiation. The ZnO—CuPc composite can be stable and recyclable under solar irradiation.

First claim

The invention claimed is:

1. A method of synthesizing a composite including hollow micro (hemi) spheres and/or nanospheres, comprising:
mixing a zinc compound with a solvent mixture of ethanol/diethylene glycol to form a solution, then mixing the solution with a copper phthalocyanine compound to form a reaction mixture, wherein the solution and the reaction mixture comprise the same solvent mixture; and
heating the reaction mixture at a temperature in a range of 100 to 200° C. for a treatment time in a range of 10 to 30 hours to form the composite,
wherein a molar ratio of the zinc compound to the copper phthalocyanine compound is in a range 3:1 to 1:3.

2. The method of claim 1 , wherein the copper phthalocyanine compound comprises at least 75 wt. % of sulfonated tetra thiophenyl copper phthalocyanine.

3. The method of claim 1 , wherein the solvent mixture comprises at least 75 wt. %, relative to total solvent weight, of ethanol and diethylene glycol.

4. The method of claim 1 , wherein the zinc compound comprises at least 75 wt. %, relative to total zinc salt weight, of zinc acetonylacetonate.

5. The method of claim 1 , wherein the heating is conducted at a pressure in a range of from greater than 1 to 50 atm.

6. The method of claim 1 , wherein the hollow micro (hemi) spheres have a diameter in a range of from 0.5 to 5.0 μm, and/or
wherein the hollow nanospheres have a diameter in a range of from 50 to 450 nm.

7. The method of claim 1 , wherein the composite has a molar ratio of Cu to Zn in a range of from 3:1 to 1:3.

8. The method of claim 1 , wherein the copper phthalocyanine compound has a structure of a formula

wherein Ar is an aryl group,
Y is independently O or S,
Z is independently a sulfonate, phosphonate, or carboxylate,
m is independently 0 or 1, and
n is independently 0, 1, or 2.

9. The method of claim 8 , wherein the aryl group is phenyl, naphthyl, biphenyl, pyridyl, pyrrole, thiophene, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, isoxazole, isothiazole, thiazole, pyrimidine, pyridazine, pyrazine, 1,2,4-triazine, 1,3,5-triazine, indole, isoindole, indolizine, indazole, benzimidazole, 7-azaindole, 4-azaindole, 5-azaindole, 6-azaindole, 7-azaindazole, pyrazolo[1,5-a]pyrimidine, purine, benzofuran, isobenzofuran, benzo[c]thiophene, benzo[b]thiophene, benzo[d]isoxazole, benzo[c]isoxazole, benzo[d]isothiazole, benzo[c]isothiazole, benzo[d]oxazole, benzo[d]thiazole, benzo[c][1,2,5]thiadiazole, adenine, quinoline, isoquinoline, 4-quinolizine, quinoxaline, phthalazine, quinazoline, cinnoline, 1,8-naphthyridine, pyrido[3,2-d]pyrimidine, pyrido[4,3-d]pyrimidine, pyrido[3,4-b]pyrazine, pyrido[2,3-b]pyrazine, pteridine, acridine, or phenazine.

10. The method of claim 8 , wherein Ar is phenyl, Y is S, Z is sulfonate, m is 1, and n is independently 0 or 1.

11. The method of claim 1 , wherein the zinc compound is ZnO particles, and
wherein the ZnO particles include first spheroid particles and second spheroid particles, wherein the first spheroid particles have an average outer diameter in a range of from 50 to 450 nm and the second spheroid particles have an average outer diameter in a range of from 0.5 to 5 μm.

12. The method of claim 11 , wherein the first spheroid particles have a sphericity of at least 0.85, and/or are hollow.

13. The method of claim 11 , wherein the second spheroid particles are hollow spheres having a sphericity of at least 0.9, and/or hollow hemispheres, which when extrapolated to spheres, have a sphericity of at least 0.9.

14. The method of claim 11 , wherein the second spheroid particles have nanorods, protruding outwardly, orthogonally to spherical surfaces, and
wherein the nanorods have an average diameter in a range of from 1 to 250 nm.

Assignees

• Univ Imam Abdulrahman Bin Faisal

Inventors

• Moustafa Tamer Ezzat Youssef
• Besisa Hanan Hussein Amin Mohamed

Classifications

• H01B1/00

  Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors · CPC title

• C01P2002/84

  by UV- or VIS- data · CPC title

• C09B67/0032

  Treatment of phthalocyanine pigments (C09B67/0016, C09B67/0019 take precedence) · CPC title

• C02F2305/10

  Photocatalysts · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title