Thiol-functionalized hyper-crosslinked polymers with hierarchical porosities for the capture and recovery of heavy metal contaminants

1. A crosslinked vinylbenzylchloride-divinylbenzene copolymer that is thiol-functionalized and has a mole ratio of vinylbenzylchloride monomer to divinylbenzene monomer in a range from 99:1 to 80:20, wherein the crosslinked vinylbenzylchloride-divinylbenzene copolymer comprises both mesopores and micropores and further wherein the mesopores make up at least 20% of a total pore volume of the crosslinked vinylbenzylchloride-divinylbenzene copolymer.

2. A method for extracting metal ions from a sample, the method comprising:

contacting a thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer with a sample comprising metal ions, whereby the metal ions are adsorbed by the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer; and

removing the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer with the adsorbed metal ions from the sample.

3. The method of claim 2 , wherein the metal ions are Au 1 ions and the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer adsorbs the Au 1 ions with an Au 1 uptake of at least 90% of a maximum possible Au 1 uptake.

4. The method of claim 2 , wherein the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer comprises mesopores and micropores.

5. The method of claim 4 , wherein the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer has a total pore volume comprising at least 40% mesopore volume.

6. The method of claim 5 , wherein the mesopore volume makes up between 40% and 60% of the total pore volume.

7. The method of claim 2 , wherein the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer has a BET surface area of at least 500 m 2 /g.

8. The method of claim 2 , wherein a mole ratio of vinylbenzylchloride monomer to divinylbenzene monomer in the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer is in a range from 99:1 to 75:25.

9. The method of claim 2 , wherein the metal ions comprise heavy metal ions.

10. The method of claim 9 , wherein the heavy metal ions comprise gold ions, silver ions, copper ions, lead ions, mercury ions, cadmium ions, or a combination of two or more thereof.

11. The method of claim 9 , wherein the heavy metal ions are gold ions.

12. A method of forming a thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer, the method comprising:

copolymerizing vinylbenzylchloride monomers and divinylbenzene monomers into a vinylbenzylchloride-divinylbenzene copolymer in the presence of a porogenic solvent;

crosslinking the vinylbenzylchloride-divinylbenzene copolymer;

chloromethylating the vinylbenzylchloride-divinylbenzene copolymer to form a chloromethylated vinylbenzylchloride-divinylbenzene copolymer; and

thiolating the chloromethylated vinylbenzylchloride-divinylbenzene copolymer using a thiourea to form the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer.

13. The method of claim 12 , wherein the porogenic solvent is dioxane, tetrahydrofuran, toluene, a xylene, or a combination of two or more thereof.

14. The method of claim 13 , wherein the porogenic solvent is 1,4-dioxane.

15. The method of claim 12 , wherein a mole ratio of vinylbenzylchloride monomer to divinylbenzene monomer in the thiol-functionalized crosslinked vinylbenzylchloride-divinylbenzene copolymer is in a range from 99:1 to 85:15.

16. The method of claim 12 , wherein the thiolation of the chloromethylated vinylbenzylchloride-divinylbenzene copolymer is carried out in the presence of the porogenic solvent.