Functionalized porous organic polymers as uranium nano-traps for efficient uranium extraction
Compositions are provided for efficient uranium extraction, for example from wastewater, seawater, or other water sources. The compositions can include a functionalized porous organic polymer functionalized with one or more uranium binding moieties, e.g. having a plurality of amidoxime or amidrazone groups covalently attached thereto. The compositions can include covalent organic frameworks, porous aromatic frameworks, and various porous organic polymers, especially those having a hierarchical pore size distribution over a range of pore sizes. The compositions can have functional groups such as amidoxime or an amidrazone covalently attached thereto. The hierarchical pore size distribution can be determined based upon at least 60% of the pore sizes in the range of pore sizes having a pore volume of at least 0.01 cm 3 g −1 in the pore size distribution at 77 K. Methods of making the compositions and methods of using the compositions are also provided.
1. A composition for uranium uptake, the composition comprising a porous organic polymer (POP) comprising:
(i) a plurality of repeat units each having a structure according to any one of Formula 1A-Formula 1C
and
(ii) a plurality of pores having a hierarchical pore size distribution over a range of pore sizes;
where each occurrence of R 1 is independently a hydrogen, a halide, an alkyl or heteroalkyl having 1 to 3 carbon atoms, a hydrogen-bond donor, an amidoxime, or an amidrazone so long as at least one occurrence of R 1 is an amidoxime or an amidrazone;
where each occurrence of R 2 is independently an alkyl having 1 to 3 carbon atoms; and
where each occurrence of A 2 is independently none or a substituted or unsubstituted phenyl.
2. The composition according to claim 1 , wherein the repeat units in the plurality of repeat units each have a structure according to any one of Formula 2A-Formula 2C
where R 1 is as defined in claim 1 .
3. The composition according to claim 1 , wherein each occurrence of R 1 is independently a hydrogen, a hydrogen-bond donor, or an amidoxime;
wherein as at least one occurrence of R 1 is an amidoxime; and
wherein at least one occurrence of R 1 is a hydrogen-bond donor.
4. The composition according to claim 1 , wherein the range of pore sizes is at least 5 nm, at least 8 nm, or at least 10 nm.
5. The composition according to claim 1 , wherein the range of pore sizes is about 1 nm to 10 nm, about 1 nm to 8 nm, about 1 nm to 5 nm, or about 5 nm to 10 nm.
6. The composition according to claim 1 , wherein the range of pore sizes is about 1 nm to about 10 nm; and
wherein at least 80% of the pore sizes in the pore size distribution have a pore volume of at least 0.01 cm 3 g −1 .
7. A method of making the composition of claim 1 , the method comprising:
forming a mixture comprising a precursor monomer and a free radical initiator in an aprotic solvent, wherein the precursor monomer has a structure according to the formula CH 2 ═CHA 1 CH═CH 2 where A 1 is a conjugated core having one or more nitrile moieties covalently attached thereto;
heating the mixture to a first elevated temperature for a first period of time to form the porous organic polymer having nitrile moieties covalently attached thereto; and
converting the nitrile moieties into an amidoxime or an amidrazone to form the porous organic polymer having one or more amidoxime or amidrazone moieties covalently attached thereto.