Copper complex for capturing carbon dioxide
A composition and method are disclosed for capturing CO 2 . A pollutant/greenhouse gas can be converted into a valuable organic compound using a nontoxic reducing agent. CO 2 may be economically captured from the atmosphere, from products of combustion, or from byproducts of various chemical processes. The method reduces CO 2 in a three-step reaction cycle, in which a binuclear metal-organic compound converts CO 2 to oxalate in a redox cycle under mild conditions.
1. A binuclear compound having the structure [Cu 2 L 2 (μ-C 2 O 4 ) p ]X n m+ wherein:
p is 0 or 1;
n is 0, 2, or 4;
m is 0, 2, or 4;
X is a monovalent anion; wherein if n is 2 or 4, the various X anions may be the same or different; and
L is:
wherein:
R 1 is chosen from the group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl, —NH 2 , —OH, and —CO 2 H;
R 2 , R 3 , and R 4 are independently chosen from the group consisting of H, substituted or unsubstituted C 1 -C 8 alkyl, substituted or unsubstituted arene or heteroarene radical, —OH, —OC k H 2k+1 , —O(CH 2 CH 2 O) k CH 3 , —O(CH 2 CH 2 O) k C 2 H 5 , N(CH 3 ) 3 + , —SO 3 − , —NO 2 , and —CN; wherein k is 1, 2, 3, 4, 5, 6, 7, or 8;
R 5 , R 6 , R 7 , and R 8 are independently chosen from the group consisting of H, —OCH 3 , —N(CH 3 ) 2 , halogen, —NO 2 , —CN, substituted or unsubstituted C 1 -C 8 alkyl, substituted or unsubstituted arene or heteroarene radical, —OH, OC j H 2j+1 , —O(CH 2 CH 2 O) j CH 3 , —O(CH 2 CH 2 O) j C 2 H 5 , —N(CH 3 ) 3 + , —SO 3 − , —NO 2 , and —CN, wherein j is 1, 2, 3, 4, 5, 6, 7, or 8;
and wherein:
said compound has the property that it can cycle between a Cu(I) form of the compound and a Cu(II) form of the compound, as a function of redox potential;
and wherein:
the Cu(I) form of the compound has the property that it can react with carbon dioxide to reduce carbon dioxide to oxalate, whereby the compound is oxidized to the Cu(II) form of the compound.
2. The compound of claim 1 , wherein L is m-xylylenebis(pyridyltriazole).
3. The compound of claim 1 , wherein said compound is selected from the group consisting of [Cu 2 L 2 (μ-C 2 O 4 )] 2+ ; [Cu 2 L 2 (μ-C 2 O 4 )](PF 6 ) 2 ; [Cu 2 L 2 (NO 3 ) 2 ](PF 6 ) 2 ; [Cu 2 L 2 (NO 3 ) 2 ](NO 3 ) 2 ; [Cu 2 L 2 ](PF 6 ) 2 ; [Cu 2 L 2 Cl 2 ]Cl 2 ; [Cu 2 L 2 Cl 2 ](PF 6 ) 2 ; [Cu 2 L 2 ] 2+ ; and [Cu 2 L 2 ] 4+ .
4. The compound of claim 3 , wherein L is m-xylylenebis(pyridyltriazole).
5. A method for reducing carbon dioxide to oxalate; said method comprising the sequential steps of:
(a) reacting carbon dioxide with the Cu(I) form of the compound of claim 1 to produce oxalate complexed to the Cu(II) form of the compound of claim 1 ;
(b) reacting the oxalate complex from step (a) with a mineral acid to liberate oxalate from the Cu(II) form of the compound of claim 1 ;
(c) reducing the Cu(II) form of the compound of claim 1 from step (b) to regenerate the Cu(I) form of the compound of claim 1 .
6. A method for reducing carbon dioxide to oxalate; said method comprising the sequential steps of:
(a) reacting carbon dioxide with the Cu(I) form of the compound of claim 2 to produce oxalate complexed to the Cu(II) form of the compound of claim 2 ;
(b) reacting the oxalate complex from step (a) with a mineral acid to liberate oxalate from the Cu(II) form of the compound of claim 2 ;
(c) reducing the Cu(II) form of the compound of claim 2 from step (b) to regenerate the Cu(I) form of the compound of claim 2 .
7. A method for reducing carbon dioxide to oxalate; said method comprising the sequential steps of:
(a) reacting carbon dioxide with the Cu(I) form of the compound of claim 3 to produce oxalate complexed to the Cu(II) form of the compound of claim 3 ;
(b) reacting the oxalate complex from step (a) with a mineral acid to liberate oxalate from the Cu(II) form of the compound of claim 3 ;
(c) reducing the Cu(II) form of the compound of claim 3 from step (b) to regenerate the Cu(I) form of the compound of claim 3 .
8. A method for reducing carbon dioxide to oxalate; said method comprising the sequential steps of:
(a) reacting carbon dioxide with the Cu(I) form of the compound of claim 4 to produce oxalate complexed to the Cu(II) form of the compound of claim 4 ;
(b) reacting the oxalate complex from step (a) with a mineral acid to liberate oxalate from the Cu(II) form of the compound of claim 4 ;
(c) reducing the Cu(II) form of the compound of claim 4 from step (b) to regenerate the Cu(I) form of the compound of claim 4 .