IP Library Granted Patent US 12,655,078
Granted Patent B2
US 12,655,078 · App. 18/391,358 · Granted Jun 16, 2026

Selective photocatalytic reduction of alkynes to alkenes powered by a cobalt-porphyrin metal-organic frameworks

Inventors: Aaron Edward Stone (Evanston, IL); Francesca Arcudi (Evanston, IL); Luka Dordevic (Evanston, IL); Emily Allyn Weiss (Evanston, IL); Joseph T. Hupp (Northfield, IL); Samuel Isaac Stupp (Evanston, IL)
Assignee: Northwestern University
C07C5/09B01J31/1691B01J31/183B01J35/39B01J2231/645B01J2531/0216B01J2531/48B01J2531/821B01J2531/845
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Quick Facts
Patent No.
US 12,655,078
App. No.
18/391,358
Granted
Jun 16, 2026
Kind
B2
Abstract

Methods for the photocatalytic reduction of alkynes to alkenes with high conversion yields and selectivities using a heterogeneous system that incorporates a cobalt-porphyrin into a metal-organic framework (MOF) are provided. The cobalt-porphyrin-based MOFs carry out the photocatalytic reductions in the presence of a visible-light activated photosensitizer molecule and a sacrificial electron donor.

Claims (22)

1 . A method for photocatalytic reduction of an alkyne to an alkene, the method comprising:

exposing the alkyne to a solution comprising: a metal-organic framework comprising inorganic metal ions or clusters connected by polytopic organic linkers, the polytopic organic linkers comprising cobalt-porphyrin groups; a photosensitizer; and a sacrificial donor; and

irradiating the photosensitizer with visible radiation to induce the photocatalytic reduction of the alkyne to the alkene.

2 . The method of claim 1 , wherein the alkyne comprises acetylene, propyne, or a mixture thereof.

3 . The method of claim 2 , wherein the solution is simultaneously exposed to the acetylene and ethylene and the acetylene is selectively reduced relative to the ethylene.

4 . The method of claim 2 , wherein the metal-organic framework is Co-(Zr)PCN-222.

5 . The method of claim 2 , wherein the photosensitizer is a rubidium polypyridine complex.

6 . The method of claim 5 , wherein the rubidium polypyridine complex comprises tris (bipyridine) ruthenium (II).

7 . The method of claim 2 , wherein the sacrificial donor is a tertiary aliphatic amine.

8 . The method of claim 7 , wherein the tertiary aliphatic amine is triethanolamine.

9 . The method of claim 2 , wherein irradiating the photosensitizer with visible radiation comprises exposing the photosensitizer and the solution to solar radiation.

10 . The method of claim 3 , wherein the photosensitizer is a rubidium polypyridine complex and the sacrificial donor is a tertiary aliphatic amine.

11 . The method of claim 10 , wherein the rubidium polypyridine complex comprises tris(bipyridine)ruthenium(II) and the tertiary aliphatic amine is triethanolamine.

12 . The method of claim 11 , wherein the solution is simultaneously exposed to the acetylene and ethylene and at least 90 mol. % of the acetylene is reduced with a selectivity of acetylene reduction over ethylene reduction of at least 90%.

13 . The method of claim 11 , wherein the solution is simultaneously exposed to the acetylene and ethylene and the cobalt-porphyrin groups catalyze the reduction of at least 99 mol. % of the acetylene with a selectivity of acetylene reduction over ethylene reduction of at least 99%.

14 . The method of claim 13 , wherein the metal-organic framework is Co-(Zr)PCN-222.

15 . The method of claim 1 , wherein the reduction of the alkyne is carried out at a temperature in the range from 20° C. to 25° C.

16 . The method of claim 1 , wherein the metal-organic framework is Co-(Zr)PCN-222.

17 . The method of claim 1 , wherein the photosensitizer is a rubidium polypyridine complex.

18 . The method of claim 17 , wherein the rubidium polypyridine complex comprises tris(bipyridine)ruthenium(II).

19 . The method of claim 1 , wherein the sacrificial donor is a tertiary aliphatic amine.

20 . The method of claim 19 , wherein the tertiary aliphatic amine is triethanolamine.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 13, 2024
From: STONE, AARON EDWARD; ARCUDI, FRANCESCA; DORDEVIC, LUKA; WEISS, EMILY ALLYN; HUPP, JOSEPH T.; STUPP, SAMUEL ISAAC
To: NORTHWESTERN UNIVERSITY
Reel/Frame 069249/0636 →
Continuity (2)
Provisional Application 63434354 · Dec 21, 2022
Related Publication 20240208884A1 · Jun 27, 2024
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