Three-Dimensional Phthalocyanine Metal-Catecholates for High Electrochemical Carbon Dioxide Reduction

Abstract

The synthesis of a new anionic 3D metalcatecholate framework, termed MOF-1992, is achieved by l i n k i n g t e t r a t o p i c c o b a l t p h t h a l o c y a n i n-2 , 3 , 9 , 1 0 , 1 6 , 1 7 , 2 3 , 2 4-o c t a o l l i n k e r s w i t h Fe 3 (−C 2 O 2 −) 6 (OH 2) 2 trimers into an extended framework of roc topology. MOF-1992 exhibits sterically accessible Co active sites together with charge transfer properties. Cathodes based on MOF-1992 and carbon black (CB) display a high coverage of electroactive sites (270 nmol cm −2) and a high current density (−16.5 mA cm −2 ; overpotential, −0.52 V) for the CO 2 to CO reduction reaction in water (faradaic efficiency, 80%). Over the 6 h experiment, MOF-1992/CB cathodes reach turnover numbers of 5800 with turnover frequencies of 0.20 s −1 per active site.

Transition metal-based catalysts for the electrochemical CO2reduction: from atoms and molecules to nanostructured materials

“…In a recent report, Co phthalocyanine catechol building blocks have been implemented into a novel metal-catecholate framework, namely MOF-1992. 196 The system displayed an original topology with more accessible CoPc sites, as well as improved charge transfer properties, leading to significantly higher electroactive surface area than the previously reported reticular Co/Fe catalysts. 76,78,140,141,165 At neutral pH, MOF-1992 was able to mediate a selective conversion of CO 2 to CO (FE 80%) at À0.63 V vs. RHE (Z = 520 mV) with relevant current densities (416 mA cm À2 ).…”

Electrically Conductive Metal–Organic Frameworks

“…MOFs with conductivities between 10 –5 to 60 S/cm have been explored for different reactions, including oxygen reduction, 17 , 20 hydrogen evolution, 16 and carbon dioxide reduction. 102 …”

A self‐penetrating and chemically stable zinc (ii)‐organic framework as multi‐responsive chemo‐sensor to detect pesticide and antibiotics in water

“…One thing to note is the fast‐growing metal organic frameworks (MOFs), which are designed from the perspective of molecules, making full use of the high stability of metal units and versatility of organic linkers, have attracted more and more attention for their potential applications in the fields of adsorption and separation, [ 4–10 ] electrode and photoelectric materials, [ 11–17 ] sensing and detection, [ 18–31 ] catalysis and photocatalysis. [ 32–34 ] Compared with other sensors, such as the conjugated organic probes, nanomaterials, carbon dots, oligomers, the luminescent metal–organic frameworks (LMOFs) possess obvious advantages of enormous structural diversity, adjustable pore size, large surface areas, readily function groups assisted analyte binding, and purposefully implanted active sites, render those LMOFs with the greatest potential as the sensory materials in detecting the POPs.…”