New Heterometallic Zirconium Metalloporphyrin Frameworks and Their Heteroatom-Activated High-Surface-Area Carbon Derivatives

Four cubic zirconium-porphyrin frameworks, CPM-99­(H2, Zn, Co, Fe), were synthesized by a molecular-configuration-guided strategy. Augmentation of meso-substituted side arms (with double-torsional biphenyl rings) of tetratopic porphyrin linkers leads to a successful implementation of zirconium-carbo...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2015-02, Vol.137 (6), p.2235-2238
Main Authors: Lin, Qipu, Bu, Xianhui, Kong, Aiguo, Mao, Chengyu, Zhao, Xiang, Bu, Fei, Feng, Pingyun
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Four cubic zirconium-porphyrin frameworks, CPM-99­(H2, Zn, Co, Fe), were synthesized by a molecular-configuration-guided strategy. Augmentation of meso-substituted side arms (with double-torsional biphenyl rings) of tetratopic porphyrin linkers leads to a successful implementation of zirconium-carboxylate frameworks with cubic 2.5 nm cage. The hard-templating effect of Zr6-polyoxo-cluster and uniformly embedded (metallo)­porphyrin centers endow CPM-99 with highly desirable properties as precursors for oxygen reduction reaction (ORR) catalysts. The pyrolytic products not only retain the microcubic morphology of the parent CPM-99 but also possess porphyrinic active sites, hierarchical porosity, and highly conducting networks. CPM-99Fe-derived material, denoted CPM-99Fe/C, exhibits the best ORR activity, comparable to benchmark 20% Pt/C in alkaline and acidic media, but CPM-99Fe/C is more durable and methanol-tolerant. This work demonstrates a new route for the development of nonprecious metal ORR catalysts from stable metalloporphyrinic MOFs.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b00076