title: New heterometallic zirconium metalloporphyrin frameworks and their heteroatom-activated high-surface-area carbon derivatives.
abstract: 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.
authors: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors: Qipu
authors: Q
authors: Lin
authors: Xianhui
authors: X
authors: Bu
authors: Aiguo
authors: A
authors: Kong
authors: Chengyu
authors: C
authors: Mao
authors: Xiang
authors: X
authors: Zhao
authors: Fei
authors: F
authors: Bu
authors: Pingyun
authors: P
authors: Feng