It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal-organic frameworks (MOFs) have been synthesized based on a novel mixed-ligand strategy to afford high-content (1.76 wt %) single-atom (SA) iron-implanted N-doped porous carbon (Fe -N-C) via pyrolysis. Thanks to the single-atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe -N-C exhibits excellent oxygen reduction activity and stability, surpassing almost all non-noble-metal catalysts and state-of-the-art Pt/C, in both alkaline and more challenging acidic media. More far-reaching, this MOF-based mixed-ligand strategy opens a novel avenue to the precise fabrication of efficient single-atom catalysts.

The great interest in fuel cells inspires a substantial amount of research on nonprecious metal catalysts as alternatives to Pt-based oxygen reduction reaction (ORR) electrocatalysts. In this work, bimodal template-based synthesis strategies are proposed for the scalable preparation of hierarchically porous M-N-C (M = Fe or Co) single-atom electrocatalysts featured with active and robust MN 2 active moieties. Multiscale tuning of M-N-C catalysts regarding increasing the number of active sites and boosting the intrinsic activity of each active site is realized simultaneously at a singleatom scale. In addition to the antipoisoning power and high affinity for O 2 , the optimized Fe-N-C catalysts with FeN 2 active site presents a superior electrocatalytic activity for ORR with a half-wave potential of 0.927 V (vs reversible hydrogen electrode (RHE)) in an alkaline medium, which is 49 and 55 mV higher than those of the Co-N-C counterpart and commercial Pt/C, respectively. Density functional theory calculations reveal that the FeN 2 site is more active than the CoN 2 site for ORR due to the lower energy barriers of the intermediates and products involved. The present work may help rational design of more robust ORR electrocatalysts at the atomic level, realizing the significant advances in electrochemical conversion and storage devices. Single-Atom ElectrocatalystsThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.

The tailorable structure and electronic structure of metal−organic frameworks (MOFs) greatly facilitate their modulated light harvesting, redox power, and consequently photocatalysis. Herein, a representative MOF, UiO-66, was furnished by installing Fe 3+ onto the Zr-oxo clusters, to give Fe-UiO-66, which features extended visible light harvesting, based on metal-to-cluster charge transfer (MCCT). The Fe-UiO-66 with unique electronic structure and strong oxidizing power exhibits visible light-driven water oxidation, which is impossible for pristine UiO-66. More strikingly, under visible irradiation, the generated holes over Fe-UiO-66 are able to exclusively convert H 2 O to hydroxide radicals, initiating and driving the activation of stubborn C-H bond, such as toluene oxidation. The electrons reduce O 2 to O 2•radicals that further promote the oxidation reaction. The related catalytic mechanism and the structure−activity relationship have been investigated in detail. As far as we know, this is not only an unprecedented report on activating "inert" MOFs for photocatalytic C-H activation but also the first work on extended light harvesting and enhanced photocatalysis for MOFs by introducing an MCCT process.