Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a “precursor-preselected” wet-chemistry strategy to synthesize highly dispersed Fe2 clusters that are supported on mesoporous carbon nitride (mpg-C3N4). The obtained Fe2/mpg-C3N4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd2 and Ir2, which lays the foundation for discovering diatomic cluster catalysts.

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Development of single-atomic-site catalysts with high metal loading is highly desirable but proved to be very challenging. Although utilizing defects on supports to stabilize independent metal atoms has become a powerful method to fabricate single-atomic-site catalysts, little attention has been devoted to cation vacancy defects. Here we report a nickel hydroxide nanoboard with abundant Ni2+ vacancy defects serving as the practical support to achieve a single-atomic-site Pt catalyst (Pt1/Ni(OH)x) containing Pt up to 2.3 wt% just by a simple wet impregnation method. The Ni2+ vacancies are found to have strong stabilizing effect of single-atomic Pt species, which is determined by X-ray absorption spectrometry analyses and density functional theory calculations. This Pt1/Ni(OH)x catalyst shows a high catalytic efficiency in diboration of a variety of alkynes and alkenes, yielding an overall turnover frequency value upon reaction completion for phenylacetylene of ~3000 h−1, which is much higher than other reported heterogeneous catalysts.

An unprecedented dioxygen-triggered oxidative radical process was explored using dioxygen as the solely terminal oxidant, realizing aerobic oxidaitve difunctionalization of terminal alkynes toward β-keto sulfones with high selectivity. Operando IR experiments revealed that pyridine not only acts as a base to successfully surpress ATRA (atom transfer radical addition) process, but also plays a vital role in reducing the activity of sulfinic acids.

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