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Rational design and synthesis of superior electrocatalysts for ethanol oxidation is crucial to practical applications of direct ethanol fuel cells. Here, we report that the construction of Pd-Zn dual sites with well exposure and uniformity can significantly improve the efficiency of ethanol electro-oxidation. Through synthetic method control, Pd-Zn dual sites on intermetallic PdZn nanoparticles, Pd-Pd sites on Pd nanoparticles and individual Pd sites are respectively obtained on the same N-doped carbon coated ZnO support. Compared with Pd-Pd sites and individual Pd sites, Pd-Zn dual sites display much higher activity for ethanol electro-oxidation, exceeding that of commercial Pd/C by a factor of ~24. Further computational studies disclose that Pd-Zn dual sites promote the adsorption of ethanol and hydroxide ion to optimize the electro-oxidation pathway with dramatically reduced energy barriers, leading to the superior activity. This work provides valuable clues for developing high-performance ethanol electro-oxidation catalysts for fuel cells.

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Utilizing heterogeneous catalysts to overcome obstacles for homogeneous reactions is fascinating but very challenging owing to the difficult fabrication of such catalysts based on the character of target reactions. Herein, we report a Al 3+ doping strategy to construct single-atom Cu on MgO nanosheets (Cu 1 /MgO(Al)) for boosting the free-radical hydrophosphinylation of alkenes. Al 3+ dopants in MgO bring about abundant Mg 2+ vacancies for stabilizing dense independent Cu atoms (6.3 wt %), while aggregated Cu nanoparticles are formed without Al 3+ dopants (Cu/MgO). Cu 1 /MgO(Al) exhibits preeminent activity and durability in the hydrophosphinylation of various alkenes with great anti-Markovnikov selectivity (99%). The turnover frequency (TOF) value reaches up to 1272 h −1 , exceeding those of Cu/MgO by ∼6-fold and of traditional homogeneous catalysts drastically. Further experimental and theoretical studies disclose that the prominent performance of Cu 1 /MgO(Al) derives from the accelerated initiating step of phosphinoyl radical triggered by individual Cu atoms.