Coordination tailoring of Cu single sites on CN realizes selective CO hydrogenation at low temperature.

CO hydrogenation has attracted great attention, yet the quest for highly-efficient catalysts is driven by the current disadvantages of poor activity, low selectivity, and ambiguous structure-performance relationship. We demonstrate here that CN-supported Cu single atom catalysts with tailored coordination structures, namely, Cu-N and Cu-N, can serve as highly selective and active catalysts for CO hydrogenation at low temperature. The modulation of the coordination structure of Cu single atom is readily realized by simply altering the treatment parameters. Further investigations reveal that Cu-N favors CO hydrogenation to form CHOH via the formate pathway, while Cu-N tends to catalyze CO hydrogenation to produce CO via the reverse water-gas-shift (RWGS) pathway. Significantly, the CHOH productivity and selectivity reach 4.2 mmol g h and 95.5%, respectively, for Cu-N single atom catalyst. We anticipate this work will promote the fundamental researches on the structure-performance relationship of catalysts.