Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single‐Atom Gold Catalyst Supported on Amino‐Substituted Graphdiyne

Abstract Regulating the second sphere of homogeneous molecular catalysts is a common and effective method to boost their catalytic activities, while the second sphere effects have rarely been investigated for heterogeneous single‐atom catalysts primarily due to the synthetic challenge for installing functional groups in their second spheres. Benefiting from the well‐defined and readily tailorable structure of graphdiyne (GDY), an Au single‐atom catalyst on amino‐substituted GDY is constructed, where the amino group is located in the second sphere of the Au center. The Au atoms on amino‐decorated GDY displayed superior activity for formic acid dehydrogenation compared with those on unfunctionalized GDY. The experimental studies, particularly the proton inventory studies, and theoretical calculations revealed that the amino groups adjacent to an Au atom could serve as proton relays and thus facilitate the protonation of an intermediate Au−H to generate H 2 . Our study paves the way to precisely constructing the functional second sphere on single‐atom catalysts.