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 H2. Our study paves the way to precisely constructing the functional second sphere on single‐atom catalysts.

Two-Dimensional Carbon Graphdiyne: Advances in Fundamental and Application Research

“…158 Liu et al reported the Au SAs anchored on amino-substituted graphdiyne for efficient formic acid dehydrogenation (Figure 17m−n). 159 After 5 h of catalyst reaction by Au/GDY-NH 2 , the conversion of formic acid could reach over 99% (Figure 17o). Mao and co-workers fabricated the selective electrocatalysis by interfacing redox-active methylene green and graphdiyne.…”

“…(o) Dehydrogenation of formic acid with different catalysts. Reproduced with permission from ref . Copyright 2023, Wiley-VCH.…”

“…The incorporation of sulfur minimized the band gap, improved the charge distribution of the SGDY network, and increased the density of active sites, which resulted in significant peroxidase-like activity . Liu et al reported the Au SAs anchored on amino-substituted graphdiyne for efficient formic acid dehydrogenation (Figure m–n) . After 5 h of catalyst reaction by Au/GDY-NH 2 , the conversion of formic acid could reach over 99% (Figure o).…”

Overall water electrolysis on a graphdiyne-iron oxyhydroxide heterostructure

“…Moreover, the unique incomplete charge transfer between GDY and metal atoms could increase the number and the stability of the active site. [15][16][17][18] Benetting from these superiorities, GDY has shown excellent performances and attracted greatly increasing interest from the elds of electrocatalysis, [19][20][21][22][23][24][25][26][27][28] photocatalysis, [29][30][31] energy conversion, [32][33][34][35][36][37] etc. [38][39][40] In this study, the highly active and stable OER, HER, as well as OWS were achieved on the heterostructure of FeOOH@GDY with electronic-donating and withdrawing interface structures, resulting in innite active sites which guarantee excellent catalytic activity.…”

“…Moreover, the unique incomplete charge transfer between GDY and metal atoms could increase the number and the stability of the active site. 15–18 Benefitting from these superiorities, GDY has shown excellent performances and attracted greatly increasing interest from the fields of electrocatalysis, 19–28 photocatalysis, 29–31 energy conversion, 32–37 etc . 38–40…”