Graphdiyene enables ultrafine Cu nanoparticles to selectively reduce CO2 to C2+ products

• Published in: Nano research Vol. 15; no. 1; pp. 195 - 201
• Main Authors: Chang, Yong-Bin, Zhang, Chao, Lu, Xiu-Li, Zhang, Wen, Lu, Tong-Bu
• Format: Journal Article
• Language: English
• Published: Beijing Tsinghua University Press 2022; Springer Nature B.V
• Subjects: Alkynes; Atomic/Molecular Structure and Spectra; Binding; Biomedicine; Biotechnology; Carbon dioxide; Carbon nanotubes; Catalysts; Chemistry and Materials Science; Condensed Matter Physics; Electrocatalysts; Graphene; Intermediates; Materials Science; Nanoparticles; Nanotechnology; Research Article; Selectivity; Ultrafines; multicarbon products; graphdiyne nanofibers; CO; reduction; electrocatalysis; ultrafine copper nanoparticles
• ISSN: 1998-0124; 1998-0000
• DOI: 10.1007/s12274-021-3456-2

Reducing the size of heterogeneous nanocatalysts is generally conducive to improving their atomic utilization and activities in various catalytic reactions. However, this strategy has proven less effective for Cu-based electrocatalysts for the reduction of CO
2
to multicarbon (C
2+
) products, owing to the overly strong binding of intermediates on small-sized (< 15 nm) Cu nanoparticles (NPs). Herein, by incorporating pyrenyl-graphdiyne (Pyr-GDY), we successfully endowed ultrafine (∼ 2 nm) Cu NPs with a significantly elevated selectivity for CO
2
-to-C
2+
conversion. The Pyr-GDY can not only help to relax the overly strong binding between adsorbed H* and CO* intermediates on Cu NPs by tailoring the d-band center of the catalyst, but also stabilize the ultrafine Cu NPs through the high affinity between alkyne moieties and Cu NPs. The resulting Pyr-GDY-Cu composite catalyst gave a Faradic efficiency (FE) for C
2+
products up to 74%, significantly higher than those of support-free Cu NPs (C
2+
FE, ~ 2%), carbon nanotube-supported Cu NPs (CNT-Cu, C
2+
FE, ~ 18%), graphene oxide-supported Cu NPs (GO-Cu, C
2+
FE, ~ 8%), and other reported ultrafine Cu NPs. Our results demonstrate the critical influence of graphdiyne on the selectivity of Cu-catalyzed CO
2
electroreduction, and showcase the prospect for ultrafine Cu NPs catalysts to convert CO
2
into value-added C
2+
products.