Size‐Dependent Activity and Selectivity of Atomic‐Level Copper Nanoclusters during CO/CO₂ Electroreduction

Abstract

As af avorite descriptor,t he size effect of Cu-based catalysts has been regularly utilized for activity and selectivity regulation toward CO 2 /CO electroreduction reactions (CO 2 / CORR). However,l ittle progress has been made in regulating the sizeofCunanoclusters at the atomic level. Herein, the sizegradient Cu catalysts from single atoms (SAs) to subnanometric clusters (SCs,0.5-1 nm) to nanoclusters (NCs,1-1.5 nm) on graphdiyne matrix are readily prepared via an acetylenicbond-directed site-trapping approach.E lectrocatalytic measurements showasignificant sizeeffect in both the activity and selectivity towardC O 2 /CORR. Increasing the sizeo fC u nanoclusters will improve catalytic activity and selectivity towardC 2+ productions in CORR. Ahigh C 2+ conversion rate of 312 mA cm À2 with the Faradaic efficiency of 91.2 %a re achieved at À1.0 Vv ersus reversible hydrogen electrode (RHE) over Cu NCs.T he activity/selectivity-sizer elations provideaclear understanding of mechanisms in the CO 2 / CORR at the atomic level.

The Role of Cu1-O3 Species in Single-Atom Cu Catalyst for Directional Methanol Synthesis from CO2 Hydrogenation

“…Auger centred at 915.5eV without any shifting in CAZ-1 and CAZ-1-U also con rmed the stable Cu δ+ species in catalyst surface (Figure S15) 31 . However, the satellite peaks of Cu 2p 3/2 that appeared in CAZ-15, suggesting that Cu 2+ species were formed in CuO clusters or nanoparticles (Fig.…”

“…In comparison to the CAZ-15, the absence of Cu 2p satellite peaks between 940eV and 945eV implied that no Cu 2+ species exited in the fresh and used CAZ-1 catalysts 15,44 . Identical peaks situated at 932.9eV between Cu 0 (932.4eV) and Cu 2+ (934.6eV) were observed in CAZ-1 and CAZ-1-U (U: used), indicating the Cu species were at cationic Cu δ+ state 31,45 . The position of Cu 2p 3/2 was not shifted after the reaction, giving another strong evidence that the active Cu δ+ species was very stable in the CAZ-1 catalyst, at the same time as no metallic Cu nanoparticles forming to make sure supplying enough stable active sites in CO 2 hydrogenation process (Fig.…”

Graphdiyne‐Based Single‐Atom Catalysts with Different Coordination Environments

“…[42] Later, Duan et al used the same method to achieve GDY-based Cu materials with different sizes, including single atoms, sub-nanometric clusters and nanoclusters by adjusting the amount of CuI precursor. [43]…”

Impaired conjugation boosts CO2 electroreduction by Ni(ii) macrocyclic catalysts immobilized on carbon nanotubes

“…Encouraged by the high performance of NiPc-B@CNT in the Hcell set-up, we further fabricated gas-diffusion electrodes 5,49,50 (GDEs; see the set-up in Fig. S20 †) to pursue industrially relevant efficiency.…”