Single‐Unit‐Cell Catalysis of CO2 Electroreduction over Sub‐1 nm Cu9S5 Nanowires

As a bridge between nanocrystal catalysts and single‐atom catalysts, single‐unit‐cell catalysts seem at first glance to be unavailable for catalysis due to quantum effects and synthetic difficulties. Here, 24 nm Cu9S5 nanowires are synthesized via the LaMer pathway. Interestingly, when polyoxometalate (POM) clusters are introduced during the nucleation process, the 0.9 nm Cu9S5 nanowires are finally formed via covalent co‐assembly, analog to A–B–A–B‐type block co‐polymerization in the polymer field (“A” and “B” represent Cu9S5 unit cells and POM clusters, respectively). Multiple characterizations show that Cu9S5 exists as single‐unit‐cell structure. Therefore, each unit cell can work as an isolated active site. The single‐unit‐cell structure exhibits higher electrocatalytic activity and Faradaic efficiency (FE) of formic acid (82.0% at −0.8 V vs reversible hydrogen electrode (RHE)) during CO2 electroreduction, while the nanocrystal structure generates HCOO−, methanol, and ethanol with low FEs. This study suggests that the single‐unit‐cell catalyst displays great potential for precise catalysis by the finite size effect. Analog to A–B–A–B‐type block co‐polymerization, Cu9S5 unit cells, and polyoxometalate clusters can assemble into sub‐1 nm Cu9S5 nanowires. Multiple characterizations indicate that each Cu9S5 unit cell works as an isolated active site during CO2 electroreduction, achieving a highest faradaic efficiency (HCOO‐) of 82.0%. This work opens up the novel possibility of designing a catalytic pathway on single‐unit‐cell catalyst.