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At the same time, the adjacent Cu x effectively promotes the protonation of *CO 2 - by accelerating water dissociation and offering *H to the Cu-S 1 N 3 active sites. Consequently, the fine-tuned single Cu atoms and Cu clusters integrated in carbon matrix play a synergistic role in lowering the energy barrier of the rate-determining step (*COOH formation) and cooperatively improving the reductive conversion of CO 2 to CO. This work provides a tandem strategy for facilitating proton-coupled electron transfer over the atomic-level catalyti
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