Direct conversion of CO2 to CH4 on Pd/graphdiyne single-crystalline

Abstract

ABSTRACT A major impediment to the development of the efficient use of artificial photosynthesis is the lack of highly selective and efficient photocatalysts toward the conversion of CO2 by sunlight energy at room temperature and ambient pressure. After many years of hard work, we finally completed the synthesis of graphdiyne-based palladium quantum dot catalysts containing high-density metal atom steps for selective artificial photosynthesis. The well-designed interface structure of the catalyst is composed of electron-donor and acceptor groups, resulting in the obvious incomplete charge-transfer phenomenon between graphdiyne and plasmonic metal nanostructures on the interface. These intrinsic characteristics are the origin of the high performance of the catalyst. Studies on its mechanism reveal that the synergism between ‘hot electron’ from local surface plasmon resonance and rapid photogenerated carrier separation at the ohmic contact interface accelerates the multi-electron reaction kinetics. The catalyst can selectively synthesize CH4 directly from CO2 and H2O with selectivity of near 100% at room temperature and pressure, and exhibits transformative performance, with an average CH4 yield of 26.2 μmol g−1 h−1 and remarkable long-term stability.