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Mechanistic investigation of alkali treated photocatalytic CO2 reduction: the role of OH‐ and metal cations for almost 100% selectivity of CO

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In this work, the modulation of activity and selectivity via photoreduction of carbon dioxide under simulated sunlight was achieved by treating P25 and P25/Pt NPs with KOH. It found that KOH treatment could significantly improve the overall conversion efficiency and switch the selectivity for CO. Photoelectric characterizations and CO 2 -TPD demonstrated that the synergistic effect of K +  and OH -  accelerated the separation and migration of photogenerated charges, and promoted CO 2  adsorption level. Significantly, the K +  could act active site for CO 2  adsorption and further activation.   I n - situ  FTIR measurements and DFT theoretical calculations also confirmed that K ions enhanced the charge density of adjacent atoms and stabilized CO* groups, thereby reducing the reaction energy barrier and inducing the switching of original CH 4  to CO, which played a selective regulatory role. This study provides insights into the photocatalytic activity and selectivity of alkali-treated photocatalysts and facilitates the design of efficient and product-specific photocatalysis.

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