Journal
CHEMICAL ENGINEERING JOURNAL
Volume 468, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2023.143569
Keywords
Zn2GeO4; D band center; PhotocatalyticCO2 reduction; Oxygen vacancy; Mn doping
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This study presents a d-band center tuning strategy to enhance the photocatalytic activity for CO2 activation. By engineering Mn dopants and oxygen vacancies in Zn2GeO4 nanorods, a strong interaction between CO2 molecules and the catalysts was achieved, resulting in significantly accelerated CO2 photoreduction.
Enabling catalysts to be highly active for CO2 activation is a crucial priority in photocatalytic CO2 reduction, but extremely challenging. To achieve this, significant electronic modulations based on the atomic-level knowledge of the operational catalytic site are necessary. Herein, a d-band center tuning strategy is proposed to promote the photocatalytic CO2 activation. In a model system taking Zn2GeO4 as photocatalysts, Mn dopants and oxygen vacancies (Vo) were engineered in Zn2GeO4 nanorods (denoted as Mn-ZGO-Vo) to collectively uplift the d-band centers, induced by the ligand and electron redistribution effects. This leads to a strong interaction between the CO2 molecules and Mn-ZGO-Vo, which weakens the C = O bonds for breaking. Temperature-dependent experiments and theoretical calculations reveal that Mn-ZGO-Vo exhibits a low energy barrier of CO2 photoreduction to CO, thereby significantly accelerating the rate-determining step, *COOH formation. Our optimal Mn-ZGO-Vo catalysts, without cocatalyst and sacrificing reagent, demonstrate a high selectivity of 82.9% for photoreducing CO2 to CO, with a CO yield of up to 40.02 & mu;mol g-1h- 1, which is nearly 8 times higher compared to pristine Zn2GeO4. Overall, this work not only demonstrates an effective strategy for promoting photocatalytic CO2 adsorption/activation/reduction, but also enriches the application of the d-band tuning concept in the field of photocatalysis.
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