Search

Wide application of novel materials often requires low-cost preparation methods. In this study, we present a simplified and facile preparation method for the [Ca24Al28O64]4+(e−)4 electride material (C12A7:e−). Successful preparation of the C12A7:e− electride was confirmed by XRD patterns and magnetic behavior analysis. The concentration of electrons in the prepared C12A7:e− powder was calculated to be approximately 2.23 × 1021 cm−3, as evaluated by iodometry and TPD. DFT calculations provided insight into the unique electronic structure of C12A7:e−. Additionally, the substitution of the Ca reductant with CaH2 led to a reduction in the solid-state reaction temperature from 1100 to 950 °C, which can be attributed to thermodynamic effects such as a reduction in ΔG°. [ABSTRACT FROM AUTHOR]

In catalysis science, the electronic structure of the active site determines the structure–activity relationship of the catalyst to a large extent. Therefore, modulating the electronic structure has become a main route for the rational design of metal‐based catalyst materials. In this work, we prepared a LaCoSiHx material that has more electronegativity and a lower workfunction than traditional supported Co‐based catalysts. Using CO2 methanation as a model catalytic reaction, the facile dissociation of CO2 and CO (a key reaction intermediate) on the surface of the LaCoSiHx catalyst is observed by various experimental methods (e.g., in situ Raman and FTIR) at room temperature. Moreover, theoretical calculation results further show that LaCoSiHx has a much stronger capacity for carbon–oxygen bond activation than the Co surface. The intrinsic mechanism is attributed to the marked electron transfer from catalysts into the antibonding orbital of CO2 and CO. [ABSTRACT FROM AUTHOR]

[Display omitted] • The CO/H 2 ratio can be readily tuned via varying the Zn doping level. • Zn incorporation enhances CO 2 activation and facilitates CO desorption. • Zn doping inhibits the HER activity. Photochemical reduction of CO 2 (CO 2 RR) to syngas is an attractive approach for carbon–neutral recycling. Manipulating binding strength to reactive species on catalyst surfaces is challenging but essential for achieving efficient syngas production with a desired CO/H 2 ratio. Here, we demonstrate that the binding strength to key reaction intermediates (*CO 2 , *H and *CO) on the Co 3 O 4 surface can be fine-tuned by incorporating varying amount of Zn atoms. Dedicated experiments and theoretical simulations unveil that Zn doping allows for simultaneous control of both CO 2 adsorption/activation and the adsorption affinity of *CO on Zn-Co 3 O 4 catalysts, resulting in a significant enhancement in CO 2 to CO conversion. Moreover, Zn doping can alter the hydrophilicity of the catalyst surface, affecting the water adsorption behavior and adjusting the hydrogen evolution reaction (HER) activity. As a result, the CO/H 2 ratio can be readily tuned via varying the Zn doping level. This study presents an effective and economical method approach to manipulate the electronic structure of catalyst surfaces for controlling the kinetics of CO 2 RR and HER reactions, providing valuable insight into the design of highly active transition metal oxides (TMOs) based photocatalysts for syngas production with a tailored CO/H 2 ratio. [ABSTRACT FROM AUTHOR]