Mechanical stimulation of gasless reaction in inorganic systems: A mini review
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Nanoparticles with well-defined facets enable quantitative correlations between surface features and catalytic activity. In this work, we explore the role of geometric and acid–base properties in the mechanism of aldol condensation catalyzed by ceria nanoshapes. In the crucial C–C coupling step, the two carbonyl adsorbates are bound to two adjacent cations. On the CeO 2 (110) plane, all atoms lie on the same layer, favoring the interaction between adsorbates and facilitating the bimolecular C–C coupling. Thus, the initial unimolecular deprotonation is rate-limiting. In contrast, the (100) and (111) planes have an open structure with O on the top layer and Ce on the layer below. The former O layer interferes between adsorbates linked to Ce sites, making the C–C coupling rate-limiting. Water helps in overcoming this spatial hindrance by remote bond polarization via H-bonds. Therefore, water promotion is only observed on those planes for which the bimolecular step is rate-limiting.
The extremely large surface area offered by quasi-two-dimensional (2D) nanostructures is a great advantage for catalytic applications. While bimetallic materials have been discovered as a group of promising catalysts for electrochemical water splitting, a facile and reliable synthesis approach toward 2D morphology to fully release its electrochemical catalytic potential is still lacking. In this work, bimetallic Co–Mo–O ultrathin nanosheets were synthesized by ionic layer epitaxy with controlled composition ratio. The Co–Mo–O nanosheets exhibited a quadrangle shape with a uniform thickness of ~2.5 nm. This 2D morphology largely enriched the surface catalytic active site ratio. Particularly, nanosheets with 2:1 Co-to-Mo ratio showed a substantially enhanced OER catalytic activity with a 3 orders of magnitude higher mass activity compared to benchmark IrO 2 and RuO 2 in an alkaline environment. Furthermore, this study introduces a promising possibility for creating high-performance electrocatalysts from 2D bimetallic materials with a high efficiency for material utilization.
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