Tunable Heterostructured Nanomaterials for Efficient Hydrogenation Reactions at Intermediate Temperatures

To address rising environmental concerns and energy challenges, it is highly desirable to develop green technologies for a sustainable future. Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds. Electrochemical CO₂ and N₂ hydrogenation using renewable electricity is considered one of the most promising pathways to reach the environmental economics. Among various electrochemical devices, a solid state electrolyzer working at intermediate temperatures has the advantages of high reaction rates and low overpotentials. As CO₂ and N₂ molecules are quite stable, it is critical to develop electrocatalysts with high activity to reduce electricity engagement. Also, CO₂ hydrogenation has multiple pathways which normally results in low selectivity for a target product. A tunable electrocatalyst with high selectivity to different products is desirable for CO₂ hydrogenations. Heterostructured nanomaterials attracts great attentions in electrochemical systems. With careful design, they can show very high activity and selectivity towards an electrochemical reaction. In this work, we combine theoretical simulations, including density functional theory (DFT) and ab initio molecular dynamics (AIMD) calculations, with experimental methods (characterizations and electrochemical measurements) for rational design of highly efficient heterostructured nanomaterials for CO₂ and N₂ hydrogenations.

We studied the strong metal-support interaction (SMSI) in a doped CeO₂ supported noble metal nanoparticles (NPs) system using theoretical calculations. The results indicate that SMSI largely depends on chemical conditions of the support and particle size of dispersed metal NPs. By tuning the SMSI, we can successfully change the catalytic activity and selectivity towards CO₂ and N₂ hydrogenation reactions. Based on these findings, we designed tunable heterostructured nanomaterials for efficient hydrogenation reactions at intermediate temperatures. These predictions were further confirmed by experimental method. By using a combination of high-throughput theoretical calculations and electrochemical measurements, we developed highly active catalysts for electrochemical CO₂ and N₂ hydrogenation reactions. This framework is also applicable to other electrochemical systems using heterostructured materials.