High‐Throughput DFT‐Assisted Design of Electrode for Efficient High‐Temperature Electrochemical Dehydrogenation

Abstract Protonic ceramic electrolysis cell (PCEC) is a promising technique to enable efficient dehydrogenation reactions for producing valuable chemicals, but is still limited by the lack of stable electrocatalysts to achieve efficient O─H/C─H dissociation. In this work, upon high‐throughput first‐principles calculations, Ba(Zr,Co,Fe,M)O 3 ‐based (M represents dopants) perovskite is formulated, and oxygen vacancy formation energy ( Δ E v f ${{\Delta}}E_{\mathrm{v}}^{\mathrm{f}}$ ) and hydration energy (Δ E hydr ) are taken as two key performance indicators to screen potential PCEC electrode materials derived from this category. Trivalent doping elements, particularly Y, Yb, Er, and Tm, achieve a good balance betweenΔ E v f ${{\Delta}}E_{\mathrm{v}}^{\mathrm{f}}$ and Δ E hydr . Experiments further validate that the BaZr 0.125 Co 0.375 Fe 0.375 Tm 0.125 O 3−δ showed impressive dehydrogenation reaction activity, with faradaic efficiency as high as 98.90% in water electrolysis, and outstanding ethane conversion rate (67.60%) and ethylene yield (62.62%) for ethane dehydrogenation reaction at 700 °C. The computational approach can be applied to the rational design of novel electrode materials for other electrochemical reactions in energy and environment devices.