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

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)O₃-based (M represents dopants) perovskite is formulated, and oxygen vacancy formation energy ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mi>Δ</mml:mi> <mml:msubsup><mml:mi>E</mml:mi> <mml:mi>v</mml:mi> <mml:mi>f</mml:mi></mml:msubsup> </mml:mrow> <mml:annotation>${{\Delta}}E_{\mathrm{v}}^{\mathrm{f}}$</mml:annotation></mml:semantics> </mml:math> ) and hydration energy (ΔE_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 between <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mi>Δ</mml:mi> <mml:msubsup><mml:mi>E</mml:mi> <mml:mi>v</mml:mi> <mml:mi>f</mml:mi></mml:msubsup> </mml:mrow> <mml:annotation>${{\Delta}}E_{\mathrm{v}}^{\mathrm{f}}$</mml:annotation></mml:semantics> </mml:math> and ΔE_hydr. Experiments further validate that the BaZr_0.125Co_0.375Fe_0.375Tm_0.125O_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.