Precise Modulation of Triple‐Phase Boundaries towards a Highly Functional Exsolved Catalyst for Dry Reforming of Methane under a Dilution‐Free System

Abstract Dry reforming of methane (DRM) has been emerging as a viable solution to achieving carbon neutrality enhanced by the Paris Agreement as it converts the greenhouse gases of CO 2 and CH 4 into industrially useful syngas. However, there have been limited studies on the DRM catalyst under mild operating conditions with a high dilution gas ratio due to their deactivation from carbon coking and metal sintering. Herein, we apply the triple‐phase boundary (TPB) concept to DRM catalyst via exsolution phenomenon that can secure elongated TPB by controlling the Fe‐doping ratio in perovskite oxide. Remarkably, the exsolved catalyst with prolongated TPB shows exceptional CO 2 and CH 4 conversion rates of 95.9 % and 91.6 %, respectively, stable for 1000 hours under a dilution‐free system. DFT calculations confirm that the Lewis acid of support and Lewis base of metal at the TPB promote the adsorption of reactants, resulting in lowering the overall CO 2 dissociation and CH 4 dehydrogenation energy.