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 CO2 and CH4 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 CO2 and CH4 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 CO2 dissociation and CH4 dehydrogenation energy.

General Synthesis of High-Entropy Oxide Nanofibers

“…This seemed understandable considering that the small-sized Ni particles of (Ni 3 MoCoZn)Al 12 O 24 -Electrospinning-700(6 nm) possessed a stronger ability to inhibit carbon deposition. 49,62 2.3.4. CO 2 Activation.…”

Fluorine-Stabilized BO6 Octahedron of Host Perovskites for Robust Carbon Dioxide Electrolysis on Exsolved Catalysts

“…The significant enhancement in the catalytic activity of perovskites through an in situ exsolution technique has stimulated extensive studies to promote the exsolution of nanoparticles. − Although the increased surface nanoparticles and oxygen vacancies significantly extend the triple phase boundaries, − it should also be pointed out that the facilitated process is at the cost of consuming the host perovskite, which accelerates A-site surface segregation, formation of B-site vacancies, and even phase reconstruction of the host perovskite in the extreme case of promoting exsolution. − …”

Atypical Stability of Exsolved Ni-Fe Alloy Nanoparticles on Double Layered Perovskite for Co2 Dry Reforming of Methane

“…The support and its integration with the metal also play a crucial role in catalyst activity, selectivity, and stability [17]. Conventionally, the synthesis, such as wet impregnation or vapor deposition, lacks control of particle size, dispersion, morphology, and metal-support interaction, leading to faster sintering and coking [18,19].…”