In Situ Exsolution of High-Density Ni Nanoparticles in LaAl 0.3 Mn 0.2 Ni 0.5 O 3−δ Cathode for the Electro-Thermocatalytic CO 2 -Intensified Dry Reforming of Methane

The tandem electro-thermocatalytic system, which integrates dry reforming of methane with reverse water–gas shift and H2O electrolysis reactions within a solid oxide electrolysis cell, offers an innovative path for the utilization of CO2-rich feedstocks. The identification of the correlation between the interface-dependent characteristics and both catalytic activity and stability remains a formidable challenge. Herein, we focus on the exsolution of high-density and well-dispersed nanoparticles semiembedded on the LaAl0.3Mn0.2Ni0.5O3−δ cathode by modulating the Al and Mn co-doping strategy. The substantial and stable metal@perovskite interfacial sites exhibit high intrinsic activity for the tandem electro-thermocatalytic system, which provides high single-pass CO2 and CH4 conversion over 92%, syngas yield over 93%, apparent CH4 reducibility up to 3.91, and a CH4 turnover frequency of 73.77 molCH4 molNi–1 s–1 using various CO2-rich feedstocks (CO2/CH4 = 2–4) at 800 °C. In situ electrochemical diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations demonstrate the crucial role of *OH electrolysis in the tandem catalysis process. This work elucidates the structure–activity relationship between the metal@support interfacial sites and catalytic activity and stability for the tandem electro-thermocatalytic system.