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Oxidative coupling of methane (OCM) can be performed electrocatalytically by utilizing solid oxide cells, which provide a readily controlled oxygen supply through dense electrolytes. La_0.7Sr_0.2Ni_0.2Fe_0.8O₃(LSNF) perovskite is an effective anode for OCM. Its surface characteristics and electrocatalytic activity can be improved by reduction and the resultant exsolution of bimetallic NiFe nanoparticles from its bulk. X‐ray diffraction (XRD) and environmental transmission electron microscopy proved that the evolution of hetero‐phases under reducing environment resulted in bimetallic NiFe nanoparticles being formed on the surface. A 36 % improvement in C₂₊hydrocarbon production rate was achieved due to the reduction of LSNF with the exsolved NiFe nanoparticles. Co‐feeding of H₂O enhanced selective conversion of CH₄resulting in the production rate of C₂₊hydrocarbons being increased by 56 %. Analysis of impedance spectra and in‐situ DRIFTS under a CH₄+H₂O atmosphere provided an understanding for the enhancement on the electrocatalytic OCM.

 

La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF), having thermochemical stability, superior ionic and electronic conductivity, and structural flexibility, was investigated as a cathode in SOECs. Exsolution of nanoparticles by reduction of LSNF at elevated temperatures can modulate the characteristics of adsorption, electron transfer, and oxidation states of catalytically active atoms, consequently improving the electrocatalytic activity. The exsolution of NiFe and La 2 NiO 4 nanoparticles to the surface of LSNF under reducing atmosphere (5% H 2 /N 2 ) was verified at various temperatures (500–800 °C) by IFFT from ETEM, TPR and in situ XRD. The exsolved nanoparticles obtained uniform size distribution (4.2–9.2 nm) and dispersion (1.31 to 0.61 × 10 4 particle per μm 2 ) depending on the reduction temperature (700–800 °C) and time (0–10 h). The reoxidation of the reduced LSNF (Red-LSNF) was verified by the XRD patterns, indicative of its redox ability, which allows for redistribution of the nanoparticles between the surface and the bulk. TPD-DRIFTS analysis demonstrated that Red-LSNF had superior H 2 O and CO 2 adsorption behavior as compared to unreduced LSNF, which we attributed to the abundance of oxygen vacancy sites and the exsolved NiFe and La 2 NiO 4 nanoparticles. After the reduction of LSNF, the decreases in the oxidation states of the catalytically active ions, Fe and Ni, were characterized on the surface by XPS as well as in the bulk by XANES. The electrochemical performance of the Red-LSNF cell was superior to that of the LSNF cell for electrolysis of H 2 O, CO 2 , and H 2 O/CO 2 . 

La0.7Sr0.2Ni0.2Fe0.8O3 (LSNF), having thermochemical stability, superior ionic and electronic conductivity, and structural flexibility, was investigated as a cathode in SOECs. Exsolution of nanoparticles by reduction of LSNF at elevated temperatures can modulate the characteristics of adsorption, electron transfer, and oxidation states of catalytically active atoms, consequently improving the electrocatalytic activity. The exsolution of NiFe and La2NiO4 nanoparticles to the surface of LSNF under reducing atmosphere (5% H2/N2) was verified at various temperatures (500–800 °C) by IFFT from ETEM, TPR and in situ XRD. The exsolved nanoparticles obtained uniform size distribution (4.2–9.2 nm) and dispersion (1.31 to 0.61 × 104 particle per μm2) depending on the reduction temperature (700–800 °C) and time (0–10 h). The reoxidation of the reduced LSNF (Red-LSNF) was verified by the XRD patterns, indicative of its redox ability, which allows for redistribution of the nanoparticles between the surface and the bulk. TPD-DRIFTS analysis demonstrated that Red-LSNF had superior H2O and CO2 adsorption behavior as compared to unreduced LSNF, which we attributed to the abundance of oxygen vacancy sites and the exsolved NiFe and La2NiO4 nanoparticles. After the reduction of LSNF, the decreases in the oxidation states of the catalytically active ions, Fe and Ni, were characterized on the surface by XPS as well as in the bulk by XANES. The electrochemical performance of the Red-LSNF cell was superior to that of the LSNF cell for electrolysis of H2O, CO2, and H2O/CO2. 

An operando characterization of electrode materials under electrochemical reaction conditions is important for their further development. X-ray absorption spectroscopy (XAS) presents a unique opportunity in this regard as the absence of a vacuum chamber in this technique makes it possible to collect spectroscopy data using user-designed operando cells. In the current study, the design and performance of an operando XAS cell are evaluated for characterizing solid oxide electrolysis cell working electrodes under a reaction environment that mimics high-temperature ammonia production conditions from H 2 O and N 2 . Sr 2 FeMoO 6−x N x (SFMON)-type double perovskite oxides were used as the cathode materials in these experiments. The operando cell contained a sample stage with a turnable head so that XAS data can be collected at different angles between the electrode and the X-ray beam with an accuracy of 0.5°. The mechanism to adjust the angle of incidence of the beam on the sample allows control over the depth of penetration of the X-ray photons into the electrode. At low angles, it becomes possible to collect surface sensitive data, which is of great importance as the electrochemical processes are believed to take place on the surface of the electrodes. Sr K-edge and Fe K-edge XAS collected at 2° and 45° angles showed that these the oxidation state changes occurring in these elements are different in the near-surface region compared to the bulk of the electrode. Such an ability to distinguish between the surface and bulk properties of the electrode during real reaction environment will help to understand the underlying phenomena better, which will enable electrode design targeted towards the reactions of interest.