Ceo2 /Cus Nanoplates Electroreduce Co2 to Ethanol with Stabilized Cu+ Species.

Copper-based electrocatalysts effectively produce multicarbon (C2+ ) compounds during the electrochemical CO2 reduction (CO2 RR). However, big challenges still remain because of the chemically unstable active sites. Here, cerium is used as a self-sacrificing agent to stabilize the Cu+ of CuS, due to the facile Ce3+ /Ce4+ redox. CeO2 -modified CuS nanoplates achieve high ethanol selectivity, with FE up to 54% and FEC2+ ≈ 75% in a flow cell. Moreover, in situ Raman spectroscopy and in situ Fourier-transform infrared spectroscopy indicate that the stable Cu+ species promote CC coupling step under CO2 RR. Density functional theory calculations further reveal that the stronger * CO adsorption and lower CC coupling energy, which is conducive to the selective generation of ethanol products. This work provides a facile strategy to convert CO2 into ethanol by retaining Cu+ species.

Boosting the Electrocatalytic Oxygen Evolution of Perovskite LaCo1- x Fex O3 by the Construction of Yolk-Shell Nanostructures and Electronic Modulation.

Realizing the rational design of perovskite oxides with controllable compositions and nanostructures remains a tremendous challenge for the development of efficient electrocatalysts. Herein, a ligand-assisted synthetic strategy to fabricate perovskite oxides LaCo1- x Fex O3 with yolk-shell nanostructures is developed. Benefiting from the unique structural and compositional merits, LaCo0.75 Fe0.25 O3 exhibits an overpotential of 310 mV at a current density of 10 mA cm-2 and long-term stability of 100 h for the oxygen evolution reaction. In situ Raman spectroscopy demonstrates that Fe substitution facilitates the pre-oxidation of Co sites and induces the surface reconstruction into active Co oxyhydroxides at a relatively lower applied potential, guaranteeing excellent catalytic performances. Density functional theory calculations unravel that the appropriate introduction of Fe into perovskite LaCoO3 leads to the improved electroactivity and durability of the catalyst for the oxygen evolution reaction (OER). Fe-3d orbitals show a pinning effect on Co-3d orbitals to maintain the stable valence state of Co sites at the low overpotential of the OER. Furthermore, Zn-air batteries (ZABs) assembled with LaCo0.75 Fe0.25 O3 display a high open circuit potential of 1.47 V, superior energy density of 905 Wh kg-1  Zn , and excellent stability in a large temperature range. This work supplies novel insights into the future developments of perovskite-based electrocatalysts.

Artificially steering electrocatalytic oxygen evolution reaction mechanism by regulating oxygen defect contents in perovskites.

The regulation of mechanism on the electrocatalysis process with multiple reaction pathways is more efficient and essential than conventional material engineering for the enhancement of catalyst performance. Here, by using oxygen evolution reaction (OER) as a model, which has an adsorbate evolution mechanism (AEM) and a lattice oxygen oxidation mechanism (LOM), we demonstrate a general strategy for steering the two mechanisms on various LaxSr1-xCoO3-δ. By delicately controlling the oxygen defect contents, the dominant OER mechanism on LaxSr1-xCoO3-δ can be arbitrarily transformed between AEM-LOM-AEM accompanied by a volcano-type activity variation trend. Experimental and computational evidence explicitly reveal that the phenomenon is due to the fact that the increased oxygen defects alter the lattice oxygen activity with a volcano-type trend and preserve the Co0 state for preferably OER. Therefore, we achieve the co-optimization between the activity and stability of catalysts by altering the mechanism rather than a specific design of catalysts.