Architecture Design and Catalytic Activity: Non-Noble Bimetallic CoFe/fe3 O4 Core-Shell Structures for CO2 Hydrogenation.

Non-noble metal catalysts now play a key role in promoting efficiently and economically catalytic reduction of CO2 into clean energy, which is an important strategy to ameliorate global warming and resource shortage issues. Here, a non-noble bimetallic catalyst of CoFe/Fe3 O4 nanoparticles is successfully designed with a core-shell structure that is well dispersed on the defect-rich carbon substrate for the hydrogenation of CO2 under mild conditions. The catalysts exhibit a high CO2 conversion activity with the rate of 30% and CO selectivity of 99%, and extremely robust stability without performance decay over 90 h in the reverse water gas shift reaction process. Notably, it is found that the reversible exsolution/dissolution of cobalt in the Fe3 O4 shell will lead to a dynamic and reversible deactivation/regeneration of the catalysts, accompanying by shell thickness breathing during the repeated cycles, via atomic structure study of the catalysts at different reaction stages. Combined with density functional theory calculations, the catalytic activity reversible regeneration mechanism is proposed. This work reveals the structure-property relationship for rational structure design of the advanced non-noble metallic catalyst materials with much improved performance.

Narrowing Working Voltage Window to Improve Layered GeP Anode Cycling Performance for Lithium-Ion Batteries.

Layered germanium phosphide (GeP), a recently developed two-dimensional material, promises highly attractive theoretical capacity for use as a lithium-ion battery anode. Here, we comprehensively investigate its electrochemical performance and the modification mechanism. GeP flakes demonstrate large initial discharge/charge capacity and high initial Coulombic efficiency. However, the cycling performance is disappointing in the potential window of 0.001-3 V in which capacity retention is only ∼18% after 100 cycles. In situ transmission electron microscopy reveals that the poor cycling behavior results in the unexpected large volume change induced by complex reaction processes in cycles. Serious cracking and fracture appear clearly on the electrode surface after cycling. Narrowing the working voltage window to 0.001-0.85 V, cycling stability will be greatly enhanced, with 75% capacity retaining after 100 cycles and ∼50% left after 350 cycles due to the absence of the dealloying of Li3P in the narrowed working voltage window. Additionally, the electric contact among the electrode components has been enhanced by the alleviation of the electrode volume change in the narrowed working voltage window. Our work provides one effective method to give a deep understanding of the high-energy-density electrode failure and helps to narrow the huge gap between the microstructure and the performance of the electrode.