The modification of the terminal electron-donating groups induces a critical change in molecular aggregation and the intermolecular charge-transfer effect of the symmetric D-A1-A2-A1-D molecules that correlate with an addressable variation of memory performance from binary to ternary.

The sluggish oxygen reaction kinetics concomitant with the high overpotentials and parasitic reactions from cathodes and solvents is the major challenge in aprotic lithium‐oxygen (Li–O2) batteries. Herein, PtIr multipods with a low Lewis acidity of the Pt atoms are reported as an advanced cathode for improving overpotentials and stabilities. DFT calculations disclose that electrons have a strong disposition to transfer from Ir to Pt, since Pt has a higher electronegativity than Ir, resulting in a lower Lewis acidity of the Pt atoms than that on the pure Pt surface. The low Lewis acidity of Pt atoms on the PtIr surface entails a high electron density and a down‐shifting of the d‐band center, thereby weakening the binding energy towards intermediates (LiO2), which is the key in achieving low oxygen‐reduction‐reaction (ORR) and oxygen‐evolution‐reaction (OER) overpotentials. The Li–O2 cell based on PtIr electrodes exhibits a very low overall discharge/charge overpotential (0.44 V) and an excellent cycle life (180 cycles), outperforming the bulk of reported noble‐metal‐based cathodes.

Constructing well-designed catalysts to accelerate OER catalytic activity and alleviate the charge overpotential is prevailing for achieving sophisticated LiÀ O 2 batteries. Herein, we report a concept for engineering the e g occupancy of Pt with M alloying (M = Au, Ru) to tune the charge overpotentials for achieving high-performance LiÀ O 2 batteries. The X-ray photoelectron spectroscopy results coupled with density functional theory (DFT) calculations reveal that the highly electronegative Au can capture more e g electrons from Pt, leading to less e g electrons of Pt in PtAu than that in PtRu. The lower e g occupancy of Pt atoms in PtAu alloys entails the upward shift of the Pt d band, which causes a strong binding strength towards the intermediates (LiO 2 ), thereby decreasing the OER energy barrier. As a consequence, the LiÀ O 2 battery with a PtAu cathode delivers a low charge overpotential of 0.36 V and superior cycle life of 220 cycles at a cutoff capacity of 1000 mAh g À 1 , which is among the best in the reported noble metal-based cathodes.

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