An effective modulation of the active sites in a bifunctional electrocatalyst is essentially desired, and it is a challenge to outperform the state-of-the-art catalysts toward oxygen electrocatalysis. Herein, we report the development of a bifunctional electrocatalyst having target-specific Fe–N4/C and Co–N4/C isolated active sites, exhibiting a symbiotic effect on overall oxygen electrocatalysis performances. The dualism of N-dopants and binary metals lower the d-band centers of both Fe and Co in the Fe,Co,N–C catalyst, improving the overpotential of the overall electrocatalytic processes (ΔE ORR‑OER = 0.74 ± 0.02 V vs RHE). Finally, the Fe,Co,N–C showed a high areal power density of 198.4 mW cm–2 and 158 mW cm–2 in the respective liquid and solid-state Zn–air batteries (ZABs), demonstrating suitable candidature of the active material as air cathode material in ZABs.

Tuning the electronic structure of perovskite oxides via aliovalent substitution is a promising strategy to attain inexpensive and efficient electrocatalysts for energy conversion and storage devices. Herein, following the d-band center positions and using a simple sol–gel method followed by a pyrolysis step, LaNi1–x Co0.5x Fe0.5x O3 (LNFCO-x; x = 0.0, 0.4, 0.5, and 0.6) electrocatalysts are designed and synthesized for oxygen redox reactions in 1 M KOH. Among them, LNFCO-0.5 has exhibited the lowest overpotential and the highest charge transfer kinetics in oxygen redox reactions. Overall, a 90 mV lower overpotential was observed in oxygen redox activity of LNFCO-0.5 compared to that of pristine LaNiO3. The mass activity of LNFCO-0.5 in the oxygen reduction reaction (at 0.7 V vs RHE) and oxygen evolution reaction (1.60 V vs RHE) was calculated to be 2.5 and 2.13 times higher than that of LaNiO3, respectively. The bifunctionality index (potential difference between the oxygen evolution at a current density of 10 mA cm–2 and the oxygen reduction at a current density of −1 mA cm–2) of LNFCO-0.5 was found to be 0.98. The substitution of Fe and Co for the Ni-site shifted the d-band center close to the Fermi level, which can increase the binding strength of the *OH intermediate in the rate-determining step. Also, the surface was enriched with Fe3+Δ, Co3+, and partially oxidized Ni3+ states, which is susceptible to tune the eg-orbital filling for superior oxygen redox activity.

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Despite numerous advantages over the traditional light absorbing materials, colloidal cesium lead halide (CsPbX 3 , X = Cl, Br, or I) perovskite nanocrystals (NCs) suffer from enormous defect density, leading to shorter lifetime of charge carriers and material instability. A large number of positively and negatively charged ionic defects are inevitably formed from crystallization via high temperature. Herein, we have studied a simple post-synthesis defect passivation of blue emitting CsPbCl 3 NCs using monovalent metal ion LiCl as a dual-passivating agent. The observed effect (on optical properties) went up by leaps and bounds. Photoluminescence (PL) quantum yield increases from 2.8 to 47.6%, while PL life time increases from 0.56 to 20.79 ns. Various other chloride salts (CaCl 2 , NH 2 Cl, KCl, and NaCl) and Li salts (LiBr and LiI) with different cation and anion combinations, respectively, did not give this effect. All these together with the enhanced overall stability of NCs suggest the synergistic effect of dual passivation and deep defect passivation that leads to significant suppression of non-radiative recombination. An X-ray photoelectron spectroscopy study also reveals that this simple strategy promotes simultaneous passivation of both defects (vacancies) formed from negatively (chlorine) and positively charged ions (lead) of CsPbCl 3. Theoretical study and experimental analysis in this work, together delivers a perceptive understanding of cationic and anionic vacancy healing by LiCl in CsPbCl 3 NCs, thus enhancing its utilization as efficient blue light emitters.