The widespread use of proton exchange membrane water electrolysis requires the development of more efficient electrocatalysts containing reduced amounts of expensive iridium for the oxygen evolution reaction (OER). Here we present the identification of 6H-phase SrIrO3 perovskite (6H-SrIrO3) as a highly active electrocatalyst with good structural and catalytic stability for OER in acid. 6H-SrIrO3 contains 27.1 wt% less iridium than IrO2, but its iridium mass activity is about 7 times higher than IrO2, a benchmark electrocatalyst for the acidic OER. 6H-SrIrO3 is the most active catalytic material for OER among the iridium-based oxides reported recently, based on its highest iridium mass activity. Theoretical calculations indicate that the existence of face-sharing octahedral dimers is mainly responsible for the superior activity of 6H-SrIrO3 thanks to the weakened surface Ir-O binding that facilitates the potential-determining step involved in the OER (i.e., O* + H2O → HOO* + H+ + e¯).

Few-layer black phosphorus (BP) with an anisotropic two-dimensional (2D)-layered structure shows potential applications in photoelectric conversion and photocatalysis, but is easily oxidized under ambient condition preferentially at its edge sites. Improving the ambient stability of BP nanosheets has been fulfilled by chemical functionalization, however this functionalization is typically non-selective. Here we show that edge-selective functionalization of BP nanosheets by covalently bonding stable C60 molecules leads to its significant stability improvement. Owing to the high stability of the hydrophobic C60 molecule, C60 functions as a sacrificial shield and effectively protects BP nanosheets from oxidation under ambient condition. C60 bonding leads to a rapid photoinduced electron transfer from BP to C60, affording enhanced photoelectrochemical and photocatalytic activities. The selective passivation of the reactive edge sites of BP nanosheets by sacrificial C60 molecules paves the way toward ambient processing and applications of BP.

For electrochemical energy conversion, highly efficient and inexpensive electrocatalysts are required, which are principally designed and synthesized by virtue of structural regulations. Herein, we propose a rational linker scission approach to induce lattice strain in metal–organic framework (MOF) catalysts by partially replacing multicoordinating linkers with nonbridging ligands. Strained NiFe-MOFs with 6% lattice expansion exhibit a superior catalytic performance for the oxygen evolution reaction (OER) under alkaline conditions; the overpotential is reduced to 230 mV (86.6 mV dec–1) from 320 mV (164.9 mV dec–1) for the unstrained NiFe-MOFs at a current density of 10 mA cm–2. Operando studies by using synchrotron radiation X-ray absorption and infrared spectroscopy identified the emergence of a key *OOH intermediate on Ni3+/4+ sites during OER, providing strong evidence that the Ni3+/4+ sites are the active sites and the formation of *OOH is the rate-limiting step. The first-principles calculations were performed to reveal the strain-induced electronic structure changes of the NiFe-MOFs and the Gibbs free energy profile during OER. It is found that the optimized Ni 3d eg-orbital facilitates the formation of *OOH, thus enhancing the OER performance of the strained MOFs.

Graphene is extremely promising for next-generation spintronics applications; however, realizing graphene-based room-temperature magnets remains a great challenge. Here, we demonstrate that robust room-temperature ferromagnetism with TC up to ∼400 K and saturation magnetization of 0.11 emu g−1 (300 K) can be achieved in graphene by embedding isolated Co atoms with the aid of coordinated N atoms. Extensive structural characterizations show that square-planar Co-N4 moieties were formed in the graphene lattices, where atomically dispersed Co atoms provide local magnetic moments. Detailed electronic structure calculations reveal that the hybridization between the d electrons of Co atoms and delocalized pz electrons of N/C atoms enhances the conduction-electron mediated long-range magnetic coupling. This work provides an effective means to induce room-temperature ferromagnetism in graphene and may open possibilities for developing graphene-based spintronics devices.

Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrO x particles anchored on 9R-BaIrO3 (IrO x /9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrO x /9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr –1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr –1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm–2 geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrO x nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+O x H y /IrO6 octahedrons and then to amorphous Ir5+O x /IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+O x species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+O x /9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

Tuning the local reaction environment is an important and challenging issue for determining electrochemical performances. Herein, we propose a strategy of intentionally engineering the local reaction environment to yield highly active catalysts. Taking Ptδ− nanoparticles supported on oxygen vacancy enriched MgO nanosheets as a prototypical example, we have successfully created a local acid-like environment in the alkaline medium and achieve excellent hydrogen evolution reaction performances. The local acid-like environment is evidenced by operando Raman, synchrotron radiation infrared and X-ray absorption spectroscopy that observes a key H3O+ intermediate emergence on the surface of MgO and accumulation around Ptδ− sites during electrocatalysis. Further analysis confirms that the critical factors of the forming the local acid-like environment include: the oxygen vacancy enriched MgO facilitates H2O dissociation to generate H3O+ species; the F centers of MgO transfers its unpaired electrons to Pt, leading to the formation of electron-enriched Ptδ− species; positively charged H3O+ migrates to negatively charged Ptδ− and accumulates around Ptδ− nanoparticles due to the electrostatic attraction, thus creating a local acidic environment in the alkaline medium.

Single-atom catalysts with high activity and efficient atom utilization have great potential in the electrocatalysis field, especially for rechargeable zinc−air batteries (ZABs). However, it is still a serious challenge to rationally construct a single-atom catalyst with satisfactory electrocatalytic activity and long-term stability. Here, we simultaneously realize the atomic-level dispersion of cobalt and the construction of carbon nanotube (CNT)-linked N-doped porous carbon nanofibers (NCFs) via an electrospinning strategy. In this hierarchical structure, the Co−N 4 sites provide efficient oxygen reduction/evolution electrocatalytic activity, the porous architectures of NCFs guarantee the active site's accessibility, and the interior CNTs enhance the flexibility and mechanical strength of porous fibers. As a binder-free air cathode, the as-prepared catalysts deliver superdurability of 600 h at 10 mA cm −2 for aqueous ZABs and considerable flexibility and a small voltage gap for all-solid-state ZABs. This work provides an effective single-atom design/ nanoengineering for superdurable zinc−air batteries.

Transition-metal sulfides are investigated as promising electrocatalysts for oxygen evolution reaction (OER) in alkaline media; however, the real active species remain elusive and the development of oxyhydroxides reconstructed from sulfides delivering stable large current density at low applied potentials is a great challenge. Here, we report a synergistic hybrid catalyst, composed of nanoscale heterostructures of Co9S8 and Fe3O4, that exhibits only a low potential of 350 mV and record stability of 120 h at the 500 mA cm–2 in 1.0 M KOH. Voltage-dependent soft X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy demonstrate that the initial Co9S8@Fe3O4 is reconstructed into CoOOH/CoO x @Fe3O4 and further to complete CoOOH@Fe3O4. Operando XAS and electron microscopy imaging analyses reveal that the completely reconstructed CoOOH acts as active species and Fe3O4 components prevent the aggregation of CoOOH. Operando infrared spectroscopy indicates cobalt superoxide species (*OOH) as the active intermediates during the OER process. Density functional theory calculations demonstrate the formation of *OOH as the rate-determining step of OER and CoOOH@Fe3O4 exhibits a lower energy barrier for OER. Our results provide an in-depth understanding of the dynamic surface structure evolutions of sulfide electrocatalysts for alkaline OER and insights into the design of excellent nanocatalysts for stable large current density.