While the carbon-based metal-free electrocatalysts for oxygen reduction reaction (ORR) have experienced great progress in recent years, the fundamental issue on the origin of ORR activity is yet far from being clarified. To date, the ORR activities of these electrocatalysts are usually attributed to different dopants, while the contribution of intrinsic carbon defects has been little touched. Herein, we report the high ORR activity of the defective carbon nanocages, which is better than that of the B-doped carbon nanotubes and comparable to that of the N-doped carbon nanostructures. Density functional theory (DFT) calculations indicate that pentagon and zigzag edge defects are responsible for the high ORR activity. The mutually corroborated experimental and theoretical results reveal the significant contribution of the intrinsic carbon defects to ORR activity, which is crucial for understanding the ORR origin and exploring the advanced carbon-based metal-free electrocatalysts.

The synergism of large surface area, multiscale porous structure, and good conductivity endows hierarchical carbon nanocages with high-level supercapacitive performances. Further nitrogen doping greatly improves the hydrophilicity, which boosts the supercapacitive performances to an ultrahigh specific capacitance of up to 313 F g(-1) at 1 A g(-1).

Aprotic Li-O batteries represent promising alternative devices for electrical energy storage owing to their extremely high energy densities. Upon discharge, insulating solid LiO forms on cathode surfaces, which is usually governed by two growth models, namely the solution model and the surface model. These LiO growth models can largely determine the battery performances such as the discharge capacity, round-trip efficiency and cycling stability. Understanding the LiO formation mechanism and controlling its growth are essential to fully realize the technological potential of Li-O batteries. In this review, we overview the recent advances in understanding the electrochemical and chemical processes that occur during the LiO formation. In the beginning, the oxygen reduction mechanisms, the identification of O/LiO intermediates, and their influence on the LiO morphology have been discussed. The effects of the discharge current density and potential on the LiO growth model have been subsequently reviewed. Special focus is then given to the prominent strategies, including the electrolyte-mediated strategy and the cathode-catalyst-tailoring strategy, for controlling the LiO growth pathways. Finally, we conclude by discussing the profound implications of controlling LiO formation for further development in Li-O batteries.

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Black phosphorus (BP) shows great potential in electronic and optoelectronic devices owing to its semiconducting properties, such as thickness-dependent direct bandgap and ambipolar transport characteristics. However, the poor stability of BP in air seriously limits its practical applications. To develop effective schemes to protect BP, it is crucial to reveal the degradation mechanism under various environments. To date, it is generally accepted that BP degrades in air via light-induced oxidation. Herein, we report a new degradation channel via water-catalyzed oxidation of BP in the dark. When oxygen co-adsorbs with highly polarized water molecules on BP surface, the polarization effect of water can significantly lower the energy levels of oxygen (i.e. enhanced electron affinity), thereby facilitating the electron transfer from BP to oxygen to trigger the BP oxidation even in the dark environment. This new degradation mechanism lays important foundation for the development of proper protecting schemes in black phosphorus-based devices.

Aprotic Li-O 2 batteries are promising candidates for next-generation energy storage technologies owing to their high theoretical energy densities. However, their practically achievable specific energy is largely limited by the need for porous conducting matrices as cathode support and the passivation of cathode surface by the insulating Li 2 O 2 product. Herein, a self-standing and hierarchically porous carbon framework is reported with Co nanoparticles embedded within developed by 3D-printing of cobalt-based metal-organic framework (Co-MOF) using an extrusion-based printer, followed by appropriate annealing. The novel self-standing framework possesses good conductivity and necessary mechanical stability, so that it can act as a porous conducting matrix. Moreover, the porous framework consists of abundant micrometer-sized pores formed between Co-MOF-derived carbon flakes and meso-and micropores formed within the flakes, which together significantly benefit the efficient deposition of Li 2 O 2 particles and facilitate their decomposition due to the confinement of insulating Li 2 O 2 within the pores and the presence of Co electrocatalysts. Therefore, the self-standing porous architecture significantly enhances the cell's practical specific energy, achieving a high value of 798 Wh kg −1 cell . This study provides an effective approach to increase the practical specific energy for Li-O 2 batteries by constructing 3D-printed framework cathodes.

Controllable synthesis of single atom catalysts (SACs) with high loading remains challenging due to the aggregation tendency of metal atoms as the surface coverage increases. Here we report the synthesis of graphene supported cobalt SACs (Co1/G) with a tuneable high loading by atomic layer deposition. Ozone treatment of the graphene support not only eliminates the undesirable ligands of the pre-deposited metal precursors, but also regenerates active sites for the precise tuning of the density of Co atoms. The Co1/G SACs also demonstrate exceptional activity and high selectivity for the hydrogenation of nitroarenes to produce azoxy aromatic compounds, attributable to the formation of a coordinatively unsaturated and positively charged catalytically active center (Co–O–C) arising from the proximal-atom induced partial depletion of the 3d Co orbitals. Our findings pave the way for the precise engineering of the metal loading in a variety of SACs for superior catalytic activities.

For mass production of high‐purity hydrogen fuel by electrochemical water splitting, seawater electrolysis is an attractive alternative to the traditional freshwater electrolysis due to the abundance and low cost of seawater in nature. However, the undesirable chlorine ion oxidation reactions occurring simultaneously with seawater electrolysis greatly hinder the overall performance of seawater electrolysis. To tackle this problem, electrocatalysts of high activity and selectivity with purposely modulated coordination and an alkaline environment are urgently required. Herein, it is demonstrated that atomically dispersed Ni with triple nitrogen coordination (Ni‐N3) can achieve efficient hydrogen evolution reaction (HER) performance in alkaline media. The atomically dispersed Ni electrocatalysts exhibit overpotentials as low as 102 and 139 mV at 10 mA cm–2 in alkaline freshwater and seawater electrolytes, respectively, which compare favorably with those previously reported. They also deliver large current densities beyond 200 mA cm–2 at lower overpotentials than Pt/C, as well as show negligible current attenuation over 14 h. The X‐ray absorption fine structure (XAFS) experimental analysis and density functional theory (DFT) calculations verify that the Ni‐N3 coordination, which exhibits a lower coordination number than Ni‐N4, facilitates water dissociation and hydrogen adsorption, and hence enhances the HER activity.