We investigated the fundamental properties of MAPbBr3 single crystal by applying temperature-dependent x-ray diffraction and photoluminescence (PL) measurements from 10 K to 270 K. The structural and spectral analyses illustrate the phase transitions of MAPbBr3 single crystal from cubic phase (-MAPbBr3) to tetragonal phases (-MAPbBr3 and -MAPbBr3), and then to orthorhombic phase (-MAPbBr3) at ~230 K, ~160 K and ~150 K, respectively. The Time-resolved PL results show that both free excitons (FE) and bound excitons (BE) have contributions to the PL emissions. The PL at high temperature mainly originates from the BE transitions, while the PL at low temperature (-MAPbBr3 phase) comes from both BE and FE transitions, and the FE related PL becomes more and more dominant at lower temperatures. The first-principle calculation at zero temperature reveals that the BE-related PL was caused by defects from the anti-site substitution of MA and Br ions.

The ability to tune both local and global environments of a singlemetal active center on a support is crucial for the development of highly robust and efficient single-atom electrocatalysts (SAECs) that can surmount both thermodynamic and kinetic constraints in electrocatalysis. Here, we designed a core−shellstructured SAEC (Co 1 -SAC) with superior oxygen reduction reaction (ORR) performance. Co 1 -SAC consists of a locally engineered single Co-N 3 C 1 site on a Ndoped microporous amorphous carbon support enveloped by a globally engineered highly conductive mesoporous graphitic carbon shell. Theoretical calculations reveal that Co-N 3 C 1 exhibits near-Fermi electronic states distinct from those of Co-N 2 C 2 and Co-N 4 , which facilitate both the electronic hybridization with O 2 and the subsequent protonation of adsorbed O 2 * toward the formation of OOH*. Engineering Co-N 3 C 1 -SAC into a micro/mesoporous core−shell structure dramatically enhances the mass transport and electron transfer, which further boosts the ORR and Zn-air battery performance (slightly outperforming Pt/C). Our findings open an avenue toward engineering of the local and global environment of SACs for a wide range of efficient electrochemical conversions.

Membranes based on two-dimensional (2D) nanomaterials have shown great potential to alleviate the worldwide freshwater crisis due to their outstanding performance of freshwater extraction from saline water via ion rejection. However, it is still very challenging to achieve high selectivity and high permeance of water desalination through precise d-spacing control of 2D nanomaterial membranes within subnanometer. Here, we developed functionalized graphene oxide membranes (FGOMs) with nitrogen groups such as amine groups and polarized nitrogen atoms to enhance metal ion sieving by one-step controlled plasma processing. The nitrogen functionalities can produce strong electrostatic interactions with metal ions and result in a mono/divalent cation selectivity of FGOMs up to 90 and 28.3 in single and binary solution, which is over 10-fold than that of graphene oxide membranes (GOMs). First-principles calculation confirms that the ionic selectivity of FGOMs is induced by the difference of binding energies between metal ions and polarized nitrogen atoms. Besides, the ultrathin FGOMs with a thickness of 50 nm can possess a high water flux of up to 120 mol m–2 h–1 without sacrificing rejection rates of nearly 99.0% on NaCl solution, showing an ultrahigh water/salt selectivity of around 4.31 × 103. Such facile and efficient plasma processing not only endows the GOMs with a promising future sustainable water purification, including ion separation and water desalination, but also provides a new strategy to functionalize 2D nanomaterial membranes for specific purposes.

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