Due to their layered structure, two-dimensional Ruddlesden-Popper perovskites (RPPs), composed of multiple organic/inorganic quantum wells, can in principle be exfoliated down to few and single layers. These molecularly thin layers are expected to present unique properties with respect to the bulk counterpart, due to increased lattice deformations caused by interface strain. Here, we have synthesized centimetre-sized, pure-phase single-crystal RPP perovskites (CH(CH)NH)(CHNH)PbI (n = 1-4) from which single quantum well layers have been exfoliated. We observed a reversible shift in excitonic energies induced by laser annealing on exfoliated layers encapsulated by hexagonal boron nitride. Moreover, a highly efficient photodetector was fabricated using a molecularly thin n = 4 RPP crystal, showing a photogain of 10 and an internal quantum efficiency of ~34%. Our results suggest that, thanks to their dynamic structure, atomically thin perovskites enable an additional degree of control for the bandgap engineering of these materials.

Among van der Waals layered ferromagnets, monolayer vanadium diselenide (VSe2) stands out due to its robust ferromagnetism. However, the exfoliation of monolayer VSe2 is challenging, not least because the monolayer flake is extremely unstable in air. Using an electrochemical exfoliation approach with organic cations as the intercalants, monolayer 1T‐VSe2 flakes are successfully obtained from the bulk crystal at high yield. Thiol molecules are further introduced onto the VSe2 surface to passivate the exfoliated flakes, which improves the air stability of the flakes for subsequent characterizations. Room‐temperature ferromagnetism is confirmed on the exfoliated 2D VSe2 flakes using a superconducting quantum interference device (SQUID), X‐ray magnetic circular dichroism (XMCD), and magnetic force microscopy (MFM), where the monolayer flake displays the strongest ferromagnetic properties. Se vacancies, which can be ubiquitous in such materials, also contribute to the ferromagnetism of VSe2, although density functional theory (DFT) calculations show that such effect can be minimized by physisorbed oxygen molecules or covalently bound thiol molecules.

Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal-air batteries. Herein, we report a directional freeze-casting and annealing approach for the construction of 3D honeycomb nanostructured, N, P-doped carbon aerogel incorporating in situ grown FeP/Fe 2 O 3 nanoparticles as the cathode for flexible Zn-air battery. The aqueous rechargeable Zn-air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g -1 at current density of 20 mA cm -2 with good long-term durability, outperforming those assembled with commercial Pt/C+RuO 2 catalyst. Furthermore, such foldable carbon aerogel with directional channels can serve as freestanding air cathode for flexible solid state Zn-air battery without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mA h g -1 and an energy density of 517 W

The development of efficient electrocatalysts that lower the overpotential of oxygen evolution reaction (OER) is of great importance in improving the overall efficiency of hydrogen fuel production by water electrolysis. [1] Commercially, precious metal oxides catalysts such as IrO 2 are used. [2] However, their elemental scarcity and high cost have triggered a search for cost-effective OER electrocatalysts such as 3d transition metal oxides. Among them, families such as the perovskite ABO 3 and the spinel AB 2 O 4 ones have attracted great attention due to their tunable structural/elemental properties allowed by A and B site cation substitution. [3,4] Perovskite ABO 3 oxides have a simple structure with rare-earth or alkaline earth element occupying cuboctahedral A-site while the B-site transition metal (TM) sites in an octahedral environment. [3] Spinel oxides, however, can be either normal or inverse structure depending on the relative occupancy of divalent and trivalent cations in the octahedral and Developing highly active electrocatalysts for oxygen evolution reaction (OER) is critical for the effectiveness of water splitting. Low-cost spinel oxides have attracted increasing interest as alternatives to noble metalbased OER catalysts. A rational design of spinel catalysts can be guided by studying the structural/elemental properties that determine the reaction mechanism and activity. Here, using density functional theory (DFT) calculations, it is found that the relative position of O p-band and M Oh (Co and Ni in octahedron) d-band center in ZnCo 2−x Ni x O 4 (x = 0-2) correlates with its stability as well as the possibility for lattice oxygen to participate in OER. Therefore, it is testified by synthesizing ZnCo 2−x Ni x O 4 spinel oxides, investigating their OER performance and surface evolution. Stable ZnCo 2−x Ni x O 4 (x = 0-0.4) follows adsorbate evolving mechanism under OER conditions. Lattice oxygen participates in the OER of metastable ZnCo 2−x Ni x O 4 (x = 0.6, 0.8) which gives rise to continuously formed oxyhydroxide as surface-active species and consequently enhances activity. ZnCo 1.2 Ni 0.8 O 4 exhibits performance superior to the benchmarked IrO 2 . This work illuminates the design of highly active metastable spinel electrocatalysts through the prediction of the reaction mechanism and OER activity by determining the relative positions of the O p-band and the M Oh d-band center.

oxygen evolution reaction or OER) processes. [1][2][3][4][5] To avoid the use of costly noble metal catalysts, nitrogen-doped porous carbon materials are proposed as the electrode materials in these batteries since they can be derived from naturally abundant biomass. The performance of these porous carbon materials as electrodes depends on the chemistry that results in the generation of OER-active pyridinic N and ORR-active quaternary N groups in a high density as well as the porosity of the materials. [6] This is because these factors determine the extent of exposure of the active sites to the relevant chemical species such as O 2 , OH − , and H 2 O and help prevent the rapid clogging of the planar electrode surface. [7][8][9][10] SiO 2 [8,11,12] and Al 2 O 3[13] microbeads have been employed widely as templates for generating nanopores in carbon-based catalysts. However, this requires multiple steps such as the bottom-up synthesis of the catalysts from carbon precursors as well as etching and purification processes to remove the templates, which increases the cost for mass production. [14][15][16][17][18] In addition, porous carbon materials synthesized by bottom-up methods are generally in the powder form and are thus not self-supporting. Thus, the fabrication of air electrodes requires an additional process, wherein the powder carbon materials are electrosprayed onto carbon cloth/paper, which then lead to the inevitable decreases Porous carbon electrodes have emerged as important cathode materials for metal-air battery systems. However, most approaches for fabricating porous carbon electrodes from biomass are highly energy inefficient as they require the breaking down of the biomass and its subsequent reconstitution into powder-like carbon. Here, enzymes are explored to effectively hydrolyze the partial cellulose in bulk raw wood to form a large number of nanopores, which helps to maximally expose the inner parts of the raw wood to sufficiently dope nitrogen onto the carbon skeletons during the subsequent pyrolysis process. The resulting carbons exhibit excellent catalytic activity with respect to the oxygen reduction and oxygen evolution reactions. As-fabricated cellulosedigested, carbonized wood plates are mechanically strong, have high conductivity, and contain a crosslinked network and natural ion-transport channels and can be employed directly as metal-free electrodes without carbon paper, polymer binders, or carbon black. When used as metal-free cathodes in zincair batteries, they result in a specific capacity of 801 mA h g −1 and an energy density of 955 W h kg −1 with the long-term stability of the batteries being as high as 110 h. This work paves the way for the ready conversion of abundant biomass into high-value engineering products for energy-related applications.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201900341.Rechargeable Zn-air batteries have emerged as a promising technology for coping with future energy demands owin...

Two-dimensional hybrid organic-inorganic Ruddlesden-Popper perovskites (RPPs) have attracted considerable attention due to their rich photonic and optoelectronic properties. The natural multi-quantum-well structure of 2D RPPs has been predicted to exhibit a large third-order nonlinearity. However, nonlinear optical studies on 2D RPPs have previously been conducted only on bulk polycrystalline samples, in which only weak third-harmonic generation (THG) has been observed. Here, we perform parametric nonlinear optical characterization of 2D perovskite nanosheets mechanically exfoliated from four different lead halide RPP single crystals, from which we observe ultrastrong THG with a maximum effective third-order susceptibility (χ) of 1.12 × 10 m V. A maximum conversion efficiency of 0.006% is attained, which is more than 5 orders of magnitude higher than previously reported values for 2D materials. The THG emission is resonantly enhanced at the excitonic band gap energy of the 2D RPP crystals and can be tuned from violet to red by selecting the RPP homologue with the requisite resonance. Due to signal depletion effects and phase-matching conditions, the strongest nonlinear response is achieved for thicknesses less than 100 nm.

Ultrathin ferroelectrics hold great promise for modern miniaturized sensors, memories, and optoelectronic devices. However, in most ferroelectric materials, polarization is destabilized in ultrathin films by the intrinsic depolarization field. Here we report robust in-plane ferroelectricity in fewlayer tin sulfide (SnS) 2D crystals that is coupled anisotropically to lattice strain. Specifically, the intrinsic polarization of SnS manifests as nanoripples along the armchair direction due to a converse piezoelectric effect. Most interestingly, such nanoripples show an odd-and-even effect in terms of its layer dependence, indicating that it is highly sensitive to changes in inversion symmetry. Ferroelectric switching is demonstrated in field-effect transistor devices fabricated on ultrathin SnS films, in which a stronger ferroelectric response is achieved at negative gate voltages. Our work shows the promise of 2D SnS in ultrathin ferroelectric field-effect transistors as well as nanoscale electromechanical systems.

High-current density (≥1 A cm–2) is a critical factor for large-scale industrial application of water-splitting electrocatalysts, especially seawater-splitting. However, it still remains a great challenge to reach high-current density due to the lack of active and stable intrinsic catalytic active sites in catalysts. Herein, we report an original three-dimensional self-supporting graphdiyne/molybdenum oxide (GDY/MoO3) material for efficient hydrogen evolution reaction via a rational design of “sp C–O–Mo hybridization” on the interface. The “sp C–O–Mo hybridization” creates new intrinsic catalytic active sites (nonoxygen vacancy sites) and increases the amount of active sites (eight times higher than pure MoO3). The “sp C–O–Mo hybridization” facilitates charge transfer and boosts the dissociation process of H2O molecules, leading to outstanding HER activity with high-current density (>1.2 A cm–2) in alkaline electrolyte and a decent activity and stability in natural seawater. Our results show that high-current density electrocatalysts can be achieved by interfacial chemical bond engineering, three-dimensional structure design, and hydrophilicity optimization.