Polarization-Switchable Electrochemistry of 2D Layered Bi2O2Se Bifunctional Microreactors by Ferroelectric Modulation.

Ferroelectric catalysts are known for altering surface catalytic activities by changing the direction of their electric polarizations. This study demonstrates polarization-switchable electrochemistry using layered bismuth oxyselenide (L-Bi2O2Se) bifunctional microreactors through ferroelectric modulation. A selective-area ionic liquid gating is developed with precise control over the spatial distribution of the dipole orientation of L-Bi2O2Se. On-chip microreactors with upward polarization favor the oxygen evolution reaction, whereas those with downward polarization prefer the hydrogen evolution reaction. The microscopic origin behind polarization-switchable electrochemistry primarily stems from enhanced surface adsorption and reduced energy barriers for reactions, as examined by nanoscale scanning electrochemical cell microscopy. Integrating a pair of L-Bi2O2Se microreactors consisting of upward or downward polarizations demonstrates overall water splitting in a full-cell configuration based on a bifunctional catalyst. The ability to modulate surface polarizations on a single catalyst via ferroelectric polarization switching offers a pathway for designing catalysts for water splitting.

Manipulating Ferroelectric Polarization and Spin Polarization of 2D CuInP2S6 Crystals for Photocatalytic CO2 Reduction.

Manipulating electronic polarizations such as ferroelectric or spin polarizations has recently emerged as an effective strategy for enhancing the efficiency of photocatalytic reactions. This study demonstrates the control of electronic polarizations modulated by ferroelectric and magnetic approaches within a two-dimensional (2D) layered crystal of copper indium thiophosphate (CuInP2S6) to boost the photocatalytic reduction of CO2. We investigate the substantial influence of ferroelectric polarization on the photocatalytic CO2 reduction efficiency, utilizing the ferroelectric-paraelectric phase transition and polarization alignment through electrical poling. Additionally, we explore enhancing the CO2 reduction efficiency by harnessing spin electrons through the synergistic introduction of sulfur vacancies and applying a magnetic field. Several advanced characterization techniques, including piezoresponse force microscopy, ultrafast pump-probe spectroscopy, in situ X-ray absorption spectroscopy, and in situ diffuse reflectance infrared Fourier transformed spectroscopy, are performed to unveil the underlying mechanism of the enhanced photocatalytic CO2 reduction. These findings pave the way for manipulating electronic polarizations regulated through ferroelectric or magnetic modulations in 2D layered materials to advance the efficiency of photocatalytic CO2 reduction.

Single-Layer Hexagonal Boron Nitride Nanopores as High-Performance Ionic Gradient Power Generators.

Atomically thin two-dimensional (2D) materials have emerged as promising candidates for efficient energy harvesting from ionic gradients. However, the exploration of robust 2D atomically thin nanopore membranes, which hold sufficient ionic selectivity and high ion permeability, remains challenging. Here, the single-layer hexagonal boron nitride (hBN) nanopores are demonstrated as various high-performance ion-gradient nanopower harvesters. Benefiting from the ultrathin atomic thickness and large surface charge (also a large Dukhin number), the hBN nanopore can realize fast proton transport while maintaining excellent cation selectivity even in highly acidic environments. Therefore, a single hBN nanopore achieves the pure osmosis-driven proton-gradient power up to ≈3 nW under 1000-fold ionic gradient. In addition, the robustness of hBN membranes in extreme pH conditions allows the ionic gradient power generation from acid-base neutralization. Utilizing 1 m HCl/KOH, the generated power can be promoted to an extraordinarily high level of ≈4.5 nW, over one magnitude higher than all existing ionic gradient power generators. The synergistic effects of ultrathin thickness, large surface charge, and excellent chemical inertness of 2D single-layer hBN render it a promising membrane candidate for harvesting ionic gradient powers, even under extreme pH conditions.

Spin-Polarized Photocatalytic CO2 Reduction of Mn-Doped Perovskite Nanoplates.

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr3 halide perovskite nanoplates (NPLs) to boost the photocatalytic CO2 reduction reaction (CO2RR) efficiencies by doping manganese cations (Mn2+) and applying an external magnetic field. Mn-doped CsPbBr3 (Mn-CsPbBr3) NPLs exhibit an outstanding photocatalytic CO2RR compared to pristine CsPbBr3 NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO2RR of Mn-CsPbBr3 NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr3 NPLs exhibit 5.7 times improved performance of photocatalytic CO2RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr3 NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO2RR efficiencies of Mn-CsPbBr3 NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO2RR efficiencies.

π-Extended Coumarins Derived with Nonhydrolyzable Iminophosphoranes as Two-Photon-Excited Fluorophores.

Novel coumarin-iminophosphorane (IPP) fluorophores that have stable resonance contributions from aza-ylides were formed by using the nonhydrolysis Staudinger reaction. The N═P formation reaction kinetics obey the conventional Staudinger reaction. The absorption and emission profiles of the coumarin-IPP derivatives can be fine-tuned: an electron-donating group at PPh3 enhances absorption and fluorescence, whereas an electron-withdrawing group at C-3 drives absorption and emission peaks toward blue-light wavelengths. Two-photon adsorption, accompanied by anti-Stokes fluorescence, is achieved under near-infrared femtosecond laser excitation.

Hysteresis-Free Contact Doping for High-Performance Two-Dimensional Electronics.

Contact doping is considered crucial for reducing the contact resistance of two-dimensional (2D) transistors. However, a process for achieving robust contact doping for 2D electronics is lacking. Here, we developed a two-step doping method for effectively doping 2D materials through a defect-repairing process. The method achieves strong and hysteresis-free doping and is suitable for use with the most widely used transition-metal dichalcogenides. Through our method, we achieved a record-high sheet conductance (0.16 mS·sq-1 without gating) of monolayer MoS2 and a high mobility and carrier concentration (4.1 × 1013 cm-2). We employed our robust method for the successful contact doping of a monolayer MoS2 Au-contact device, obtaining a contact resistance as low as 1.2 kΩ·µm. Our method represents an effective means of fabricating high-performance 2D transistors.

Bifunctional Monolayer WSe2/Graphene Self-Stitching Heterojunction Microreactors for Efficient Overall Water Splitting in Neutral Medium.

Developing efficient bifunctional electrocatalysts in neutral media to avoid the deterioration of electrodes or catalysts under harsh environments has become the ultimate goal in electrochemical water splitting. This work demonstrates the fabrication of an on-chip bifunctional two-dimensional (2D) monolayer (ML) WSe2/graphene heterojunction microreactor for efficient overall water splitting in a neutral medium (pH = 7). Through the synergistic atomic growth of the metallic Cr dopant and graphene stitching contact on the 2D ML WSe2, the bifunctional WSe2/graphene heterojunction microreactor consisting of a full-cell configuration demonstrates excellent performance for overall water splitting in a neutral medium. Atomic doping of metallic Cr atoms onto the 2D ML WSe2 effectively facilitates the charge transfer at the solid-liquid interface. In addition, the direct growth of the self-stitching graphene contact with the 2D WSe2 catalyst largely reduces the contact resistance of the microreactor and further improves the overall water splitting efficiency. A significant reduction of the overpotential of nearly 1000 mV at 10 mA cm-2 at the Cr-doped WSe2/graphene heterojunction microreactor compared to the ML pristine WSe2 counterpart is achieved. The bifunctional WSe2/graphene self-stitching heterojunction microreactor is an ideal platform to investigate the fundamental mechanism of emerging bifunctional 2D catalysts for overall water splitting in a neutral medium.

Using Exciton/Trion Dynamics to Spatially Monitor the Catalytic Activities of MoS2 during the Hydrogen Evolution Reaction.

The adsorption and desorption of electrolyte ions strongly modulates the carrier density or carrier type on the surface of monolayer-MoS2 catalyst during the hydrogen evolution reaction (HER). The buildup of electrolyte ions onto the surface of monolayer MoS2 during the HER may also result in the formation of excitons and trions, similar to those observed in gate-controlled field-effect transistor devices. Using the distinct carrier relaxation dynamics of excitons and trions of monolayer MoS2 as sensitive descriptors, an in situ microcell-based scanning time-resolved liquid cell microscope is set up to simultaneously measure the bias-dependent exciton/trion dynamics and spatially map the catalytic activity of monolayer MoS2 during the HER. This operando probing technique used to monitor the interplay between exciton/trion dynamics and electrocatalytic activity for two-dimensional transition metal dichalcogenides provides an excellent platform to investigate the local carrier behaviors at the atomic layer/liquid electrolyte interfaces during electrocatalytic reaction.

Two-Dimensional Bis(dithiolene)iron(II) Self-Powered UV Photodetectors with Ultrahigh Air Stability.

Organometallic two-dimensional (2D) nanosheets with tailorable components have recently fascinated the optoelectronic communities due to their solution-processable nature. However, the poor stability of organic molecules may hinder their practical application in photovoltaic devices. Instead of conventional organometallic 2D nanosheets with low weatherability, an air-stable π-conjugated 2D bis(dithiolene)iron(II) (FeBHT) coordination nanosheet (CONASH) is synthesized via bottom-up liquid/liquid interfacial polymerization using benzenehexathiol (BHT) and iron(II) ammonium sulfate [Fe(NH4)2(SO4)2] as precursors. The uncoordinated thiol groups in FeBHT are easily oxidized, but the Fe(NH4)2(SO4)2 dissociation rate is slow, which facilitates the protection of sulfur groups by iron(II) ions. The density functional theory calculates that the resultant FeBHT network gains the oxygen-repelling function for oxidation suppression. In air, the FeBHT CONASH exhibits self-powered photoresponses with short response times (<40 ms) and a spectral responsivity of 6.57 mA W-1, a specific detectivity of 3.13 × 1011 Jones and an external quantum efficiency of 2.23% under 365 nm illumination. Interestingly, the FeBHT self-powered photodetector reveals extremely high long-term air stability, maintaining over 94% of its initial photocurrent after aging for 60 days without encapsulation. These results open the prospect of using organometallic 2D materials in commercialized optoelectronic fields.

Fast growth of large-grain and continuous MoS2 films through a self-capping vapor-liquid-solid method.

Most chemical vapor deposition methods for transition metal dichalcogenides use an extremely small amount of precursor to render large single-crystal flakes, which usually causes low coverage of the materials on the substrate. In this study, a self-capping vapor-liquid-solid reaction is proposed to fabricate large-grain, continuous MoS2 films. An intermediate liquid phase-Na2Mo2O7 is formed through a eutectic reaction of MoO3 and NaF, followed by being sulfurized into MoS2. The as-formed MoS2 seeds function as a capping layer that reduces the nucleation density and promotes lateral growth. By tuning the driving force of the reaction, large mono/bilayer (1.1 mm/200 µm) flakes or full-coverage films (with a record-high average grain size of 450 µm) can be grown on centimeter-scale substrates. The field-effect transistors fabricated from the full-coverage films show high mobility (33 and 49 cm2 V-1 s-1 for the mono and bilayer regions) and on/off ratio (1 ~ 5 × 108) across a 1.5 cm × 1.5 cm region.