Flexo-/Piezoelectric Polarization Boosting Exciton Dissociation in Curved Two-Dimensional Carbon Nitride Photocatalyst.

Two-dimensional (2D) carbon nitride (CN) materials have received tremendous attention as photocatalysts for clean energy and environmental treatment. However, the photocatalytic efficiency of CN is constrained by the high exciton binding energy and sluggish charge kinetics due to weak dielectric screening, impeding the overall process. Herein, localized flexo-/piezoelectric polarization is introduced via strain engineering, boosting exciton dissociation and promoting charge separation to enhance the multielectron photocatalytic process. Consequently, the exciton binding energy of polarized CN is reduced from 52 to 34 meV, and the hydrogen evolution yield increased by 2.9 times compared to that of the pristine CN. For other photocatalytic reactions (e.g., H2O2 production), the polarized CN also maintained a 2.1-fold increase compared to the pristine CN. This strategy of inducing localized polarization via strain engineering provides new insights for boosting photocatalytic reactions involving electrons.

Robust Carbon Nitride Homojunction Photoelectrode for Solar-Driven Water Splitting.

Achieving intimate particle-to-particle and particle-to-substrate contacts is the first priority for fabricating high-quality photoelectrodes to ensure sufficient visible light absorption and efficient charge separation/transport. To achieve this goal, a seeding strategy is designed to construct a robust carbon nitride (CN) homojunction photoelectrode, in which vaporized precursors are condensed into a compact seeding layer at low temperatures, inducing the further deposition of the top layer. This optimized photoelectrode displays an excellent photocurrent density of 320 µA cm-2 in 0.1 M NaOH electrolyte at 1.23 VRHE (V vs reversible hydrogen electrode) under AM 1.5G illumination, with H2 and O2 evolution rates of 2.98 and 1.47 µmol h-1 cm-2, respectively. Characterizations show that both the robust contact and the homojunction of the double-layered CN film contribute to enhanced photoelectrochemical performance. This work may provide a new strategy for the design of high-performing CN photoelectrodes.

Cu-Ion-Implanted and Polymeric Carbon Nitride-Decorated TiO2 Nanotube Array for Unassisted Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) water splitting over TiO2 photoanodes is a promising strategy for hydrogen production due to its eco-friendly, energy-saving, and low-cost nature. However, the intrinsic drawbacks of TiO2, i.e., the too wide band gap and rapid exciton recombination, significantly limit further enhancement of its performance. Herein, we report a TiO2 nanotube array (TNA), which is implanted by Cu ions and decorated by polymeric carbon nitride (PCN) nanosheets, as a photoanode for the high-efficiency PEC water splitting. In such designed material, Cu-ion implantation can effectively tailor the electronic structure of TiO2, thus narrowing the band gap and enhancing the electronic conductivity. Meanwhile, the PCN decoration induces TiO2/PCN heterojunctions, enhancing the visible light absorption and accelerating the exciton separation. Upon this synergistic effect, the modified TNA photoanode shows significantly improved PEC capability. Its photocurrent density, solar-to-hydrogen efficiency, and applied bias photon-to-current efficiency achieve 1.89 mA cm-2 at 1.23 VRHE (V vs reversible hydrogen electrode), 2.31%, and 1.20% at 0.46 VRHE, respectively. Importantly, this modified TNA supported on a meshlike Ti substrate can be readily integrated with a perovskite solar cell to realize unassisted PEC water splitting.

Ultralong-Discharge-Time Biobattery Based on Immobilized Enzymes in Bilayer Rolled-Up Enzymatic Nanomembranes.

Glucose biofuel cells (GBFCs) are highly promising power sources for implantable biomedical and consumer electronics because they provide a high energy density and safety. However, it remains a great challenge to combine their high power density with reliable long-term stability. In this study, a novel GBFC design based on the enzyme biocatalysts glucose dehydrogenase, diaphorase, and bilirubin oxidase immobilized in rolled-up titanium nanomembranes is reported. The setup delivers a maximum areal power density of ≈3.7 mW cm-2 and a stable power output of ≈0.8 mW cm-2 . The power discharges over 452 h, which is considerably longer than reported previously. These results demonstrate that the GBFC design is in principle a feasible and effective approach to solve the long-term discharge challenge for implantable biomedical device applications.

Investigating the behavior of various cocatalysts on LaTaON2 photoanode for visible light water splitting.

We performed a comparative study on the photoelectrochemical performance of LaTaON2 loaded with NiOx, Ni0.7Fe0.3Ox, CoOx and IrOx as cocatalysts. Ni-based oxides lead to the highest improvement on the photoelectrochemical performance, while CoOx and IrOx also enhance the performance though to a lower extent, but they simultaneously introduce more pseudocapacitive current thus resulting in an inefficient utilization of the photo-generated holes. Repetitive voltage cycling between 1.0 VRHE and 1.6 VRHE transforms the NiOx and Ni0.7Fe0.3Ox into oxyhydroxides known to possess higher catalytic activities. However, these oxyhydroxides lead to lower photoelectrochemical performance compared to the as-loaded oxides, most probably due to the decay of the passivation centers at the photoelectrode-cocatalyst interface. High catalytic activities cannot be achieved without sufficient passivation of surface recombination states. Despite that the photoelectrochemical performance of LaTaON2 can be improved by cocatalysts, the maximum achievable photocurrent density is still not comparable to that reported for other oxynitride compounds. Our study suggests that poor electronic conductivity or severe bulk recombination of the photo-generated electron-hole pairs are the main limiting factors for the photon-to-current conversion efficiency in LaTaON2 photoanodes.

Sandwich nanoarchitecture of Si/reduced graphene oxide bilayer nanomembranes for Li-ion batteries with long cycle life.

The large capacity loss and huge volume change of silicon anodes severely restricts their practical applications in lithium ion batteries. In this contribution, the sandwich nanoarchitecture of rolled-up Si/reduced graphene oxide bilayer nanomembranes was designed via a strain released strategy. Within this nanoarchitecture, the inner void space and the mechanical feature of nanomembranes can help to buffer the strain during lithiation/delithiation; the alternately stacked conductive rGO layers can protect the Si layers from excessive formation of SEI layers. As anodes for lithium-ion batteries, the sandwiched Si/rGO nanoarchitecture demonstrates long cycling life of 2000 cycles at 3 A g(-1) with a capacity degradation of only 3.3% per 100 cycles.

High-rate amorphous SnO2 nanomembrane anodes for Li-ion batteries with a long cycling life.

Amorphous SnO2 nanomembranes as anodes for lithium ion batteries demonstrate a long cycling life of 1000 cycles at 1600 mA g(-1) with a high reversible capacity of 854 mA h g(-1) and high rate capability up to 40 A g(-1). The superior performance is because of the structural features of the amorphous SnO2 nanomembranes. The nanoscale thickness provides considerably reduced diffusion paths for Li(+). The amorphous structure can accommodate the strain of lithiation/delithiation, especially during the initial lithiation. More importantly, the mechanical feature of deformation can buffer the strain of repeated lithiation/delithiation, thus putting off pulverization. In addition, the two-dimensional transport pathways in between nanomembranes make the pseudo-capacitance more prominent. The encouraging results demonstrate the significant potential of nanomembranes for high power batteries.

High-Performance Li-O2 Batteries with Trilayered Pd/MnO x /Pd Nanomembranes.

Trilayered Pd/MnO x /Pd nanomembranes are fabricated as the cathode catalysts for Li-O2 batteries. The combination of Pd and MnO x facilitates the transport of electrons, lithium ions, and oxygen-containing intermediates, thus effectively decomposing the discharge product Li2O2 and significantly lowering the charge overpotential and enhancing the power efficiency. This is promising for future environmentally friendly applications.

Free-standing Fe2O3 nanomembranes enabling ultra-long cycling life and high rate capability for Li-ion batteries.

With Fe2O3 as a proof-of-concept, free-standing nanomembrane structure is demonstrated to be highly advantageous to improve the performance of Li-ion batteries. The Fe2O3 nanomembrane electrodes exhibit ultra-long cycling life at high current rates with satisfactory capacity (808 mAh g(-1) after 1000 cycles at 2 C and 530 mAh g(-1) after 3000 cycles at 6 C) as well as repeatable high rate capability up to 50 C. The excellent performance benefits particularly from the unique structural advantages of the nanomembranes. The mechanical feature can buffer the strain of lithiation/delithiation to postpone the pulverization. The two-dimensional transport pathways in between the nanomembranes can promote the pseudo-capacitive type storage. The parallel-laid nanomembranes, which are coated by polymeric gel-like film and SEI layer with the electrolyte in between layers, electrochemically behave like numerous "mini-capacitors" to provide the pseudo-capacitance thus maintain the capacity at high rate.

Schottky contact on ultra-thin silicon nanomembranes under light illumination.

By repeating oxidation and subsequent wet chemical etching, we produced ultra-thin silicon nanomembranes down to 10 nm based on silicon-on-insulator structures in a controllable way. The electrical property of such silicon nanomembranes is highly influenced by their contacts with metal electrodes, in which Schottky barriers (SBs) can be tuned by light illumination due to the surface doping. Thermionic emission theory of carriers is applied to estimate the SB at the interface between metal electrodes and Si nanomembranes. Our work reveals that the Schottky contacts with Si nanomembranes can be influenced by external stimuli (like light luminescence or surface state) more heavily compared to those in the thicker ones, which implies that such ultra-thin-film devices could be of potential use in optical detectors.

A single rolled-up Si tube battery for the study of electrochemical kinetics, electrical conductivity, and structural integrity.

A lab-on-chip device is demonstrated for probing the electrochemical kinetics, electrical properties, and structure integrity of a single Si rolled-up tube as the anode in lithium-ion batteries. Cyclic voltammetry of the tube exhibits better-resolved peaks than of the planar film due to the enhanced diffusion. The tube is wrinkled after cycling. The tube could be used as a promising ultra-microelectrode for other voltammetry research.

A highly flexible and compact magnetoresistive analytic device.

A grand vision of realization of smart and compact multifunctional microfluidic devices for wearable health monitoring, environment sensing and point-of-care tests emerged with the fast development of flexible electronics. As a vital component towards this vision, magnetic functionality in flexible fluidics is still missing although demanded by the broad utility of magnetic nanoparticles in medicine and biology. Here, we demonstrate the first flexible microfluidic analytic device with integrated high-performance giant magnetoresistive (GMR) sensors. This device can be bent to a radius of 2 mm while still retaining its full performance. Various dimensions of magnetic emulsion droplets can be probed with high precision using a limit of detection of 0.5 pl, providing broad applicability in high-throughput droplet screening, flow cytometry and drug development. The flexible feature of this analytic device holds great promise in the realization of wearable, implantable multifunctional platforms for biomedical, pharmaceutical and chemical applications.

Hierarchically designed SiOx/SiOy bilayer nanomembranes as stable anodes for lithium ion batteries.

Hierarchically designed SiOx /SiOy rolled-up bilayer nanomembranes are used as anodes for lithium-ion batteries. The functionalities of the SiO(x,y) layers can be engineered by simply controlling the oxygen content, resulting in anodes that exhibit a reversible capacity of about 1300 mA h g(-1) with an excellent stability of over 100 cycles, as well as a good rate capability.

Highly conductive and strain-released hybrid multilayer Ge/Ti nanomembranes with enhanced lithium-ion-storage capability.

Highly conductive and hybridized microtubes relying on strain-released ultrathin Ti/Ge bilayer nanomembranes are reported. These hybrid multilayer microtubes show a remarkably enhanced reversible capacity up to 1495 mA h g(-1) with a high first-cycle Coulombic efficiency of 85%, and demonstrate an excellent capacity of ≈930 mA h g(-1) after 100 cycles.