Zinc-air batteries have recently attracted considerable interest owing to the larger storage capacity and lower cost compared to their lithium-ion counterparts. Electrode catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play a critical role in the operation of rechargeable zinc-air batteries. Herein, we report a simple and scalable strategy to fabricate porous carbon polyhedra using Zn-doped Co-based zeolitic imidazolate frameworks (ZnCo-ZIFs) as precursors. Strikingly, Zn doping leads to smaller Co nanoparticles and higher nitrogen content, which in turn enhances the ORR and OER activities of the obtained porous carbon polyhedra. The synergistic effect of the N-doped carbon and cobalt nanoparticles in the composite, the improved conductivity resulting from the high graphitization of carbon, and the large surface area of the porous polyhedral structure resulted in porous carbon polyhedra with excellent ORR and OER electrocatalytic activity in alkaline media. More importantly, air cathodes based on the optimal porous carbon polyhedra further exhibited superior performance to Pt/C catalysts in primary and rechargeable zinc-air batteries.
Hierarchical nano-architectures comprised of ultrathin ternary selenide (CoNiSe2) nanorods were directly grown on nickel foam (NF). The integrated CoNiSe2/NF functions as a robust electrocatalyst with an extremely high activity and stability for emerging renewable energy technologies, and electrochemical oxygen and hydrogen evolution reactions (OER and HER, respectively). The overpotentials required to deliver a current density of 100 mA·cm?2 are as low as 307 and 170 mV for the OER and HER, respectively; therefore, the obtained CoNiSe2 is among the most promising earth-abundant catalysts for water splitting. Furthermore, our synthetic sample validates a two-electrode electrolyzer for reducing the cell voltage in the full water splitting reaction to 1.591 V to achieve a current density of 10 mA·cm?2, which offers a novel, inexpensive, integrated selenide/NF electrode for electrocatalytic applications.
The wetting properties of an electrode surface are of significant importance to the performance of electrochemical devices because electron transfer occurs at the electrode/electrolyte interface. Described in this paper is a low-cost metal oxide electrocatalyst (CuO)-based high-performance sensing device using an enzyme electrode with a solid/liquid/air triphase interface in which the oxygen level is constant and sufficiently high. We apply the sensing device to detect glucose, a model test analyte, and demonstrate a linear dynamic range up to 50 mM, which is about 25 times higher than that obtained using a traditional enzyme electrode with a solid/liquid diphase interface. Moreover, we show that sensing devices based on a triphase assaying interface are insensitive to the significant oxygen level fluctuation in the analyte solution.
The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m2·g−1), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial processes for energy conversion/storage systems, such as fuel cells, metal–air batteries, and water splitting. However, both reactions are severely restricted by their sluggish kinetics, thus requiring highly active, cost-effective, and durable electrocatalysts. Herein, we develop novel bifunctional nanocatalysts through surface nanoengineering of dealloying-driven nanoporous gold (NPG). Pd overlayers were precisely deposited onto the NPG ligament surface by epitaxial layer-by-layer growth. More importantly, the obtained NPG-Pd overlayer nanocatalysts exhibit remarkably enhanced electrocatalytic activities toward both the ORR and OER in alkaline media, benchmarked against a stateof- the-art Pt/C catalyst. The improved electrocatalytic performance is rationalized by the unique three-dimensional nanoarchitecture of NPG, enhanced Pd utilization efficiency from precise control of the Pd overlayers, and change in electronic structure, as revealed by density functional theory calculations.
A thermal emitter composed of a frequency-selective surface metamaterial layer and a hexagonal boron nitride-encapsulated graphene filament is demonstrated. The broadband thermal emission of the metamaterial (consisting of ring resonators) was tailored into two discrete bands, and the measured reflection and emission spectra agreed well with the simulation results. The high modulation frequencies that can be obtained in these devices, coupled with their operation in air, confirm their feasibility for use in applications such as gas sensing.
The development of an electrocatalyst based on abundant elements for the oxygen evolution reaction (OER) is important for water splitting associated with renewable energy sources. In this study, we develop an interconnected Ni(Fe)OxHy nanosheet array on a stainless steel mesh (SSNNi) as an integrated OER electrode, without using any polymer binder. Benefiting from the well-defined three-dimensional (3D) architecture with highly exposed surface area, intimate contact between the active species and conductive substrate improved electron and mass transport capacity, facilitated electrolyte penetration, and improved mechanical stability. The SSNNi electrode also has excellent OER performance, including low overpotential, a small Tafel slope, and long-term durability in the alkaline electrolyte, making it one of the most promising OER electrodes developed.
We have demonstrated the improved performance of oxygen evolution reactions (OER) using Au/nickel phosphide (Ni12P5) core/shell nanoparticles (NPs) under basic conditions. NPs with a Ni12P5 shell and a Au core, both of which have well-defined crystal structures, have been prepared using solution-based synthetic routes. Compared with pure Ni12P5 NPs and Au-Ni12P5 oligomer-like NPs, the core/shell crystalline structure with Au shows an improved OER activity. It affords a current density of 10 mA/cm2 at a small overpotential of 0.34 V, in 1 M KOH aqueous solution at room temperature. This enhanced OER activity may relate to the strong structural and effective electronic coupling between the single-crystal core and the shell.
Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotential of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. This increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.
This paper offers a comprehensive overview on the role of nanostructures in the development of advanced anode materials for application in both lithium and sodium-ion batteries. In particular, this review highlights the differences between the two chemistries, the critical effect of nanosize on the electrode performance, as well as the routes to exploit the inherent potential of nanostructures to achieve high specific energy at the anode, enhance the rate capability, and obtain a long cycle life. Furthermore, it gives an overview of nanostructured sodium- and lithium-based anode materials, and presents a critical analysis of the advantages and issues associated with the use of nanotechnology.
In this paper, we demonstrate that for colloidal CdSe/CdS nanoplatelets, a rectangular shape induces emission asymmetry, in terms of both polarization and emission patterns. Polarimetry and emission pattern analyses are combined to provide information on the orientation of the transition dipoles involved in the nanoplatelet emission. It is shown that for rectangular nanoplatelets, the emission is polarized and the emission patterns are anisotropic, whereas they remain nonpolarized and isotropic for square nanoplatelets. This can be appropriately described by the dielectric antenna effect induced by the elongated shape of the rectangular platelet.
A highly active and stable oxygen evolution reaction (OER) electrocatalyst is critical for hydrogen production from water splitting. Herein, three-dimensional Ni3S2@graphene@Co92S8 (Ni3S2@G@Co9S8), a sandwich-structured OER electrocatalyst, was grown in situ on nickel foam; it afforded an enhanced catalytic performance when highly conductive graphene is introduced as an intermediary for enhancing the electron transfer rate and stability. Serving as a free-standing electrocatalytic electrode, Ni3S2@G@Co9S8 presents excellent electrocatalytic activities for OER: A low onset overpotential (2 mA·cm?2 at 174 mV), large anode current density (10 mA·cm?2 at an overpotential of 210 mV), low Tafel slope (66 mV·dec?1), and predominant durability of over 96 h (releasing a current density of ～14 mA·cm?2 with a low and constant overpotential of 215 mV) in a 1 M KOH solution. This work provides a promising, cost-efficient electrocatalyst and sheds new light on improving the electrochemical performance of composites through enhancing the electron transfer rate and stability by introducing graphene as an intermediary.
Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium. As a critical component of sodium-ion batteries, anode materials, especially nanostructured anodes, have a significant effect on the electrochemical performance of sodium-ion batteries. Recent research indicates that phosphorus and metal phosphides show great promise as anode candidates for sodium-ion batteries because of their low cost and relatively high theoretical gravimetric and volumetric specific capacities. In this review, we systematically summarize recent research progress on state-of-the-art nanostructured phosphorus and phosphides, including the synthetic strategies, Na-storage mechanisms, and the relationship between the nanostructure and electrochemical performance. Moreover, we present an overview of future challenges and opportunities based on current developments.
Solid polymer electrolytes are light-weight, flexible, and non-flammable and provide a feasible solution to the safety issues facing lithium-ion batteries through the replacement of organic liquid electrolytes. Substantial research efforts have been devoted to achieving the next generation of solid-state polymer lithium batteries. Herein, we provide a review of the development of solid polymer electrolytes and provide comprehensive insights into emerging developments. In particular, we discuss the different molecular structures of the solid polymer matrices, including polyether, polyester, polyacrylonitrile, and polysiloxane, and their interfacial compatibility with lithium, as well as the factors that govern the properties of the polymer electrolytes. The discussion aims to give perspective to allow the strategic design of state-of-the-art solid polymer electrolytes, and we hope it will provide clear guidance for the exploration of high-performance lithium batteries.
Understanding how small molecules interface with amyloid fibrils at the nanoscale is of importance for developing therapeutic treatments against amyloid-based diseases. Here, we show for the first time that human islet amyloid polypeptides (IAPP) in the fibrillar form are polymorphic, ambidextrous, and possess multiple periodicities. Upon interfacing with the small molecule epigallocatechin gallate (EGCG), IAPP aggregation was rendered off-pathway and assumed a form with soft and disordered clusters, while mature IAPP fibrils displayed kinks and branching but conserved the twisted fibril morphology. These nanoscale phenomena resulted from competitive interactions between EGCG and the IAPP amyloidogenic region, as well as end capping of the fibrils by the small molecule. This information is crucial in delineating IAPP toxicity implicated in type 2 diabetes and for developing new inhibitors against amyloidogenesis.
Carbon quantum dots (CQDs) have emerged as potential alternatives to classical metal-based semiconductor quantum dots (QDs) due to the abundance of their precursors, their ease of synthesis, high biocompatibility, low cost, and particularly their strong photoresponsiveness, tunability, and stability. Light is a versatile, tunable stimulus that can provide spatiotemporal control. Its interaction with CQDs elicits interesting responses such as wavelength-dependent optical emissions, charge/electron transfer, and heat generation, processes that are suitable for a range of photomediated bioapplications. The carbogenic core and surface characteristics of CQDs can be tuned through versatile engineering strategies to endow specific optical and physicochemical properties, while conjugation with specific moieties can enable the design of targeted probes. Fundamental approaches to tune the responses of CQDs to photo-interactions and the design of bionanoprobes are presented, which enable biomedical applications involving diagnostics and therapeutics. These strategies represent comprehensive platforms for engineering multifunctional probes for nanomedicine, and the design of QD probes with a range of metal-free and emerging 2D materials.
ABSTRACT NiFe layered double hydroxide(NiFe-LDH)nanosheets and metal-nitrogen-carbon materials(M-N-C,M=Ni,Fe,Co,etc.)are supreme catalysts in the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)process,respectively.Nevertheless,the monotonic performance and insufficient stability severely hamper their practical application in rechargeable batteries.Herein,we simultaneously combine ultrathin NiFe-LDH nanowalls with renewable soybean-derived Fe-N-C matrix to obtain a hybrid materials(NiFe-LDH/FeSoy-CNSs-A),which exhibits robust catalytic activities for OER(Ej=10=1.53 V vs.RHE)and ORR(E1/2=0.91 V vs.RHE),with a top-notch battery parameters and stability in assembled rechargeable Zn-air batteries.Intensive investigations indicate that the vertically dispersed NiFe-LDH nanosheets,Fe-N-C matrix derived from soybean and the strong synergy between them are responsible for the unprecedented OER and ORR performances.The key role of intrinsic N defects involved in the hybrid materials is firstly specified by ultrasoundassisted extraction of soy protein from soybean.The exquisite design can facilitate the utilization of sustainable biomass-derived catalysts,and the mechanism investigations of N defects and oxygenic groups on the structure-activity relationship can stimulate the progress of other functional hybrid electrocatalysts. 相似文献
Despite the extensive application of porous nanostructures as oxygen electrocatalysts, it is challenging to synthesize single-metal state materials with porous structures, especially the ultrasmall ones due to the uniform diffusion of the same metal. Herein, we pioneer demonstrate a new size effect-based controllable synthesis strategy for the homogeneous Co nanokarstcaves assisted by Co-CN hybrids (CCHs). The preferential migration of cobalt atoms on the surface of small size zeolitic imidazolate framework (ZIF) with high surface energy during pyrolysis is the key factor for the formation of nanokarstcave structure. Furthermore, graphene can act as a diffusion barrier to prevent the agglomeration of nanoparticles in the synthesis process, which also plays an important role in the formation of porous nanostructures. In alkali media, CCHs achieve overpotential of 287 mV (@10 mA·cm−2) for oxygen evolution reaction (OER) and a half wave potential of 0.86 V (vs. RHE) for oxygen reduction reaction (ORR).
The development of high-efficiency electrocatalysts for oxygen evolution reactions (OERs) plays an important role in the water-splitting process. Herein, we report a facile way to obtain two-dimensional (2D) single-unit-cell-thick layered double hydroxide (LDH) nanosheets (NSs, ～1.3 nm) within only 5 min. These nanosheets presented significantly enhanced OER performance compared to bulk LDH systems fabricated using the conventional co-precipitation method. The current strategy further allowed control over the chemical compositions and electrochemical activities of the LDH NSs. For example, CoFe-LDH NSs presented the lowest overpotential of 0.28 V at 10 mA/cm2, and the NiFe-LDHs NSs showed Tafel slopes of 33.4 mV/decade and nearly 100% faradaic efficiency, thus outperforming state-of-the-art IrO2 water electrolysis catalysts. Moreover, positron annihilation lifetime spectroscopy and high-resolution transmission electron microscopy observations confirmed that rich defects and distorted lattices occurred within the 2D LDH NSs, which could supply abundant electrochemically active OER sites. Periodic calculations based on density functional theory (DFT) further showed that the CoFe- and NiFe-LDHs presented very low energy gaps and obvious spin-polarization behavior, which facilitated high electron mobility during the OER process. Therefore, this work presents a combined experimental and theoretical study on 2D single-unit-cell-thick LDH NSs with high OER activities, which have potential application in water splitting for renewable energy.
By combining ab initio calculations and experiments, we demonstrate how the band gap of the transition metal trichalcogenide TiS3 can be modified by inducing tensile or compressive strain. In addition, using our calculations, we predicted that the material would exhibit a transition from a direct to an indirect band gap upon application of a compressive strain in the direction of easy electrical transport. The ability to control the band gap and its nature could have a significant impact on the use of TiS3 for optical applications. We go on to verify our prediction via optical absorption experiments that demonstrate a band gap increase of up to 9% (from 0.99 to 1.08 eV) upon application of tensile stress along the easy transport direction.
