Cu-Sn Aerogels for Electrochemical CO2 Reduction with High CO Selectivity.

This work reports the synthesis of CuxSny alloy aerogels for electrochemical CO2 reduction catalysts. An in situ reduction and the subsequent freeze-drying process can successfully give CnxSny aerogels with tuneable Sn contents, and such aerogels are composed of three-dimensional architectures made from inter-connected fine nanoparticles with pores as the channels. Density functional theory (DFT) calculations show that the introduction of Sn in Cu aerogels inhibits H2 evolution reaction (HER) activity, while the accelerated CO desorption on the catalyst surface is found at the same time. The porous structure of aerogel also favors exposing more active sites. Counting these together, with the optimized composition of Cu95Sn5 aerogel, the high selectivity of CO can be achieved with a faradaic efficiency of over 90% in a wide potential range (-0.7 V to -1.0 V vs. RHE).

Rational Design of Porous Structured Nickel Manganese Sulfides Hexagonal Sheets-in-Cage Structures as an Advanced Electrode Material for High-Performance Electrochemical Capacitors.

The design of hierarchical electrodes comprising multiple components with a high electrical conductivity and a large specific surface area has been recognized as a feasible strategy to remarkably boost pseudocapacitors. Herein, we delineate hexagonal sheets-in-cage shaped nickel-manganese sulfides (Ni-Mn-S) with nanosized open spaces for supercapacitor applications to realize faster redox reactions and a lower charge-transfer resistance with a markedly enhanced specific capacitance. The hybrid was facilely prepared through a two-step hydrothermal method. Benefiting from the synergistic effect between Ni and Mn active sites with the improvement of both ionic and electric conductivity, the resulting Ni-Mn-S hybrid displays a high specific capacitance of 1664 F g-1 at a current density of 1 A g-1 and a capacitance of 785 F g-1 is maintained at a current density of 50 A g-1 , revealing an outstanding capacity and rate performance. The asymmetric supercapacitor device assembled with the Ni-Mn-S hexagonal sheets-in-cage as the positive electrode delivers a maximum energy density of 40.4 Wh kg-1 at a power density of 750 W kg-1 . Impressively, the cycling retention of the as-fabricated device after 10 000 cycles at a current density of 10 A g-1 reaches 85.5 %. Thus, this hybrid with superior capacitive performance holds great potential as an effective charge-storage material.

Synthesis of porous Ag2S-NiCo2S4 hollow architecture as effective electrode material with high capacitive performances.

Fabrication of highly reactive and cost-effective electrode materials is a key to efficient functioning of green energy technologies. Decorating redox-active metal sulfides with conductive dopants is one of the most effective approaches to enhance electric conductivity and consequently boost capacitive properties. Herein, hierarchically hollow Ag2S-NiCo2S4 architectures are designed with an enhanced conductivity by a simple solvothermal approach. With the favorable porous characteristics and composition, the optimized Ag2S-NiCo2S4-5 electrode exhibits higher specific capacitance (276.5 mAh g-1 at a current density of 1 A g-1), a good rate performance (56.3% capacity retention at 50 A g-1), and an improved cycling stability (92.4% retention after 2000 cycles). This finding originates from the enhanced charge transportation ability within the hierarchical structure, abundant electroactive sites, and low contact resistance. In addition, a battery supercapacitor device constructed with the Ag2S-NiCo2S4-5 as a positive electrode displays a maximum energy density of 63.3Wh kg-1 at an energy density of 821.8 W kg-1 with an excellent cycling stability (89.4% capacity retention after 10 000 cycles). Therefore, the present work puts forward new possibility to develop composite electrodes for energy storage battery-supercapacitor.

N2 plasma-activated NiO nanosheet arrays with enhanced water splitting performance.

NiO is a promising electrocatalyst for electrochemical energy conversion due to its rich redox sites, low cost, and ease of synthesis. However, hindered by low electrical conductivity and limited electrocatalytic active sites, bare NiO usually exhibits poor electrochemical performance towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we develop an N2 plasma activation approach to simultaneously improve both HER and OER activity of NiO by constructing heterostructured Ni/Ni3N/NiO nanosheet arrays on Ni foam. The optimized N2 plasma-activated NiO nanosheet arrays for HER and OER (denoted as P-NiO-HER and P-NiO-OER) only need an overpotential of 46 and 294 mV, respectively, to achieve 10 mA cm-2. Moreover, for overall water splitting, the assembled electrolysis cell with P-NiO-HER and P-NiO-OER as the cathode and anode, respectively, only requires a small voltage of 1.57 V to deliver 10 mA cm-2. Remarkably, the plasma-activated NiO nanosheet arrays exhibit excellent stability for up to 50 h for HER, OER, and full water electrolysis. The strategy developed here to activate the electrocatalytic performance of metal oxides opens a new door for water splitting.

Electrospinning metal Phosphide/Carbon nanofibers from Phytic Acid for hydrogen evolution reaction catalysts.

This paper reports a general electrospinning method to prepare various metal phosphide/carbon nanofibers composite for electrochemical hydrogen evolution reaction (HER) catalysts. An earth-abundant organic acid-phytic acid is successfully incorporated into a conventional electrospinning precursor as the phosphorus source, and continuous nanofibers can be obtained through spinning. After heat treatment, metal phosphide/carbon composite nanofibers can be obtained, with fine phosphide nanoparticles well dispersed on the surface of an interconnected carbon backbone network. Such fibrous structures offer fast charge transfer pathways and enlarged active surface area, which are beneficial for electrocatalysts. As a result, enhance HER catalytic activity can be achieved.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances.

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g-1) and large pore volume (0.87 cm3 g-1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g-1 at 1 A g-1), good rate capability (74.3% capacitance retention from 1 to 20 A g-1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Mesoporous Piezoelectric Polymer Composite Films with Tunable Mechanical Modulus for Harvesting Energy from Liquid Pressure Fluctuation.

Harvesting mechanical energy from biological systems possesses great potential for in vivo powering implantable electronic devices. In this paper, a development of flexible piezoelectric nanogenerator (NG) is reported based on mesoporous poly(vinylidene fluoride) (PVDF) films. Monolithic mesoporous PVDF is fabricated by a template-free sol-gel-based approach at room temperature. By filling the pores of PVDF network with poly(dimethylsiloxane) (PDMS) elastomer, the composite's modulus is effectively tuned over a wide range down to the same level of biological systems. A close match of the modulus between NG and the surrounding biological component is critical to achieve practical integration. Upon deformation, the composite NG exhibits appreciable piezoelectric output that is comparable to or higher than other PVDF-based NGs. An artificial artery system is fabricated using PDMS with the composite NG integrated inside. Effective energy harvesting from liquid pressure fluctuation (simulating blood pressure fluctuation) is successfully demonstrated. The simple and effective approach for fabricating mesoporous PVDF with tunable mechanical properties provides a promising route toward the development of self-powered implantable devices.

Hierarchical NiCo2 O4 Hollow Microcuboids as Bifunctional Electrocatalysts for Overall Water-Splitting.

Bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline electrolyte may improve the efficiency of overall water splitting. Nickel cobaltite (NiCo2 O4 ) has been considered a promising electrode material for the OER. However, NiCo2 O4 that can be used as an electrocatalyst in HER has not been studied yet. Herein, we report self-assembled hierarchical NiCo2 O4 hollow microcuboids for overall water splitting including both the HER and OER reactions. The NiCo2 O4 electrode shows excellent activity toward overall water splitting, with 10 mA cm(-2) water-splitting current reached by applying just 1.65 V and 20 mA cm(-2) by applying just 1.74 V across the two electrodes. The synthesis of NiCo2 O4 microflowers confirms the importance of structural features for high-performance overall water splitting.

TiO2 Microboxes with Controlled Internal Porosity for High-Performance Lithium Storage.

Titanium dioxide (TiO2) is considered a promising anode material for high-power lithium ion batteries (LIBs) because of its low cost, high thermal/chemical stability, and good safety performance without solid electrolyte interface formation. However, the poor electronic conductivity and low lithium ion diffusivity of TiO2 result in poor cyclability and lithium ion depletion at high current rates, which hinder them from practical applications. Herein we demonstrate that hierarchically structured TiO2 microboxes with controlled internal porosity can address the aforementioned problems for high-power, long-life LIB anodes. A self-templating method for the synthesis of mesoporous microboxes was developed through Na2 EDTA-assisted ion exchange of CaTiO3 microcubes. The resulting TiO2 nanorods were organized into microboxes that resemble the microcube precursors. This nanostructured TiO2 material has superior lithium storage properties with a capacity of 187 mAh g(-1) after 300 cycles at 1 C and good rate capabilities up to 20 C.

Tungsten doped FeCoP2 nanoparticles embedded into carbon for highly efficient oxygen evolution reaction.

Designing active and stable electrocatalysts with economic efficiency for oxygen evolution reaction (OER) is essential for developing water splitting process at an industrial scale. Herein, we rationally designed a tungsten doped iron cobalt phosphide incorporated with carbon (Wx-FeCoP2/C), prepared by a mechanochemical approach. X-ray photoelectron spectroscopy (XPS) revealed that the doping of W led to an increasing of Co3+/Co2+ and Fe3+/Fe2+ molar ratios, which contributed to the enhanced OER performance. As a result, a current density of 10 mA cm-2 was achieved in 1 M KOH at an overpotential of 264 mV on the optimized W0.1-FeCoP2/C. Moreover, at high current density of 100 mA cm-2, the overpotential value was 310 mV, and the corresponding Tafel slope was measured to be 48.5 mV dec-1, placing it among the best phosphide-based catalysts for OER. This work is expected to enlighten the design strategy of highly efficient phosphide-based OER catalysts.

Electrolyte Design for Low-Temperature Li-Metal Batteries: Challenges and Prospects.

Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation. To get the most energy storage out of the battery at low temperatures, improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases. Herein, this review critically outlines electrolytes' limiting factors, including reduced ionic conductivity, large de-solvation energy, sluggish charge transfer, and slow Li-ion transportation across the electrolyte/electrode interphases, which affect the low-temperature performance of Li-metal batteries. Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding. Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared. Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.

Enhanced broadband near-infrared luminescence of Bi-doped oxyfluoride glasses.

Broadband near-infrared luminescence covering 900 to 1600 nm has been observed in Bi-doped oxyfluoride silicate glasses. The partial substitution of fluoride for oxide in Bi-doped silicate glasses leads to an increase of the intensity and lifetime of the near-infrared luminescence and blue-shift of the near-infrared emission peaks. Both Bi-doped silicate and oxyfluoride silicate glasses show visible luminescence with blue, green, orange and red emission bands when excited by ultra-violet light. Careful investigation on the luminescence properties indicates that the change of near-infrared luminescence is related to optical basicity, phonon energy of the glass matrix and crystal field around Bi active centers. These results offer a valuable way to control the luminescence properties of Bi-doped materials and may find some applications in fiber amplifier and fiber laser.

Localized control of light-matter interactions by using nanoscale asymmetric TiO2.

This paper reports an asymmetry structure-mediated route for highly localized control of light-matter interactions by using tapered TiO(2). We demonstrate for the first time that the growth habit of Ag nanostructures on tapered TiO(2) can be tuned by controllable photolysis. Site-selective anchoring of Ag nanoparticles or nanowires on tapered TiO(2) can be achieved by simply changing the external light. We further show that the obtained tapered TiO(2)-Ag hetero-nanostructures present excellent light-trapping ability over a wide range of wavelengths which is considered to originate from the unique synergistic effects of graded waveguiding and plasmonic light trapping. This improved photon-management capability renders the prepared substrate a very promising candidate for optical sensing application. For this purpose, an enhanced sensitivity for trace detection is confirmed. These findings open up promising avenues for tailoring of light-matter interactions which are of special interest for studying controllable photolysis activation processes and diverse applications such as nanostructure growth, trace detection, photocatalysis and solar cells.

Bi-Fe chalcogenides anchored carbon matrix and structured core-shell Bi-Fe-P@Ni-P nanoarchitectures with appealing performances for supercapacitors.

Pseudocapacitive materials based on multi-active components are attractive platforms for future portable energy devices due to their excellent redox processes and low cost. In this study, nanostructured bismuth-iron chalcogenide anchored on multiwalled carbon nanotube framework (Bi-Fe chalcogenide/C)-based electrode materials were fabricated via a simple solvothermal protocol with enhanced electrochemical performances. The obtained Bi-Fe chalcogenide/C nanocomposites combining the improved electroconductivity of carbonic frameworks and high pseudocapacitive properties of Bi/Fe reversible redox processes were employed as negative electrodes for asymmetric supercapacitor (ASC) devices. Systematic investigation of the synthesized materials and capacitive performance indicated that the Bi-Fe-P/C electrode simultaneously achieved an intrinsically appreciable specific capacitance of 532 F g-1 at a current density of 1 A g-1, high-rate capability, and cyclic stability, profiting from the structural and amorphous merits as well as the collaborative effect of multiple components. Besides, we employed an effective strategy to graft Bi-Fe-P film on a self-standing nickel phosphide (Ni-P) to manufacture a cathode with superior capacitive performances. The as-prepared core-shell Bi-Fe-P@Ni-P was used as a high-performance positive electrode and displayed a large specific capacitance of 230.6 mAh g-1 at 1 A g-1. Additionally, we also assembled an ASC system using the core-shell Bi-Fe-P@Ni-P as a positive electrode and amorphous Bi-Fe-P/C as a negative electrode with an expanded operational potential of 1.6 V. The hybrid device delivered a high specific energy density of 81.5 Wh kg-1 at a power density of 890.2 W kg-1 together with good cyclic characteristics (85.6% capacitance retention after 8000 consecutive cycles). The obtained findings offer new insights into the design of advanced energy storage materials at relatively low costs and underscore the proficiency of heterostructured multicomponent electrodes as a practical option for enhancing the electrochemical performance of ASC.

Unusual luminescence quenching and reviving behavior of Bi-doped germanate glasses.

Here for the first time, we report an unusual annealing temperature dependent near-infrared (NIR) luminescence quenching and reviving behavior in Bi-doped MgO-Al2O3-GeO2 glasses. Systematic characterizations of the samples by using differential thermal analysis (DTA), photoluminescence and absorption spectra, X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that this phenomenon is associated with the reversible reaction of Bi⁺ and Bi° initiated by the change of local glass structure. Excitingly, wavelength tunable luminescence is also observed and it can be ascribed to selective excitation of active Bi⁺ center in different sites. These results not only open a new way for controlling luminescence properties of main group elements in glass but also provide great value for improving practical active-fiber drawing process.

Biomolecule-assisted route to prepare titania mesoporous hollow structures.

Amino acids, as a particularly important type of biomolecules, have been used as multifunctional templates to intelligently construct mesoporous TiO(2) hollow structures through a simple solvothermal reaction. The structure-directing behaviors of various amino acids were systematically investigated, and it was found that these biomolecules possess the general capability to assist mesoporous TiO(2) hollow-sphere formation. At the same time, the nanostructures of the obtained TiO(2) are highly dependent on the isoelectric points (pI) of amino acids. Their molecular-structure variations can lead to pI differences and significantly influence the final TiO(2) morphologies. Higher-pI amino acids (e.g., L-lysine and L-arginine) have better structure-directing abilities to generate nanosheet-assembled hollow spheres and yolk/shell structures. The specific morphologies and mesopore size of these novel hollow structures can also be tuned by adjusting the titanium precursor concentration. Heat treatment in air and vacuum was further conducted to transform the as-prepared structures to porous nanoparticle-assembled hollow TiO(2) and TiO(2)/carbon nanocomposites, which may be potentially applied in the fields of photocatalysts, dye-sensitized solar cells, and Li batteries. This study provides some enlightenment on the design of novel templates by taking advantage of biomolecules.

Progress and Challenges Toward the Rational Design of Oxygen Electrocatalysts Based on a Descriptor Approach.

Oxygen redox catalysis, including the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), is crucial in determining the electrochemical performance of energy conversion and storage devices such as fuel cells, metal-air batteries,and electrolyzers. The rational design of electrochemical catalysts replaces the traditional trial-and-error methods and thus promotes the R&D process. Identifying descriptors that link structure and activity as well as selectivity of catalysts is the key for rational design. In the past few decades, two types of descriptors including bulk- and surface-based have been developed to probe the structure-property relationships. Correlating the current descriptors to one another will promote the understanding of the underlying physics and chemistry, triggering further development of more universal descriptors for the future design of electrocatalysts. Herein, the current benchmark activity descriptors for oxygen electrocatalysis as well as their applications are reviewed. Particular attention is paid to circumventing the scaling relationship of oxygen-containing intermediates. For hybrid materials, multiple descriptors will show stronger predictive power by considering more factors such as interface reconstruction, confinement effect, multisite adsorption, etc. Machine learning and high-throughput simulations can thus be crucial in assisting the discovery of new multiple descriptors and reaction mechanisms.

Origin of photocatalytic activity of nitrogen-doped TiO2 nanobelts.

Experiments combined with the density functional theory (DFT) calculation have been performed to understand the underlying photocatalysis mechanism of the nitrogen-doped titania nanobelts. Nitrogen-doped anatase titania nanobelts are prepared via hydrothermal processing and subsequent heat treatment in NH(3). Both the nitrogen content and the oxygen vacancy concentration increase with increasing the NH(3) treatment temperature. Nitrogen doping leads to an add-on shoulder on the edge of the valence band, the localized N 2p levels above the valence band maximum, and the 3d states of Ti(3+) below the conduction band, which is confirmed by DFT calculation and X-ray photoelectron spectroscopy (XPS) measurement. Extension of the light absorption from the ultraviolet (UV) region to the visible-light region arises from the N 2p levels near the valence band and from the color centers induced by the oxygen vacancies and the Ti(3+) species. Nitrogen doping allows visible-light-responsive photocatalytic activity but lowers UV-light-responsive photocatalytic activity. The visible-light photocatalytic activity originates from the N 2p levels near the valence band. The oxygen vacancies and the associated Ti(3+) species act as the recombination centers for the photoinduced electrons and holes. They reduce the photocatalytic activity although they contribute to the visible light absorbance.

Recent Trends in Synthesis and Investigation of Nickel Phosphide Compound/Hybrid-Based Electrocatalysts Towards Hydrogen Generation from Water Electrocatalysis.

Sustainable and high performance energy devices such as solar cells, fuel cells, metal-air batteries, as well as alternative energy conversion and storage systems have been considered as promising technologies to meet the ever-growing demands for clean energy. Hydrogen evolution reaction (HER) is a crucial process for cost-effective hydrogen production; however, functional electrocatalysts are potentially desirable to expedite reaction kinetics and supply high energy density. Thus, the development of inexpensive and catalytically active electrocatalysts is one of the most significant and challenging issues in the field of electrochemical energy storage and conversion. Realizing that advanced nanomaterials could engender many advantageous chemical and physical properties over a wide scale, tremendous efforts have been devoted to the preparation of earth-abundant transition metals as electrocatalysts for HER in both acidic and alkaline environments because of their low processing costs, reasonable catalytic activities, and chemical stability. Among all transition metal-based catalysts, nickel compounds are the most widely investigated, and have exhibited pioneering performances in various electrochemical reactions. Heterostructured nickel phosphide (NixPy) based compounds were introduced as promising candidates of a new category, which often display chemical and electronic characteristics that are distinct from those of non-precious metals counterparts, hence providing an opportunity to construct new catalysts with an improved activity and stability. As a result, the library of NixPy catalysts has been enriched very rapidly, with the possibility of fine-tuning their surface adsorption properties through synergistic coupling with nearby elements or dopants as the basis of future practical implementation. The current review distils recent advancements in NixPy compounds/hybrids and their application for HER, with a robust emphasis on breakthroughs in composition refinement. Future perspectives for modulating the HER activity of NixPy compounds/hybrids, and the challenges that need to be overcome before their practical use in sustainable hydrogen production are also discussed.

Fe ions modulated formation of hollow NiFe oxyphosphide spheres with enhanced oxygen evolution performance.

A facile template-engaged strategy is developed to synthesize hollow NiFe mixed metal oxyphosphide spheres using different Fe ions (Fe2+ and Fe3+) as modulators. Benefiting from the optimized compositional and structural features, the as-obtained hollow spheres show excellent performance for the oxygen evolution reaction.