Construction of Gold/Rhodium Freestanding Superstructures as Antenna-Reactor Photocatalysts for Plasmon-Driven Nitrogen Fixation.

Precisely controlling the architecture and spatial arrangement of plasmonic heterostructures offers unique opportunities to tailor the catalytic property, whereas the lack of a wet-chemistry synthetic approach to fabricating nanostructures with high-index facets limits their practical applications. Herein, we describe a universal synthetic strategy to construct Au/Rh freestanding superstructures (SSs) through the selective growth of ordered Rh nanoarrays on high-index-faceted Au nanobipyramids (NBPs). This synthetic strategy works on various metal nanocrystal substrates and can yield diverse Au/Rh and Pd/Rh SSs. Especially, the obtained Au NBP/Rh SSs exhibit high photocatalytic activity toward N2 fixation as a result of the spatially separated architecture, local electric field enhancement, and the antenna-reactor mechanism. Both theoretical and experimental results reveal that the Au NBPs can function as nanoantennas for light-harvesting to generate hot charge carriers for driving N2 fixation, while the Rh nanoarrays can serve as the active sites for N2 adsorption and activation to synergistically promote the overall catalytic activity in the Au NBP/Rh SSs. This work offers new avenues to rationally designing and constructing spatially separated plasmonic photocatalysts for high-efficiency catalytic applications.

Oxygen Vacancies and Interface Engineering on Amorphous/Crystalline CrOx -Ni3 N Heterostructures toward High-Durability and Kinetically Accelerated Water Splitting.

Manipulating catalytic active sites and reaction kinetics in alkaline media is crucial for rationally designing mighty water-splitting electrocatalysts with high efficiency. Herein, the coupling between oxygen vacancies and interface engineering is highlighted to fabricate a novel amorphous/crystalline CrOx -Ni3 N heterostructure grown on Ni foam for accelerating the alkaline hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory (DFT) calculations reveal that the electron transfer from amorphous CrOx to Ni3 N at the interfaces, and the optimized Gibbs free energies of H2 O dissociation (ΔGH-OH ) and H adsorption (ΔGH ) in the amorphous/crystalline CrOx -Ni3 N heterostructure are conducive to the superior and stable HER activity. Experimental data confirm that numerous oxygen vacancies and amorphous/crystalline interfaces in the CrOx -Ni3 N catalysts are favorable for abundant accessible active sites and enhanced intrinsic activity, resulting in excellent catalytic performances for HER and OER. Additionally, the in situ reconstruction of CrOx -Ni3 N into highly active Ni3 N/Ni(OH)2 is responsible for the optimized OER performance in a long-term stability test. Eventually, an alkaline electrolyzer using CrOx -Ni3 N as both cathode and anode has a low cell voltage of 1.53 V at 10 mA cm-2 , together with extraordinary durability for 500 h, revealing its potential in industrial applications.

Federation of Internet of Things Testbeds for the Realization of a Semantically-Enabled Multi-Domain Data Marketplace.

The Internet of Things (IoT) concept has attracted a lot of attention from the research and innovation community for a number of years already. One of the key drivers for this hype towards the IoT is its applicability to a plethora of different application domains. However, infrastructures enabling experimental assessment of IoT solutions are scarce. Being able to test and assess the behavior and the performance of any piece of technology (i.e., protocol, algorithm, application, service, etc.) under real-world circumstances is of utmost importance to increase the acceptance and reduce the time to market of these innovative developments. This paper describes the federation of eleven IoT deployments from heterogeneous application domains (e.g., smart cities, maritime, smart building, crowd-sensing, smart grid, etc.) with over 10,000 IoT devices overall which produce hundreds of thousands of observations per day. The paper summarizes the resources that are made available through a cloud-based platform. The main contributions from this paper are twofold. In the one hand, the insightful summary of the federated data resources are relevant to the experimenters that might be seeking for an experimental infrastructure to assess their innovations. On the other hand, the identification of the challenges met during the testbed integration process, as well as the mitigation strategies that have been implemented to face them, are of interest for testbed providers that can be considering to join the federation.

Advances in green bioproduction of marine and glycosaminoglycan oligosaccharides.

Functional oligosaccharides are a class of low-polymerization sugars with physiological functions, showing great potential in the fields of food, medicine, and agriculture, with economic and social value. Certain functional oligosaccharides (e.g., marine oligosaccharides and glycosaminoglycan oligosaccharides) are mainly prepared by degradation of natural polysaccharides using physical and chemical methods. These strategies present problems, including harsh reaction conditions, serious pollution, and variations in product quality. Recently, specific techniques have been applied to the green production of functional oligosaccharides. In this paper, the classification and biological effects of marine oligosaccharides and glycosaminoglycan oligosaccharides are firstly introduced. Then, recent research progress and related databases for green biological preparation of marine oligosaccharides and glycosaminoglycan oligosaccharides are reviewed, and optimization strategies for green bioproduction are summarized. Finally, the limitations and prospects of the current green synthesis strategies are discussed.

Steric hindrance-induced selective growth of rhodium on gold nanobipyramids for plasmon-enhanced nitrogen fixation.

The construction of an antenna-reactor plasmonic photocatalyst that is composed of a plasmonic and a catalytically active metal holds great promise in driving N2 photofixation, but its photocatalytic performance is highly dependent on the spatial distribution of the two components. Up to now, the fabrication of dumbbell-shaped nanostructures featuring spatially separated architecture has remained challenging. Herein, we develop a facile synthetic strategy for the site-selective growth of a Rh nanocrystal 'reactor' on two tips of an Au nanobipyramid (NBP) 'antenna' through the precise manipulation of steric hindrance toward Rh overgrowth. The obtained Au NBP/tip-Rh nanodumbbells (Au NBP/tip-Rh NDs) can function as an excellent antenna-reactor plasmonic photocatalyst for N2 photofixation. In this scenario, the Au nanoantenna harvests light and generates hot electrons under plasmon resonance, meanwhile the hot electrons are transferred to the active sites on Rh nanocrystals for N2 reduction. In comparison with that of classical core@shell nanostructures, the spatially separated architecture of the Au NBP/tip-Rh NDs facilitates charge separation, greatly improving the photocatalytic activity. This study sheds new light on the structure-function relationship for N2 photofixation and benefits the design and construction of spatially separated plasmonic photocatalysts.

A Pd-based plasmonic photocatalyst for nitrogen fixation through an antenna-reactor mechanism.

Plasmonic metal nanocrystals (e.g., Au, Ag, and Cu) hold great promise for driving photocatalytic reactions, but little is known about the plasmonic properties of Pd nanocrystals. Herein, we constructed a plasmonic Pd/Ru antenna-reactor photocatalyst through the controllable growth of a Ru nanoarray 'reactor' on a Pd nano-octahedron 'antenna' and demonstrated a plasmonic Pd-driven N2 photofixation process. The plasmonic properties of Pd nano-octahedrons were verified using finite-difference time-domain (FDTD) simulations and refractive index sensitivity tests in water-glycerol mixtures. Notably, the constructed plasmonic antenna-reactor nanostructures exhibited superior photocatalytic activities during N2 photofixation, with a maximum ammonia production rate of 117.5 ± 15.0 µmol g-1 h-1 under visible and near-infrared (NIR) light illumination. The mechanism can be attributed to the ability of the plasmonic Pd nanoantennas to harvest light to generate abundant hot electrons and the Ru nanoreactors to provide active sites for adsorption and activation of N2. This work paves the way for the development of Pd-based plasmonic photocatalysts for efficient N2 photofixation and sheds new light on the optimal design and construction of antenna-reactor nanostructures.

Symmetry-breaking synthesis of Janus Au/CeO2 nanostructures for visible-light nitrogen photofixation.

Precise manipulation of the reactive site spatial distribution in plasmonic metal/semiconductor photocatalysts is crucial to their photocatalytic performance, but the construction of Janus nanostructures through symmetry-breaking synthesis remains a significant challenge. Here we demonstrate a synthetic strategy for the selective growth of a CeO2 semi-shell on Au nanospheres (NSs) to fabricate Janus Au NS/CeO2 nanostructures with the assistance of a SiO2 hard template and autoredox reaction between Ag+ ions and a ceria precursor. The obtained Janus nanostructures possess a spatially separated architecture and exhibit excellent photocatalytic performance toward N2 photofixation under visible-light illumination. In this scenario, N2 molecules are reduced by hot electrons on the CeO2 semi-shell, while hole scavengers are consumed by hot holes on the exposed Au NS surface, greatly promoting the charge carrier separation. Moreover, the exposed Au NS surface in the Janus structures offers an additional opportunity for the fabrication of ternary Janus noble metal/Au NS/CeO2 nanostructures. This work highlights the genuine superiority of the spatially separated nanoarchitectures in the photocatalytic reaction, offering instructive guidance for the design and construction of novel plasmonic photocatalysts.

(Plasmonic gold core)@(ultrathin ruthenium shell) nanostructures as antenna-reactor photocatalysts toward nitrogen photofixation.

Ruthenium (Ru) is known as the optimal metal catalyst for ammonia (NH3) synthesis, but the poor light-harvesting capability restricts its application in photocatalysis. Herein, we construct an antenna-reactor nanostructure through the controllable growth of an ultrathin Ru nanocluster shell with desired catalytic activity on the plasmonic gold (Au) nanoantennas. In this nanostructure, Au nanoantennas interact strongly with light to generate hot carriers, meanwhile Ru nanoclusters adsorb and activate N2, leading to the reduction of N2 to NH3 by the generated hot electrons. This antenna-reactor plasmonic photocatalyst exhibits shell-thickness-dependent photocatalytic activity toward nitrogen (N2) photofixation under visible and near-infrared light illumination.

Water-soluble non-conjugated polymer dots with strong green fluorescence for sensitive detection of organophosphate pesticides.

Water-soluble non-conjugated polymer dots (PDs) have been synthesized using hyperbranched polyethyleneimine (PEI) and dihydroxybenzaldehyde (DHB) for the first time via the Schiff base reaction at room temperature. The yielded non-conjugated PDs of PEI-DHB could display the well-defined spheric structure and good water solubility. In contrast to the common PDs otherwise showing blue emission, the PEI-DHB PDs could give out strong green fluorescence in aqueous media. Especially, the fluorescence of the PEI-DHB PDs could be specifically quenched by MnO2 nanosheets through the inner filter effects and further restored by the thiocholine that could reduce MnO2 nanosheets into Mn2+. Herein, thiocholine could be produced in hydrolysis reaction of acetylthiocholine catalyzed by the acetylcholinesterase (AChE), of which the catalytic activity could be irreversibly inhibitted by the introduction of organophosphates. A highly selective fluorimetric method was thereby been developed for the detection of organophosphorus pesticides using dimethyl-dichloro-vinyl phosphate as a model. The linear concentrations ranges from 0.050 to 2.5 µM. Importantly, the non-conjugated PDs probes with strong green fluorescence and high water solubility may promise the extensive applications in the environmental, food, and clinical analysis fields.

Boosting the zinc ion storage capacity and cycling stability of interlayer-expanded vanadium disulfide through in-situ electrochemical oxidation strategy.

Metallic vanadium dichalcogenides with high conductivity and large layer spacing are fantastically potential to be cathode candidates for aqueous zinc ion batteries. However, simply reliance on the reversible Zn2+ intercalation/deintercalation process in the layer structure of vanadium dichalcogenides makes it suffer from low specific capacity and limited cycling number. Here we report a facile in-situ electrochemical oxidation strategy to boost the zinc ion storage capacity of interlayer-expanded vanadium disulfide (VS2·NH3) hollow spheres with satisfying cyclic stability. The hydrated vanadium oxide (V2O5·nH2O) generated from oxidized VS2·NH3, are endowed with reduced nanosheet size and subordinated porous structure, which provides abundant accessible sites and accelerates the zinc ion diffusion process. As a result, the VS2·NH3 derived cathode after the electrochemical oxidation process delivers a high reversible capacity of 392 mA h g-1 at 0.1 A g-1 and long cyclic stability (110% capacity retention at 3 A g-1 after 2000 cycles). The efficient oxidation process of VS2·NH3 cathode and the storage mechanism in the subsequent cycles are schematically investigated. This work not only reveals the zinc ion storage mechanism of the oxidized VS2·NH3 but also sheds light on advanced design for high-performance Zn ion cathode materials.