Modulating the Electrolyte Microenvironment in Electrical Double Layer for Boosting Electrocatalytic Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction reaction (NO3RR) is a promising approach to achieve remediation of nitrate-polluted wastewater and sustainable production of ammonia. However, it is still restricted by the low activity, selectivity and Faraday efficiency for ammonia synthesis. Herein, we propose an effective strategy to modulate the electrolyte microenvironment in electrical double layer (EDL) by mediating alkali metal cations in the electrolyte to enhance the NO3RR performance. Taking bulk Cu as a model catalyst, the experimental study reveals that the NO3--to-NH3 performance in different electrolytes follows the trend Li+ < Cs+ < Na+ < K+. Theoretical studies illustrate that the proton transport rate in NO3RR and the activity of the rate-determining step (NO3- to NO2-) increase in the order Li+ < Cs+ < Na+ < K+. The cation effects are also general for two typical nanostructured catalysts including copper/cuprous oxide and nickel phosphides, achieving near-100% Faradaic efficiency and over 99% conversion of NO3- to NH3. Furthermore, we demonstrate that NO3- can be converted to high-purity NH4Cl by copper/cuprous oxide catalyst in K+-containing electrolyte.

Mode localization in plasmonic optomechanical resonators for ultrasensitive infrared sensing.

Uncooled infrared thermal detectors are gaining increasing attention owing to their ability to operate at room-temperature and their low cost. This study proposes a plasmonic optomechanical resonator for ultrasensitive long-wave infrared wave sensing based on mode localization mechanism. The mode-localized effect confines the plasmonic energy in the resonators and induces a significant modal amplitude shift through infrared irradiation, thus achieving highly sensitive detection. The results show that the detection sensitivity can reach 1.304 /mW, which is three-order improvement compared to the frequency-shift sensing metrics. The research provides a new approach to further improve the detection sensitivity of uncooled infrared sensors.

Highly sensitive determination of L-glutamic acid in pig serum with an enzyme-free molecularly imprinted polymer on a carbon-nanotube modified electrode.

Through electrochemical polymerization using L-glutamic acid (L-Glu) as a template and 4,6-diaminoresorcinol as a functional monomer, an enzyme-free molecularly imprinted polymer (MIP) based L-Glu sensor with multi-walled carbon nanotubes (MWCNTs) decorated on a glassy carbon electrode (GCE), namely G-MIP/MWCNTs/GCE, was developed in this work. The reaction conditions were optimized as follows: electrochemical polymerization of 23 cycles, pH of 3.0, molar ratio of template/monomer of 1 : 4, volume ratio of elution reagents of acetonitrile/formic acid of 1 : 1, and elution time of 2 min. The prepared materials and molecularly imprinted polymer were characterized by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) as well as electrochemical methods. The electrochemical properties of different electrodes were investigated via differential pulse voltammetry (DPV), showing that the electrode of G-MIP/MWCNTs/GCE exhibited excellent catalytic oxidation activity towards L-Glu. A good linear relationship between peak-currents and L-Glu concentrations in a range from 1.00 × 10-8 to 1.00 × 10-5 mol L-1 was observed, with a detection limit of 5.13 × 10-9 mol L-1 (S/N = 3). The imprinted sensor possesses excellent selectivity, high sensitivity, and good stability, which have been successfully applied for the detection of L-Glu in pig serum samples with a recovery rate of 97.4-105.5%, being comparable to commercial high-performance liquid chromatography, demonstrating a simple, rapid, and accurate way for the determination of L-Glu in the fields of animal nutrition and biomedical engineering.

In situ reconstructed AgZn3 nanoparticles supported on zinc nanoplates for efficient CO2 electroreduction to tunable syngas.

Developing efficient electrocatalysts for CO2 reduction to syngas with tunable H2/CO ratios and high total faradaic efficiency is challenging. Herein, we report an effective catalyst composed of in situ reconstructed AgZn3 nanoparticles and Zn nanoplates for syngas synthesis, showing nearly 100% Faraday efficiency to syngas with a tunable H2/CO ratio from 2 : 1 to 1 : 2. Moreover, the in situ electrochemical measurements coupled with theoretical calculations disclose that the Zn site in AgZn3 nanoparticles and the hollow site between Ag and Zn in AgZn3 are the possible active sites for CO and H2 generation, respectively. This work has guiding significance for designing dual site catalysts for CO2 electroreduction to tunable syngas.

Designing flower-like MOFs-derived N-doped carbon nanotubes encapsulated magnetic NiCo composites with multi-heterointerfaces for efficient electromagnetic wave absorption.

In order to acquire exceptional electromagnetic wave absorption properties, the microstructure design and component modification of composites are essential. Metal-organic frameworks (MOFs), due to the unique metal-organic crystalline coordination, tunable morphology, high surface area, and well-defined pores, have been regarded as promising electromagnetic wave absorption materials precursors. However, the inadequate contact abilities between adjacent MOFs nanoparticles endow it with undesirable electromagnetic wave dissipation capacity at a low filler loading, which is a great challenge to break size effect of nanoparticles to achieve efficient absorption. Herein, NiCo-MOFs derived N-doped carbon nanotubes encapsulated with NiCo nanoparticles anchored on flowers-like composites (denoted as NCNT/NiCo/C) were successfully prepared through facile hydrothermal method followed by thermal chemical vapor deposition with melamine-assisted catalyst. By controlling the Ni/Co ratio in precursor, the tunable morphology and microstructure of MOFs are achieved. Most importantly, the derived N-doped carbon nanotubes tightly connect the adjacent nanosheets to construct the special 3D interconnected conductive network, which effectively accelerates the charge transfer and improves the conduction loss. And notably, the NCNT/NiCo/C composite delivers excellent electromagnetic wave absorption performance with minimum reflection loss of -66.1 dB and wide effective absorption bandwidth up to 4.64 GHz when the Ni/Co ratio is 1:1. This work provides a novel method for the preparation of morphology controllable MOFs-derived composites and realizes high-performance electromagnetic wave absorption properties.

Viscosity-Responsive Electrochemiluminescence of Diphenylbenzofulvene Derivatives.

The development of superior probes is highly desirable and valuable for viscosity measurement. Herein, we designed and reported a series of diphenylbenzofulvene (DPBF)-based organic luminophores according to the molecular regulation strategy. There are two free-rotating phenyl groups attached to the rigid fluorene skeleton in the DPBF, enabling its unique propeller-like noncoplanar chemical structure. Benefiting from this, DPBFs could feature outstanding PL and ECL emissions with intriguing aggregation-induced characteristics. Experimental and theoretical investigations revealed that substituent, spatial structure, and molecular orbital energy profoundly affected their luminescent behaviors. It was disclosed that fluoro-substituted DPBF(F)2 with a smaller LUMO-HOMO band gap demonstrated the strongest ECL emission and was selected as the optimal ECL emitter. Finally, DPBF(F)2 featured a linear response to the viscosity and VC content with lower limits of detection (LOD) of 5.69 µcP and 38.2 nM, respectively. This study represents the first example of the ECL probe toward viscosity and will be of great significance for both ECL application and viscosity measurement.

Dynamic Reconstructed RuO2 /NiFeOOH with Coherent Interface for Efficient Seawater Oxidation.

Developing efficient oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis is still a big challenge. Herein, a facile one-pot approach is reported to synthesize RuO2 -incorporated NiFe-metal organic framework (RuO2 /NiFe-MOF) with unique nanobrick-nanosheet heterostructure as precatalyst. Driven by electric field, the RuO2 /NiFe-MOF dynamically reconstructs into RuO2 nanoparticles-anchored NiFe oxy/hydroxide nanosheets (RuO2 /NiFeOOH) with coherent interface, during which the dissolution and redeposition of RuO2 are witnessed. Owing to the synergistic interaction between RuO2 and NiFeOOH, the as-reconstructed RuO2 /NiFeOOH exhibits outstanding alkaline OER activity with an ultralow overpotential of 187.6 mV at 10 mA cm-2 and a small Tafel slope of 31.9 mV dec-1 and excellent durability at high current densities of 840 and 1040 mA cm-2 in 1 m potassium hydroxide (KOH). When evaluated for seawater oxidation, the RuO2 /NiFeOOH only needs a low overpotential of 326.2 mV to achieve 500 mA cm-2 and can continuously catalyze OER at 500 mA cm-2 for 100 h with negligible activity degradation. Density function theory calculations reveal that the presence of strong interaction and enhanced charge transfer along the coherent interface between RuO2 and NiFeOOH ensures improved OER activity and stability.

Rigid Enhanced Electrochemiluminescence of 1,2,3-Triaryl Indenes as an Ultrasensitive Sensor for D2O in H2O.

The intriguing aggregation-induced emission has recently been applied in the electrochemiluminescence, called aggregation-induced electrochemiluminescence (AIE-ECL), which is conducive to solving the water insolubility and aggregation-caused quenching for most organic luminescence probes. However, AIE-ECL still has the problems of low luminous efficiency and limited practical application. In this work, we disclosed the AIE-ECL properties of 1,2,3-triaryl-substituted indenes containing rigid structures. Experimental and theoretical investigations demonstrated that such a rigid structure could significantly enhance the aromaticity and stability and thereby the luminescence performance of these indenes. Moreover, according to the finding of hydrogen/deuterium exchange for active hydrogen in indene under electrical excitation, ultrasensitive detection for D2O in H2O was realized by such an indene-based AIE-ECL system. Our research not only provided an attractive strategy to enhance the luminescence property for an AIE-active luminophore but also established a superior sensor toward D2O.

The risk variant rs11836367 contributes to breast cancer onset and metastasis by attenuating Wnt signaling via regulating NTN4 expression.

Most genome-wide association study (GWAS)-identified breast cancer-associated causal variants remain uncharacterized. To provide a framework of understanding GWAS-identified variants to function, we performed a comprehensive study of noncoding regulatory variants at the NTN4 locus (12q22) and NTN4 gene in breast cancer etiology. We find that rs11836367 is the more likely causal variant, disrupting enhancer activity in both enhancer reporter assays and endogenous genome editing experiments. The protective T allele of rs11837367 increases the binding of GATA3 to the distal enhancer and up-regulates NTN4 expression. In addition, we demonstrate that loss of NTN4 gene in mice leads to tumor earlier onset, progression, and metastasis. We discover that NTN4, as a tumor suppressor, can attenuate the Wnt signaling pathway by directly binding to Wnt ligands. Our findings bridge the gaps among breast cancer-associated single-nucleotide polymorphisms, transcriptional regulation of NTN4, and breast cancer biology, which provides previously unidentified insights into breast cancer prediction and prevention.

Aromaticity-Enhanced pH-Responsive Electrochemiluminescence of Cyclopentadienols.

Due to significantly tackling the problems of aggregation-caused quenching and water insolubility, aggregation-induced emission electrochemiluminescence (AIE-ECL) has emerged as a research highlight in aqueous detection and sensing. Herein, we reported a series of cyclopentadienols featuring excellent AIE-ECL properties on the basis of an enhanced aromaticity strategy. In detail, substituents profoundly determined ECL emission by affecting the characteristic absorption peak intensity ratio in UV-vis spectra and lowest unoccupied molecular orbital (LUMO)-highest occupied molecular orbital (HOMO) energies. It was found that 1,2,3,4,5-pentafluorophenyl cyclopentadienol (PFCD) containing an electron-withdrawing fluorine substituent, the maximum R/B band ratio, and a smaller LUMO-HOMO band gap demonstrated the best ECL performance. Meanwhile, such an AIE-ECL system displayed a wide response range toward pH (4-12) with a good linear relationship. Our research not only enriched polycyclic aromatic hydrocarbon-based AIE-ECL systems but also established an efficient pH sensor in the aqueous phase.

Optimization of quantum light sources and four-wave mixing based on a reconfigurable silicon ring resonator.

Being a key component on a photonic chip, the microring usually specializes in a certain nonlinear optical process and can not simultaneously meet different working conditions for different processes. Here, we theoretically and experimentally investigate a reconfigurable silicon microring resonator to act as a optimization strategy for both classical four-wave mixing and quantum light sources. Experimental results show that the four-wave mixing efficiency with continuous wave and pulsed pump can be both optimized to a high value well matching numerical analysis. A variety of quantum light sources - including the heralded single-photon source, two-photon source and multi-photon source - are demonstrated to present a high performance and their key parameters including the pair generation rates (PGR), the heralding efficiency (HE) and the coincidence-to-accidental ratio (CAR) are controllable and optimizable. Such tunable nonlinear converter is immune to fabrication variations and can be popularized to other nonlinear optical materials, providing a simple and compact post-fabrication trimming strategy for on-chip all-optical signal processing and photonic quantum technologies.

Oxygen Vacancy Engineering Synergistic with Surface Hydrophilicity Modification of Hollow Ru Doped CoNi-LDH Nanotube Arrays for Boosting Hydrogen Evolution.

With the development of clean hydrogen energy, the cost effective and high-performance hydrogen evolution reaction (HER) electrocatalysts are urgently required. Herein, a green, facile, and time-efficient Ru doping synergistic with air-plasma treatment strategy is reported to boost the HER performance of CoNi-layered double hydroxide (LDH) nanotube arrays (NTAs) derived from zeolitic imidazolate framework nanorods. The Ru doping and air-plasma treatment not only regulate the oxygen vacancy to optimize the electron structure but also increase the surface roughness to improve the hydrophilicity and hydrogen spillover efficiency. Therefore, the air plasma treated Ru doped CoNi-LDH (P-Ru-CoNi-LDH) nanotube arrays display superior HER performance with an overpotential of 29 mV at a current density of 10 mA cm-2 . Furthermore, by assembling P-Ru-CoNi-LDH as both cathode and anode for two-electrode urea-assisted water electrolysis, a small cell voltage of 1.36 V is needed at 10 mA cm-2 and can last for 100 h without any obvious activity attenuation that showing outstanding durability. In general, the P-Ru-CoNi-LDH can improve the HER performance from intrinsic electronic structure regulation cooperated with extrinsic surface wettability modification. These findings provide an effective intrinsic and extrinsic synergistic effect avenue to develop high performance HER electrocatalysts, which is potential to be applied to other research fields.

Raman spectrum classification based on transfer learning by a convolutional neural network: Application to pesticide detection.

Pesticide detection is of tremendous importance in agriculture, and Raman spectroscopy/Surface-Enhanced Raman Scattering (SERS) has proven extremely effective as a stand-alone method to detect pesticide residues. Machine learning may be able to automate such detection, but conventional algorithms require a complete database of Raman spectra, which is not feasible. To bypass this problem, the present study describes a transfer learning method that improves the algorithm's accuracy and speed to extract features and classify Raman spectra. The transfer learning model described here was developed through the following steps: (1) the classification model was pre-trained using an open-source Raman spectroscopy database; (2) the feature extraction layer was saved after training; and (3) the training model for the Raman spectroscopy database was re-established while using self-tested pesticides and keeping the feature extraction layer unchanged. Three models were evaluated with or without transfer learning: CNN-1D, Resnet-1D, and Inception-1D, and they have improved the accuracy of spectrum classification by 6%, 2%, and 3%, with reduced training time and increased curve smoothness. These results suggest that transfer learning can improve the feature extraction capability and therefore accuracy of Raman spectroscopy models, expanding the range of Raman-based applications where transfer learning model can be used to identify the spectra of different substances.

A Multiscale Strategy to Construct Cobalt Nanoparticles Confined within Hierarchical Carbon Nanofibers for Efficient CO2 Electroreduction.

The efficiency of CO2 electroreduction has been largely limited by the activity of the catalysts as well as the three-phase interface. Herein, a multiscale strategy is proposed to synthesize hierarchical nanofibers covered by carbon nanotubes and embedded with cobalt nanoparticles (Co/CNT/HCNF). The confinement effect of carbon nanotubes can restrict the diameter of the cobalt particles down to several nanometers and prevent the easy corrosion of these nanoparticles. The three-dimensional carbon nanofibers, in size range of several hundred nanometers, improve the electrochemically active surface area, facilitate electron transfer, and accelerate CO2 transportation. These cross-linked carbon nanofibers eventually form a freestanding Co/CNT/HCNF membrane of dozens of square centimeters. Consequently, Co/CNT/HCNF produces CO with 97% faradaic efficiency at only -0.4 VRHE cathode potential in an H-type cell. From the regulation of catalyst nanostructure to the design of macrography devices, Co/CNT/HCNF membrane can be directly used as the gas-diffusion compartment in a flow cell device. Co/CNT/HCNF membrane generates CO with faradaic efficiencies higher than 90% and partial current densities greater than 300 mA cm-2 for at least 100-h stability. This strategy provides a successful example of efficient catalysts for CO2 electroreduction and also has the feasibility in other self-standing energy conversion devices.

Accelerating the oxygen evolution reaction kinetics of Co3O4 in neutral electrolyte by decorating RuO2.

Developing efficient electrocatalysts for the neutral oxygen evolution reaction (OER) is important but still challenging. Herein, by combining density functional theory calculations and experiments, we have demonstrated that the decoration of RuO2 can effectively accelerate the OER kinetics of Co3O4 in neutral electrolyte. High activity (365 mV at 10 mA cm-2) and decent stability (up to 100 h) are achieved by RuO2-decorated Co3O4 in 1 M PBS electrolyte.

Characterizing the dissemination of misinformation on social media in health emergencies: An empirical study based on COVID-19.

The dissemination of misinformation in health emergencies poses serious threats to public health and increases health anxiety. To understand the underlying mechanism of the dissemination of misinformation regarding health emergencies, this study creatively draws on social support theory and text mining. It also explores the roles of different types of misinformation, including health advice and caution misinformation and health help-seeking misinformation, and emotional support in affecting individuals' misinformation dissemination behavior on social media and whether such relationships are contingent on misinformation ambiguity and richness. The theoretical model is tested using 12,101 textual data about COVID-19 collected from Sina Weibo, a leading social media platform in China. The empirical results show that health caution and advice, help seeking misinformation, and emotional support significantly increase the dissemination of misinformation. Furthermore, when the level of ambiguity and richness regarding misinformation is high, the effect of health caution and advice misinformation is strengthened, whereas the effect of health help-seeking misinformation and emotional support is weakened, indicating both dark and bright misinformation ambiguity and richness. This study contributes to the literature on misinformation dissemination behavior on social media during health emergencies and social support theory and provides implications for practice.

Reconfigurable multiphoton entangled states based on quantum photonic chips.

Multipartite entanglement is one of the most prominent features of quantum mechanics and is the key ingredient in quantum information processing. Seeking for an advantageous way to generate it is of great value. Here we propose two different schemes to prepare multiphoton entangled states on a quantum photonic chip that are both based on the theory of entanglement on the graph. The first scheme is to construct graphs for multiphoton states by the network of spatially anti-bunching two-photon sources. The second one is to construct graphs by the linear beam-splitter network, which can generate W and Dicke states efficiently with simple structure. Both schemes can be scaled up in the photon number and can be reconfigured for different types of multiphoton states. This study supplies a systematic solution for the on-chip generation of multiphoton entangled states and will promote the practical development of multiphoton quantum technologies.

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.

Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities.

Carbon dioxide electroreduction provides a useful source of carbon monoxide, but comparatively few catalysts could be sustained at current densities of industry level. Herein, we construct a high-yield, flexible and self-supported single-atom nickel-decorated porous carbon membrane catalyst. This membrane possesses interconnected nanofibers and hierarchical pores, affording abundant effective nickel single atoms that participate in carbon dioxide reduction. Moreover, the excellent mechanical strength and well-distributed nickel atoms of this membrane combines gas-diffusion and catalyst layers into one architecture. This integrated membrane could be directly used as a gas diffusion electrode to establish an extremely stable three-phase interface for high-performance carbon dioxide electroreduction, producing carbon monoxide with a 308.4 mA cm-2 partial current density and 88% Faradaic efficiency for up to 120 h. We hope this work will provide guidance for the design and application of carbon dioxide electro-catalysts at the potential industrial scale.

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.