Designed Synthesis and Electrochemical Performance Regulation of the Hierarchical Hollow Structure Cu2S/Cu7S4/NC Anode for Hybrid Supercapacitors.

Copper-based compounds have attracted increasing attention as electrode materials for rechargeable devices, but their poor conductivity and insufficient stability inhibit their further development. Herein, an effective method has been proposed to improve the electrochemical properties of the copper-based electrodes by coating carbon materials and generating unique micro/nanostructures. The prepared Cu2S/Cu7S4/NC with hierarchical hollow structure possesses excellent electrochemical performance, attributing to the composition and structure optimization. The superior charge storage performance has been assessed by theoretical and experimental research. Specifically, the Cu2S/Cu7S4/NC exhibits remarkably higher electrical conductivity and lower adsorption-free energy for O* and OH* than those of Cu2O. Moreover, the Cu2S/Cu7S4/NC delivers a high specific capacitance of 1261.3 F·g-1 at the current density of 1 A·g-1 and also has great rate performance at higher current densities, which are much better than those of the Cu2O nanocubes. In addition, the assembled hybrid supercapacitor using Cu2S/Cu7S4/NC as the anode exhibits great energy density, power density, and cycling stability. This study has proposed a novel and feasible method for the synthesis of high-performance copper-based electrodes and their electrochemical performance regulation, which is of great significance for the advancement of high-quality electrode materials and rechargeable devices.

Spatially selective defect management of CsPbI3 films for high-performance carbon-based inorganic perovskite solar cells.

Defects formed at the surface, buried interface and grain boundaries (GB) of CsPbI3 perovskite films considerably limit photovoltaic performance. Such defects could be passivated effectively by the most prevalent post modification strategy without compromising the photoelectric properties of perovskite films, but it is still a great challenge to make this strategy comprehensive to different defects spatially distributed throughout the films. Herein, a spatially selective defect management (SSDM) strategy is developed to roundly passivate various defects at different locations within the perovskite film by a facile one-step treatment procedure using a piperazine-1,4-diium tetrafluoroborate (PZD(BF4)2) solution. The small-size PZD2+ cations could penetrate into the film interior and even make it all the way to the buried interface of CsPbI3 perovskite films, while the BF4- anions, with largely different properties from I- anions, mainly anchor on the film surface. Consequently, virtually all the defects at the surface, buried interface and grain boundaries of CsPbI3 perovskite films are effectively healed, leading to significantly improved film quality, enhanced phase stability, optimized energy level alignment and promoted carrier transport. With these films, the fabricated CsPbI3 PSCs based on carbon electrode (C-PSCs) achieve an efficiency of 18.27%, which is among the highest-reported values for inorganic C-PSCs, and stability of 500 h at 85 °C with 65% efficiency maintenance.

Exploring the surface plasmon catalytic reactions mechanism by three-phase interface modification combining with in-situ EC-SERS methods.

Local surface plasmon resonance (LSPR) is a novel catalytic technique that has emerged in recent years, especially in the catalysis of aromatic amine compounds. However, the response process and mechanism are still unclear in current study. In the current field of study, the response process and mechanism are still unclear. In this work, the gas-liquid-solid three-phase interface (GLSTI) was innovatively utilized in this study to validate the reaction mechanism by surface-enhanced Raman spectroscopy. P-Aminothiophenol (PATP) and P-Phenylenediamine (PDA) underwent a surface plasmon-catalyzed reaction by using a silver nano-dendrites substrate with strong SERS activity. The GLSTI significantly facilitates the occurrence of surface plasmon catalytic reactions, which can supply enough oxygen by providing three-phase points. In situ SERS and EC-SERS technologies were combined in this study for the explorations. Therefore, this work is dedicated to deepening the exploration and expanding into new directions in plasmon-induced catalytic reactions.

Controlled establishment of advanced local high-entropy NiCoMnFe-based layered double hydroxide for zinc batteries and low-temperature supercapacitors.

The development of high-performance electrodes is essential for improving the charge storage performance of rechargeable devices. In this study, local high-entropy C, N co-doped NiCoMnFe-based layered double hydroxide (C/N-NiCoMnFe-LDH, C/N-NCMF) were designed using a novel method. Multi-component synergistic effects can dramatically modulate the surface electron density, crystalline structure, and band-gap of the electrode. Thus, the electrical conductivity, electron transfer, and affinity for the electrolyte can be optimized. Additionally, the C/N-NCMF yielded a high specific capacitance (1454F·g-1) at 1 A·g-1. The electrode also exhibited excellent cycling stability, with 62 % capacitance retention after 5000 cycles. Moreover, the assembled Zn||C/N-NCMF battery and the C/N-NCMF//AC hybrid supercapacitor yielded excellent energy densities of 63.1 and 35.4 Wh·kg-1 at power densities of 1000 and 825 W·kg-1, and superior cycling performance with 69 % and 88.7 % capacitance retention after 1000 and 30,000 cycles, respectively. Furthermore, the electrode maintained high electrochemical activity and stability and ensured high energy density, power density, and cycling stability of the rechargeable devices even at a low temperature (-20 °C). This study paves a new pathway for regulating the electrochemical performance of LDH-based electrodes.

Symmetry-Breaking p-Block Antimony Single Atoms Trigger N-Bridged Titanium Sites for Electrocatalytic Nitrogen Reduction with High Efficiency.

The electrochemical nitrogen reduction reaction (eNRR) under mild conditions emerges as a promising approach to produce ammonia (NH3) compared to the typical Haber-Bosch process. Herein, we design an asymmetrically coordinated p-block antimony single-atom catalyst immobilized on nitrogen-doped Ti3C2Tx (Sb SA/N-Ti3C2Tx) for eNRR, which exhibits ultrahigh NH3 yield (108.3 µg h-1 mgcat-1) and excellent Faradaic efficiency (41.2%) at -0.3 V vs RHE. Complementary in situ spectroscopies with theoretical calculations reveal that the nitrogen-bridged two titanium atoms triggered by an adjacent asymmetrical Sb-N1C2 moiety act as the active sites for facilitating the protonation of the rate-determining step from *N2 to *N2H and the kinetic conversion of key intermediates during eNRR. Moreover, the introduction of Sb-N1C2 promotes the formation of oxygen vacancies to expose more titanium sites. This work presents a strategy for single-atom-decorated ultrathin two-dimensional materials with the aim of simultaneously enhancing NH3 yield and Faradaic efficiency for electrocatalytic nitrogen reduction.

Research Progress in Boron-Modified Phenolic Resin and Its Composites.

As one of the most successful modified phenolic resins, boron-modified phenolic resin (BPF) has excellent heat resistance and ablative resistance, good mechanical and wear resistance, and flame retardancy. BPF and its composites can be widely used in areas such as aerospace, weapons and equipment, automobile brakes, and fire retardants. In this review, the current state of development of BPF and its composites is presented and discussed. After introducing various methods to synthesize BPF, functionalization of BPF is briefly summarized. Particular emphasis is placed on general methods used to fabricate BPF-based composites and the heat resistance, ablative resistance, mechanical property, wear resistance, flame retardancy, and water resistance of BPF-based composites. Finally, the challenges of this research area are summarized and its future outlook is prospected.

A novel SERS sensor array based on AuNRs and AuNSs inverse-etching for the discrimination of five antioxidants.

Antioxidants play an important role in life health and food safety. Herein, an inverse-etching platform based on gold nanorods (AuNRs) and gold nanostars (AuNSs) for high-throughput discrimination of antioxidants was constructed. Under the action of hydrogen peroxide (H2O2) and horseradish peroxidase (HRP), 3,3',5,5'-tetramethylbenzidine (TMB) would be oxidized to TMB+ or TMB2+. HRP reacts with H2O2 to release oxygen free radicals, which then react with TMB. Au nanomaterials can react with TMB2+, at the same time, Au was oxidized into Au (I), leading to the etching of the shape. Antioxidants, with good reduction ability, would prevent the further oxidation of TMB+ to TMB2+. So the presence of antioxidants will prevent further oxidation while avoiding the etching of Au in the catalytic oxidation process, thereby achieved inverse etching. Distinctive surface enhanced Raman scattering (SERS) fingerprint of five antioxidants were obtained based on the differential ability to scavenge free radicals. Five antioxidants, including ascorbic acid (AA), melatonin (Mel), glutathione (GSH), tea polyphenols (TPP), and uric acid (UA) were successfully distinguished by using linear discriminant analysis (LDA), heat map analysis and hierarchical cluster analysis (HCA). The study exhibits an effective inverse-etching based SERS sensor array for the response of antioxidants, which has great reference value in the field of human disease and food detection.

Electrochemical Performance of Corn Waste Derived Carbon Electrodes Based on the Intrinsic Biomass Properties.

The exploration of cost-effective and sustainable biomass-derived carbon materials as electrodes for energy conversion and storage has gained extensive attention in recent research studies. However, the selection of the biomass and the electrochemical performance regulation of the derived biochar, as well as their interrelationship still remain challenging for practical application. Herein, corn wastes with high carbon content (>40%), corn cob and corn silk, were selected as precursors for the preparation of high value-added and high yield carbon materials via a modified synthetic process. Uniquely, this work put emphasis on the theoretical and experimental investigations of how the biomass properties influence the composition and nanostructure regulation, the electrolyte ion adsorption free energy, and the electrical conductivity of the derived carbon materials as well as their electrochemical performance optimization. Owing to the favorable specific surface area, the hierarchical porous structure, and the diverse elemental distribution, corn cob and corn silk derived carbon materials (CBC and SBC) present great potential as promising electrodes for alkaline aqueous zinc batteries and supercapacitors. The assembled CBC//Zn and SBC//Zn zinc batteries deliver high energy densities of 63.0 Wh kg-1 and 39.1 Wh kg-1 at a power density of 575 W kg-1, with excellent cycling performance of 91.1% and 84.3% capacitance retention after 10,000 cycles. As for the assembled symmetric supercapacitors, high energy densities of 14.9 Wh kg-1 and 13.6 Wh kg-1, and superior long-term cycling stability of 99.3% and 96.6% capacitance retention after 20,000 cycles could be achieved. This study highlights the advantages of utilizing corn cob and corn silk as carbon sources on the designed synthesis of carbon electrodes, and presents a meaningful perspective in the investigation of biomass-derived carbon materials and their potential applications in rechargeable devices.

Promoting Surface Reconstruction of Low-Cost Stainless Steel Catalyst for Efficient Oxygen Evolution Reaction.

The development of cost-effective transition metal catalysts for oxygen evolution reaction (OER) is critical for the production of hydrogen fuel from water splitting. Low-cost and efficient stainless steel-based catalysts are expected to replace the scarce platinum group metals for large-scale energy applications. Here in this work, we report the conversion of commonly available inexpensive and easily accessible 434-L stainless steel (SS) into highly active and stable electrodes by corrosion and sulfuration strategies. The Nix Fe1-x S layer as a pre-catalyst and S-doped Nix Fe oxyhydroxides in situ formed on the catalyst surface are the true active species for OER. The optimized 434-L stainless steel-based electrocatalyst exhibits a low overpotential of 298 mV at 10 mA cm-2 in 1.0 M KOH with a small OER kinetics (the Tafel slope of 54.8 mV dec-1 ) and good stability. This work reveals the 434-L alloy stainless steel with Fe and Cr as the main elements can be used as qualified OER catalysts by surface modification, along with a new mentality to solve the energy and resource waste problems.

Synchronous Modulation of Energy Level Gradient and Defects for High-Efficiency HTL-Free Carbon-Based All-Inorganic Perovskite Solar Cells.

In order to improve the thermal stability of perovskite solar cells (PSCs) and reduce production costs, hole transport layer (HTL)-free carbon-based CsPbI3 PSCs (C-PSCs) have attracted the attention of researchers. However, the power conversion efficiency (PCE) of HTL-free CsPbI3 C-PSCs is still lower than that of PSCs with HTL/ metal electrodes. This is because the direct contact between the carbon electrode and the perovskite layer has a higher requirement on the crystal quality of perovskite layer and matched energy level at perovskite/carbon interface. Herein, the acyl chloride group and its derivative trichloroacetyl chloride are used to passivate CsPbI3 C-PSCs for the first time. The results show that the carbonyl group of trichloroacetyl chloride can effectively passivate the uncoordinated Pb2+ ions in perovskite. At the same time, leaving group Cl- ions can increase the grain size of perovskite and improve the crystallization quality of perovskite layer. In addition, the trichloroacetyl chloride tends to generate cesium chloride acetate, which acts as an electron blocking layer, reduces charge recombination, promotes gradient energy level arrangement, and effectively improves the separation and extraction ability of carriers. The PCE of CsPbI3 HTL-free C-PSCs is successfully increased from 13.40% to 14.82%.

Preparation of High-Efficiency (>14%) HTL-Free Carbon-Based All-Inorganic Perovskite Solar Cells by Passivation with PABr Derivatives.

Due to the advantages of low cost and good thermal stability, all-inorganic CsPbI2Br carbon-based perovskite solar cells (C-PSCs) without a hole transport layer have been rapidly developed in recent years. While the carbon electrode is in direct contact with the CsPbI2Br film, higher requirements are placed on the defects and energy level arrangement of the CsPbI2Br layer, which leads to the relatively low photoelectric conversion efficiency (PCE) of C-PSCs. Herein, propylamine hydrobromide (PABr) and its derivative 3-bromopropylamine hydrobromide (3Br-PABr) were used to passivate the surface defects of CsPbI2Br C-PSCs for the first time. The results show that passivation molecules are modulated by the substituent effect, leading to a stronger interaction between amino groups and uncoordinated Pb2+ ions, which facilitates a better passivation effect of 3Br-PABr. In addition, 3Br-PABr promotes the gradient arrangement of energy levels while passivating surface defects, which accelerates the rapid extraction of holes. After the passivation by PABr and 3Br-PABr, the PCE of HTL-free CsPbI2Br C-PSCs increased from 12.15% for the control device to 13.15 and 14.04%, respectively, which are among the highest reported values of CsPbI2Br C-PSCs.

Mechanically Robust and Flexible GO/PI Hybrid Aerogels as Highly Efficient Oil Absorbents.

Herein, mechanically robust and flexible graphene oxide/polyimide (GO/PI) hybrid aerogels (GIAs) were fabricated by a facile method, in which the mixed suspensions of the water-soluble polyimide precursor and graphene oxide (GO) sheets were freeze-dried, which was followed by a routine thermal imidation process. The porous GIAs obtained not only exhibit excellent elasticity and extremely low density values (from 33.3 to 38.9 mg.cm-3), but they also possess a superior compressive strength (121.7 KPa). The GIAs could support a weight of up to 31,250 times of its own weight, and such a weight-carrying capacity is much higher than that of other typical carbon-based aerogels. Having such a porous structure, and high strength and toughness properties make GIAs ideal candidates for oil spill cleanup materials. The oil/organic solvents' absorption capacity ranges from 14.6 to 85, which is higher than that of most other aerogels (sponges). With their broad temperature tolerance and acidic stability, the unique multifunctional GIAs are expected to further extend their application range into extreme environments.

Surface enhanced Raman scattering of adsorbates on Au-CsPbIBr2 perovskite-based nanocomposites: charge-transfer and electromagnetic enhancement.

In this study, perovskite-based nanocomposites as surface enhanced Raman scattering substrates were designed by physically sputtering Au nanoparticles onto fabricated all-inorganic CsPbIBr2 perovskite films, which provide much stronger SERS signals as compared to normal Au or perovskite substrates. Their synergism enhancement mechanisms and influence factors, including hybrid layer sequence, fabrication parameters and excitation source, are discussed. In addition, the prepared composite substrate exhibits excellent uniformity, reproducibility and time stability. This study promotes an easily prepared perovskite-based substrate for SERS-related applications and develops further understanding of molecule-semiconductor-noble metal nanostructure interfacial interactions.

A three-dimensional "turn-on" sensor array for simultaneous discrimination of multiple heavy metal ions based on bovine serum albumin hybridized fluorescent gold nanoclusters.

Traditional single sensor is designed based on the "lock-and-key" mode, which only relies on the most dominant interactions between the sensing element and the target. Although it exhibits high selectivity, there are challenges in detecting multiple analytes at the same time. Here, a sensor array with three sensing elements is developed to detect multiple heavy metal ions simultaneously and quickly. In our experiment, bovine serum albumin-encapsulated gold nanoclusters (BSA-AuNCs) were used as fluorescence probes and three different dopamine (DA) concentrations as nonspecific receptors. As we know, self-polymerized polydopamine (PDA) can quench part of the fluorescence of BSA-AuNCs. Upon the addition of the heavy metal ions, the diverse non-specific interactions between DA and heavy metal ions result in the difference in the number of the remaining PDA. Therefore it would lead to different degrees of fluorescence recovery behavior. This unique "turn-on" fluorescence response mode can be analyzed by linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA). Two-dimensional, three-dimensional and even four-dimensional mixed ions detection and quantitative detection have also been achieved. Moreover, by using this fluorescence array mode, heavy metal ions in tap water or blood samples can be detected.

In situ monitoring of the plasmon catalytic reaction of p-nitroaniline at a gas-liquid-solid three phase interface.

Localized surface plasmon resonance (LSPR) is caused by the irradiation of light on a metal surface. Here we present a surface plasmon catalytic reaction at the gas-liquid-solid three phase interface. Electrochemical deposition was used to prepare Ag nanostructure/Cu mesh surface-enhanced Raman scattering (SERS) substrates. Surface wettability was adjusted by changing the processing time of the surfactant. Then a three-phase interface platform was constructed with good SERS performance and active surface plasmon catalytic capacity by droplet detection. At the gas-liquid-solid three phase interface, different oxygen supplies for the catalytic reaction were offered on surfaces with different wettability values. Thus, in this study, surface plasmon catalytic reaction of p-nitroaniline (PNA) was successfully in situ monitored and the reaction mechanism was explored. Otherwise, density functional theory (DFT) was used to calculate the Raman spectra and energy levels of the reactants and reaction products. Moreover, this work provides a new platform for monitoring the surface plasmon reaction at the gas-liquid-solid three-phase interface and contributes to the development of the study in the surface plasmon catalytic reaction field.

A highly sensitive acetylcholinesterase electrochemical biosensor based on Au-Tb alloy nanospheres for determining organophosphate pesticides.

Accurately detect the residues of organophosphate pesticides (OPs) in food and environment is critical to our daily lives. In this study, we developed a novel acetylcholinesterase (AChE) biosensor based on Au-Tb alloy nanospheres (NSs) for rapid and sensitive detection of OPs for the first time. Au-Tb alloy NSs that with good conductivity and biocompatibility were produced with a mild hydrothermal. Under optimal conditions, the AChE biosensor was obtained by a simple assembly process, with a big linear range (10-13-10-7M) and the limit of detection was 2.51 × 10-14M for the determination of methyl parathion. Moreover, the determination of methyl parathion with the prepared biosensor presented a high sensitivity, outstanding repeatability and superior stability compared with other reported biosensors. Through the determination of tap water and Yanming lake samples, it was proved that the modified biosensor with satisfactory recoveries (96.76%-108.6%), and are realizable in the determination of OPs in real samples.

Delicate control of crystallographic Cu2O derived Ni-Co amorphous double hydroxide nanocages for high-performance hybrid supercapacitors: an experimental and computational investigation.

The reasonable design of the composition and hollow structure of electrode materials is beneficial for promoting the electrochemical properties and stability of electrode materials for high-performance supercapacitors, and it is of great significance to understand the inherent effect of these features on their performance. In this paper, the amorphous Ni-Co double hydroxide nanocages with hollow structures (Ni-Co ADHs) including quasi-sphere, cube and flower are delicately tailored via a Cu2O template-assisted approach. By combining experimental characterization and density functional theory (DFT) calculations, we systematically study the morphological growth of Cu2O templates under different conditions and the electrochemical performance of Ni-Co ADHs. Due to the coordination and synergistic effect between different components, the unique hollow structure and the nature of amorphous materials, Ni-Co ADHs deliver a high specific capacitance of 1707 F g-1 at 1 A g-1. The DFT calculations demonstrate that Ni-Co ADH nanocages exhibit an optimal redox reaction energy barrier and immensely promote the performance. In addition, a hybrid supercapacitor assembled with Ni-Co ADHs as a cathode and active carbon (AC) as an anode shows a high energy density of 33.8 W h kg-1 at a power density of 850 W kg-1 and exhibits an excellent cycling performance with a retention rate of 98% after 50 000 cycles. The successful synthesis of Ni-Co ADH nanocages, combined with rational computational simulations, indicates the excellent electrochemical performance and the potential utilization of amorphous hollow nanomaterials as electrodes for supercapacitors.

Predicting the right mechanism for hypervalent iodine reagents by applying two types of hypervalent twist models: apical twist and equatorial twist.

Since hypervalent twist followed by reductive elimination is a general reaction pattern for hypervalent iodine reagents, mechanistic studies about the hypervalent twist step could provide significant guidance for experiments. Previous studies have shown that there are two types of hypervalent twist models, i.e. apical twist and equatorial twist. We applied both hypervalent twist models to explain the isomerization mechanism of two important electrophilic trifluoromethylating reagents, Togni I and Togni II. Up to now, there are less detailed studies about the different hypervalent twist modes between both reagents. Here, we successfully identified Togni II's isomerization pathway via equatorial twist, and suggested that different hypervalent twist models should be considered to predict the right mechanisms of reactions with hypervalent iodine reagents participating. This study will also be helpful to design new Togni type reagents with higher intrinsic reactivity and stability by avoiding the formation of acyclic by-products.

Toxicity of different zinc oxide nanomaterials and dose-dependent onset and development of Parkinson's disease-like symptoms induced by zinc oxide nanorods.

With the increasing applications in various fields, the release and accumulation of zinc oxide (ZnO) nanomaterials ultimately lead to unexpected consequences to environment and human health. Therefore, toxicity comparison among ZnO nanomaterials with different shape/size and their adverse effects need better characterization. Here, we utilized zebrafish larvae and human neuroblastoma cells SH-SY5Y to compare the toxic effects of ZnO nanoparticles (ZnO NPs), short ZnO nanorods (s-ZnO NRs), and long ZnO NRs (l-ZnO NRs). We found their developmental- and neuro-toxicity levels were similar, where the smaller sizes showed slightly higher toxicity than the larger sizes. The developmental neurotoxicity of l-ZnO NRs (0.1, 1, 10, 50, and 100 µg/mL) was further investigated since they had the lowest toxicity. Our results indicated that l-ZnO NRs induced developmental neurotoxicity with hallmarks linked to Parkinson's disease (PD)-like symptoms at relatively high doses, including the disruption of locomotor activity as well as neurodevelopmental and PD responsive genes expression, and the induction of dopaminergic neuronal loss and apoptosis in zebrafish brain. l-ZnO NRs activated reactive oxygen species production, whose excessive accumulation triggered mitochondrial damage and mitochondrial apoptosis, eventually leading to PD-like symptoms. Collectively, the developmental- and neuro-toxicity of ZnO nanomaterials was identified, in which l-ZnO NRs harbors a remarkably potential risk for the onset and development of PD at relatively high doses, stressing the discretion of safe range in view of nano-ZnO exposure to ecosystem and human beings.

Revisiting the effect of f-functions in predicting the right reaction mechanism for hypervalent iodine reagents.

To understand the effect of f-functions in predicting the right reaction mechanism for hypervalent iodine reagents, we adopt the Ahlrichs basis set family def2-SVP and def2-TZVP to revisit the potential energy surfaces of IBX-mediated oxidation and Togni I's isomerisation. Our results further prove that f-functions (in either Pople, Dunning, or Ahlrichs basis set series) are indispensable to predict the correct rate-determining step of hypervalent iodine reagents. The f-functions have a significant impact on the predicted reaction barriers for processes involving the IX (X = O, OH, CF3 , etc.) bond cleavage and formation, for example, in the reductive elimination step or the hypervalent twist step. We furthermore explore two hypervalent twist modes that account for the different influences of f-functions for IBX and Togni I. Our findings may be helpful for theoretical chemists to appropriately study the reaction mechanism of hypervalent iodine reagents.