Nitrogen, sulfur co-coordinated iron single-atom catalysts with the optimized electronic structure for highly efficient oxygen reduction in Zn-air battery and fuel cell.

Atomically dispersed iron-nitrogen-carbon (FesbndNsbndC) materials have been considered ideal catalysts for the oxygen reduction. Unfortunately, designing and adjusting the electronic structure of single-atom Fe sites to boost the kinetics and activity still faces grand challenges. In this work, the coordination environment engineering is developed to synthesize the FeSA/NSC catalyst with the tailored N, S co-coordinated Fe atomic site (Fe-N3S site). The structural characterizations and theoretical calculations demonstrate that the incorporation of sulfur can optimize the charge distribution of Fe atoms to weaken the adsorption of OH* and facilitate the desorption of OH*, thus leading to enhanced kinetics process and intrinsic activity. As a result, the S-modified FeSA/NSC exhibits outstanding catalytic activity with the half-wave potentials (E1/2) of 0.915 V and 0.797 V, as well as good stability, in alkaline and acidic electrolytes, respectively. Impressively, the excellent performance of FeSA/NSC is further confirmed in Zn-air batteries (ZABs) and fuel cells, with high peak power densities (146 mW cm-2 and 0.259 W cm-2).

All-Inorganic Perovskite Solar Cells: Defect Regulation and Emerging Applications in Extreme Environments.

All-inorganic perovskite solar cells (PSCs), such as CsPbX3, have garnered considerable attention recently, as they exhibit superior thermodynamic and optoelectronic stabilities compared to the organic-inorganic hybrid PSCs. However, the power conversion efficiency (PCE) of CsPbX3 PSCs is generally lower than that of organic-inorganic hybrid PSCs, as they contain higher defect densities at the interface and within the perovskite light-absorbing layers, resulting in higher non-radiative recombination and voltage loss. Consequently, defect regulation has been adopted as an important strategy to improve device performance and stability. This review aims to comprehensively summarize recent progresses on the defect regulation in CsPbX3 PSCs, as well as their cutting-edge applications in extreme scenarios. The underlying fundamental mechanisms leading to the defect formation in the crystal structure of CsPbX3 PSCs are firstly discussed, and an overview of literature-adopted defect regulation strategies in the context of interface, internal, and surface engineering is provided. Cutting-edge applications of CsPbX3 PSCs in extreme environments such as outer space and underwater situations are highlighted. Finally, a summary and outlook are presented on future directions for achieving higher efficiencies and superior stability in CsPbX3 PSCs.

High selective electrocatalytic reduction of carbon dioxide to ethylene enabled by regulating the microenvironment over Cu-Ag nanowires.

Copper-based tandem catalysts are effective candidates for yielding multi-carbon (C2+) products in electrochemical reduction of carbon dioxide (CO2RR). However, these catalysts still face a significant challenge regarding in the low selectivity for the production of a specific product. In this study, we report a high selectivity of 77.8 %±2 % at -1.0 V (vs RHE) for the production of C2H4 by using a Cu88Ag12NW catalyst which is primarily prepared through a combined Cu-Ag co-deposition and wet chemical method, employing an attractive strategy focused on regulating the microenvironment over Cu-Ag nanowires. The experimental and computational studies show that the higher *CO coverage and lower intermediate adsorption energy are important reasons for achieving the high C2H4 selectivity of Cu88Ag12NW catalyst. Comsol simulation results indicate that dense nanowires exhibit a nano-limiting effect on OH- ions, thereby leading to an increase in local pH and promoting coupling reactions. The catalyst demonstrates no noticeable decrease in current density or selectivity even after 12 h of continuous operation. The Cu-Ag nanowire composite exhibits remarkable catalytic activity, superior faradaic efficiency, excellent stability, and easy synthesis, which highlights its significant potential for electro-reducing carbon dioxide into valuable products.

Experimental and Theoretical Study of the New Leveler Basic Blue 1 during Copper Superconformal Growth.

A novel chlorinated functional group-modified triphenylmethane derivative leveler BB1 is used to achieve superconformal electrodeposition in microvias. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are performed to study the suppressing effect of BB1, while the convection-dependent adsorption of BB1 on the copper surface is analyzed by galvanostatic measurement, and a BB1 concentration window between 100 and 200 mg/L is beneficial for superfilling. The interactions among BB1, bis-(sodium sulfopropyl) disulfide (SPS), and poly(ethylene glycol) (PEG) are also investigated. Density functional theory (DFT) calculation and in situ Raman spectroscopy are coupled to study the suppression mechanism and synergistic suppression mechanism, namely, the adsorption effect between BB1 and copper substrate, as well as the coordination effect between the modified chlorinated functional group and Cu2+, is proposed. The copper layer becomes smoother and more compact with an increase in BB1 concentration, according to scanning electron microscopy (SEM) and atomic force microscopy (AFM), while X-ray diffraction (XRD) analysis shows that the introduction of BB1 is conducive to the formation of the copper (220) plane. Besides, the solution wettability is boosted by BB1. A copper interconnecting layer with high quality is achieved with 150 mg/L BB1, while the surface deposition thickness (SDT) is about 34 µm and filling percentages (FPs) for microvias with diameters of 100, 125, and 150 µm are 81.34, 82.72, and 81.39%, respectively.

Key Roles of Interfacial OH- ion Distribution on Proton Coupled Electron Transfer Kinetics Toward Urea Oxidation Reaction.

Enhancing alkaline urea oxidation reaction (UOR) activity is essential to upgrade renewable electrolysis systems. As a core step of UOR, proton-coupled electron transfer (PCET) determines the overall performance, and accelerating its kinetic remains a challenge. In this work, a newly raised electrocatalyst of NiCoMoCuOx Hy with derived multi-metal co-doping (oxy)hydroxide species during electrochemical oxidation states is reported, which ensures considerable alkaline UOR activity (10/500 mA cm-2 at 1.32/1.52 V vs RHE, respectively). Impressively, comprehensive studies elucidate the correlation between the electrode-electrolyte interfacial microenvironment and the electrocatalytic urea oxidation behavior. Specifically, NiCoMoCuOx Hy featured with dendritic nanostructure creates a strengthened electric field distribution. This structural factor prompts the local OH- enrichment in electrical double layer (EDL), so that the dehydrogenative oxidation of the catalyst is directly reinforced to facilitate the subsequent PCET kinetics of nucleophilic urea, resulting in high UOR performance. In practical utilization, NiCoMoCuOx Hy -driven UOR coupled cathodic hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2 RR), and harvested high value-added products of H2 and C2 H4 , respectively. This work clarifies a novel mechanism to improve electrocatalytic UOR performance through structure-induced interfacial microenvironment modulation.

Solvent environment engineering to synthesize FeNC nanocubes with densely Fe-Nx sites as oxygen reduction catalysts for Zn-air battery.

Zeolitic imidazole framework (ZIF)-derived iron-nitrogen-carbon (FeNC) materials are expected to be high-efficiency catalysts for oxygen reduction reaction (ORR). However, increasing the density of active sites while avoiding metal accumulation still faces significant challenges. Herein, solvent environment engineering is used to synthesize the FeNC containing dense Fe-Nx moieties by adjusting the solvent during the ZIF precursor synthesis process. Compared with methanol and water/methanol, the aqueous media can provide a more moderate Fe content for the ZIF precursor, which facilitates the construction of high-density Fe-Nx sites and prevent the appearance of iron-based nanoparticles during pyrolysis. Therefore, the FeNC(C) nanocubes synthesized in an aqueous media have the highest single atom Fe loading (0.6 at%) among the prepared samples, which presents excellent oxygen reduction properties and durability under alkaline and acidic conditions. The advantage of FeNC(C) is proven in Zn-air batteries, with outstanding performance and long-term stability.

Bimetallic co-doping engineering over nickel-based oxy-hydroxide enables high-performance electrocatalytic oxygen evolution.

Enhancing the electrocatalytic oxygen evolution reaction (OER) performance is essential to realize practical energy-saving water electrolysis and CO2 electroreduction. Herein, we report a bimetallic co-doping engineering to design and fabricate nickel-cobalt-iron collaborative oxy-hydroxide on nickel foam that labeled as NiCoFeOxHy-NF. As expected, NiCoFeOxHy-NF exhibits an outstanding OER activity with current density of 10 mA cm-2 at 194 mV, Tafel slope of 53 mV dec-1, along with the robust long-term stability, which is significantly better than bimetallic NiCo and NiFe combinations. Comprehensive computational simulations and characterizations jointly unveil that the twisted ligand environment induced by heteroatoms ensures the balance strength between the metal-oxygen hybrid orbital states and the oxidized intermediates adsorption, thus lowering the oxygen cycling energy barriers for overcoming the sluggish OER kinetics. Moreover, a novel phase transition behavior is monitored by in-situ Raman spectra under OER operating conditions, which facilitates electron-mass transfer as well as boosts the exposure of activity sites. For practical applications, Ni2P-NF || NiCoFeOxHy-NF and Cu || NiCoFeOxHy-NF couples were constructed to realize high-efficiency water electrolysis and CO2 electrochemical reduction for the production of valuable H2 and C2H4, respectively. This work elucidates a novel mechanism by which bimetallic co-doping improves the electrocatalytic OER activity of nickel-based hydroxides.

Construction of Self-Supporting NiCoFe Nanotube Arrays Enabling High-Efficiency Alkaline Oxygen Evolution.

Enhancing the intrinsic activity and modulating the electrode-electrolyte interface microenvironment of nickel-based candidates are essential for breaking through the sluggish kinetics limitation of the oxygen evolution reaction (OER). Herein, a ternary nickel-cobalt-iron solid solution with delicate hollow nanoarrays architecture (labeled as NiCoFe-NTs) was designed and fabricated via a ZnO-templated electrodeposition strategy. Owing to the synergistic nanostructure and composition feature, NiCoFe-NT presents desirable alkaline OER performance, with a η10 and η500 of 187 and 310 mV, respectively, along with favorable long-term durability. In-depth analyses identify the heterogeneous nickel-based (oxy)hydroxide species derived from the oxidative reconstruction acting as an active contributor for oxygen evolution. Impressively, the regulatory mechanism of the catalytic performance by a rationally designed nanostructure was elucidated by compressive analyses; that is, the faster gas release processes induced by nanotube arrays can modulate the heterogeneous interface states during OER, which effectively facilitates the electrochemical charge-mass transfer to promote the reaction kinetics. To assess the practical feasibility, an alkaline water electrolyzer and a CO2 electrochemical reduction flow cell were constructed by coupling the anodic NiCoFe-NTs and cathodic nickel phosphides (Ni2P-NF) and metallic Cu electrocatalysts, respectively, both of which achieved high-efficiency operation.

Synergistic doping and structural engineering over dendritic NiMoCu electrocatalyst enabling highly efficient hydrogen production.

The development of non-precious metal electrocatalysts with remarkable activity is a major objective for achieving high-efficiency hydrogen generation. Here, a trimetallic electrocatalyst with a dendritic nanostructure, which is denoted as NiMoCu-NF, was fabricated on nickel foam via a gas-template electrodeposition strategy. By virtue of the metallic doping and structural optimization, NiMoCu-NF exhibits superior HER electrocatalytic activity with an overpotential of 52 mV at 10 mA cm-2. Additionally, the NiMoCu-NF-derived nickel-based (oxy)hydroxide species in the oxidation operating state deliver considerable electrocatalytic urea oxidation reaction (UOR) performance to match the efficient H2 generation, with a low voltage of 1.54 V to realize overall electrolysis at 50 mA cm-2. Impressively, combined experimental and simulation analysis demonstrate that the NiMoCu-NF with a favorable 3D nanostructure feature effectively regulates the heterogeneous interface states, inducing a "Gas Microfluidic Pumping" (GMP) effect that improved electron-mass transfer properties to accelerate the electrocatalytic reaction kinetics of either the HER or UOR.

Synergistic Interfacial and Doping Engineering of Heterostructured NiCo(OH)x-CoyW as an Efficient Alkaline Hydrogen Evolution Electrocatalyst.

To achieve high efficiency of water electrolysis to produce hydrogen (H2), developing non-noble metal-based catalysts with considerable performance have been considered as a crucial strategy, which is correlated with both the interphase properties and multi-metal synergistic effects. Herein, as a proof of concept, a delicate NiCo(OH)x-CoyW catalyst with a bush-like heterostructure was realized via gas-template-assisted electrodeposition, followed by an electrochemical etching-growth process, which ensured a high active area and fast gas release kinetics for a superior hydrogen evolution reaction, with an overpotential of 21 and 139 mV at 10 and 500 mA cm-2, respectively. Physical and electrochemical analyses demonstrated that the synergistic effect of the NiCo(OH)x/CoyW heterogeneous interface resulted in favorable electron redistribution and faster electron transfer efficiency. The amorphous NiCo(OH)x strengthened the water dissociation step, and metal phase of CoW provided sufficient sites for moderate H immediate adsorption/H2 desorption. In addition, NiCo(OH)x-CoyW exhibited desirable urea oxidation reaction activity for matching H2 generation with a low voltage of 1.51 V at 50 mA cm-2. More importantly, the synthesis and testing of the NiCo(OH)x-CoyW catalyst in this study were all solar-powered, suggesting a promising environmentally friendly process for practical applications.

Correction: Complexing agent study via computational chemistry for environmentally friendly silver electrodeposition and the application of a silver deposit.

[This corrects the article DOI: 10.1039/C4RA05869K.].

miR­654­3p suppresses cell viability and promotes apoptosis by targeting RASAL2 in non­small­cell lung cancer.

Non­small­cell lung cancer (NSCLC) accounts for 80% of lung cancer cases, and is the leading cause of cancer­associated mortality worldwide. The present study aimed to investigate the roles of microRNA (miR)­654­3p in NSCLC. The expression levels of miR­654­3p and its target ras protein activator like 2 (RASAL2) mRNA were determined by reverse transcription­quantitative polymerase chain reaction; protein expression was analyzed by western blotting. Plasmids expressing miR­654­3p mimics were constructed and transfected into A549 cells. In addition, the viability and apoptotic rate of cells were analyzed by an MTT assay and flow cytometry, respectively. A luciferase reporter assay was performed to verify whether RASAL2 is a target of miR­654­3p. Downregulated miR­654­3p and upregulated RASAL2 expression were observed in tumor tissues and cells. Cell viability was suppressed and the apoptotic rate was increased in the miR­654­3p mimics­transfected cells compared with the control. Luciferase activity was decreased in the RASAL2­3' untranslated region­wild type group treated with miR­654­3p mimics. Furthermore, the present study revealed that overexpression of miR­654­3p could suppress the viability and induce the apoptosis of cells by targeting RASAL2 in NSCLC. The present findings may contribute to developments in the treatment of NSCLC.

Transition Metal and Nitrogen Co-Doped Carbon-based Electrocatalysts for the Oxygen Reduction Reaction: From Active Site Insights to the Rational Design of Precursors and Structures.

Considering the urgent requirement for clean and sustainable energy, fuel cells and metal-air batteries have emerged as promising energy storage and conversion devices to alleviate the worldwide energy challenges. The key step in accelerating the sluggish oxygen reduction reaction (ORR) kinetics at the cathode is to develop cost-effective and high-efficiency non-precious metal catalysts, which can be used to replace expensive Pt-based catalysts. Recently, the transition metal and nitrogen co-doped carbon (M-Nx /C) materials with tailored morphology, tunable composition, and confined structure show great potential in both acidic and alkaline media. Herein, the mechanism of ORR is provided, followed by recent efforts to clarify the actual structures of active sites. Furthermore, the progress of optimizing the catalytic performance of M-Nx /C catalysts by modulating nitrogen-rich precursors and porous structure engineering is highlighted. The remaining challenges and development prospects of M-Nx /C catalysts are also outlined and evaluated.

A theoretical study of atomically dispersed MN4/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction.

Carbon-based, non-noble metal catalysts for the oxygen reduction reaction (ORR) are crucial for the large-scale application of metal-air batteries and fuel cells. Density functional theory calculations were performed to explore the potential of atomically dispersed MN4/C (M = Fe or Mn) as an ORR catalyst in an acidic electrolyte and the ORR mechanism on MN4/C was systematically studied. The results indicated MN4 as the active site of MN4/C and a four-electron OOH transformation pathway as the preferred ORR mechanism on the MN4/C surface. The Gibbs free energy diagram showed that the rate-determining step of the FeN4/C and MnN4/C catalysts is the formation of the second H2O molecule and OOH*, respectively. FeN4/C exhibited higher thermodynamic limiting potential (0.79 V) and, thus, higher ORR activity than MnN4/C (0.52 V) in an acidic environment; its excellent catalytic performance is due to the nice electron structure and adsorption properties of the FeN4 site. Therefore, this work demonstrates that atomically dispersed MN4/C is a promising catalyst for the ORR.

STK31 regulates the proliferation and cell cycle of lung cancer cells via the Wnt/ß­catenin pathway and feedback regulation by c­myc.

Lung cancer, which is a leading cause of cancer­related deaths, is diagnosed at a male to female ratio of 2.1:1. Serine­threonine kinase 31 (STK31) is a novel cancer/testis (CT)­related gene that is highly expressed in several types of cancers, such as lung and colorectal cancer, and plays crucial roles in cancer. In the present study, increased expression of STK31 and ß­catenin was observed in lung cancer tissues and cell lines. Downregulation of STK31 expression in lung cancer cells significantly inhibited their proliferation by arresting the cell cycle in the G1 phase concurrent with decreased ß­catenin, c­myc and cyclin D1 protein levels, while upregulation of STK31 had the opposite effects. In addition, STK31­induced lung cancer cell viability, proliferation, cell cycle progression, and expression of related genes were completely attenuated by a Wnt/ß­catenin inhibitor (XAV939). Similar to XAV939, a c­myc inhibitor (10058­F4) also significantly attenuated STK31­induced proliferation and cell cycle progression in lung cancer cells. Inhibiting c­myc and TRRAP significantly decreased the expression of STK31, and a chromatin immunoprecipitation (ChIP) assay confirmed that c­myc directly bound to the STK31 promoter. These results indicated that STK31 may act as an oncogene in lung cancer and that c­myc may be the transcription factor that promotes STK31 expression. Moreover, the results suggested that c­myc can also regulate STK31 expression in a positive feedback loop, and the downregulation of STK31 in lung cancer cells had an inhibitory effect on cell viability, cell proliferation and cell cycle progression, likely by inactivating the Wnt/ß­catenin pathway and positive feedback regulation by c­myc.

Graphite N-C-P dominated three-dimensional nitrogen and phosphorus co-doped holey graphene foams as high-efficiency electrocatalysts for Zn-air batteries.

The search for metal-free catalysts for oxygen reduction reactions (ORRs) in energy storage and conversion devices, such as fuel cells and metal-air batteries, is highly desirable but challenging. Here, we have designed and synthesized controllable 3D nitrogen and phosphorous co-doped holey graphene foams (N,P-HGFs) as a high-efficiency ORR catalyst through structural regulation and electronic engineering. The obtained catalyst shows a half-wave potential of 0.865 V in alkaline electrolytes. It is found that Zn-air batteries with the N,P-HGFs-1000 air electrode exhibit excellent discharge performance and durability. Our study suggests that the remarkable ORR performance of N,P co-doped graphene is mainly due to the graphite N-C-P structure, where an enhanced charge density and increased HOMO energy level are confirmed by both experimental results and theoretical density-functional theory calculations.

miR­140­5p regulates cell migration and invasion of non­small cell lung cancer cells through targeting VEGFA.

Lung cancer is the most common type of cancer worldwide, the most prevalent form of which is non­small cell lung cancer (NSCLC). MicroRNAs (miRs) are involved in the progression of NSCLC; however, the specific function of miR­140­5p in NSCLC remains unclear. The present study demonstrated that miR­140­5p was downregulated in the tumor tissues of patients with NSCLC, and it was associated with a poor prognosis. Furthermore, miR­140­5p significantly suppressed cell migration and invasion of the NSCLC cell line A549. In addition, the direct regulatory effect of miR­140­5p on vascular endothelial growth factor­A (VEGFA) was predicted by TargetScan and verified using a luciferase reporter gene assay. The present study also hypothesized that miR­140­5p may inhibit the expression of phosphorylated­protein kinase B by targeting VEGFA. In conclusion, miR­140­5p may be a potential target for the development of anti­neoplastic therapies in lung cancer.

Superior cycle performance and high reversible capacity of SnO2/graphene composite as an anode material for lithium-ion batteries.

SnO2/graphene composite with superior cycle performance and high reversible capacity was prepared by a one-step microwave-hydrothermal method using a microwave reaction system. The SnO2/graphene composite was characterized by X-ray diffraction, thermogravimetric analysis, Fourier-transform infrared spectroscopy, Raman spectroscopy, scanning electron microscope, X-ray photoelectron spectroscopy, transmission electron microscopy and high resolution transmission electron microscopy. The size of SnO2 grains deposited on graphene sheets is less than 3.5 nm. The SnO2/graphene composite exhibits high capacity and excellent electrochemical performance in lithium-ion batteries. The first discharge and charge capacities at a current density of 100 mA g(-1) are 2213 and 1402 mA h g(-1) with coulomb efficiencies of 63.35%. The discharge specific capacities remains 1359, 1228, 1090 and 1005 mA h g(-1) after 100 cycles at current densities of 100, 300, 500 and 700 mA g(-1), respectively. Even at a high current density of 1000 mA g(-1), the first discharge and charge capacities are 1502 and 876 mA h g(-1), and the discharge specific capacities remains 1057 and 677 mA h g(-1) after 420 and 1000 cycles, respectively. The SnO2/graphene composite demonstrates a stable cycle performance and high reversible capacity for lithium storage.

A combined theoretical and experimental study for silver electroplating.

A novel method combined theoretical and experimental study for environmental friendly silver electroplating was introduced. Quantum chemical calculations and molecular dynamic (MD) simulations were employed for predicting the behaviour and function of the complexing agents. Electronic properties, orbital information, and single point energies of the 5,5-dimethylhydantoin (DMH), nicotinic acid (NA), as well as their silver(I)-complexes were provided by quantum chemical calculations based on density functional theory (DFT). Adsorption behaviors of the agents on copper and silver surfaces were investigated using MD simulations. Basing on the data of quantum chemical calculations and MD simulations, we believed that DMH and NA could be the promising complexing agents for silver electroplating. The experimental results, including of electrochemical measurement and silver electroplating, further confirmed the above prediction. This efficient and versatile method thus opens a new window to study or design complexing agents for generalized metal electroplating and will vigorously promote the level of this research region.