Although ether‐based electrolytes have been extensively applied in anode evaluation of batteries, anodic instability arising from solvent oxidability is always a tremendous obstacle to matching with ...high‐voltage cathodes. Herein, by rational design for solvation configuration, the fully coordinated ether‐based electrolyte with strong resistance against oxidation is reported, which remains anodically stable with high‐voltage Na3V2(PO4)2O2F (NVPF) cathode under 4.5 V (versus Na+/Na) protected by an effective interphase. The assembled graphite//NVPF full cells display superior rate performance and unprecedented cycling stability. Beyond that, the constructed full cells coupling the high‐voltage NVPF cathode with hard carbon anode exhibit outstanding electrochemical performances in terms of high average output voltage up to 3.72 V, long‐term cycle life (such as 95 % capacity retention after 700 cycles) and high energy density (247 Wh kg−1). In short, the optimized ether‐based electrolyte enriches systematic options, the ability to maintain oxidative stability and compatibility with various anodes, exhibiting attractive prospects for application.
By rational design of the solvation configuration, a cation–solvent fully coordinated ether‐based electrolyte with strong oxidation resistance up to 4.5 V (versus Na+/Na) was developed and applied in graphite//NVPF and LHC//NVPF full cells which showed superior rate performance and unprecedented cycling stability.
The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence of specific interactions between active sites. Such interactions, referred to as long‐range ...interactions (LRIs), play an important role in determining the rate and selectivity of a reaction. The optimal combination of metal centres must be determined to achieve the targeted efficiency. To date, various types of DACs have been synthesised and applied in electrochemistry. However, LRIs have not been systematically summarised. Herein, the regulation, mechanism, and electrocatalytic applications of LRIs are comprehensively summarised and discussed. In addition to the basic information above, the challenges, opportunities, and future development of LRIs in DACs are proposed in order to present an overall view and reference for future research.
Diatomic catalysts have attracted much attention, especially in electrochemistry. However, there have been no comprehensive reviews on long‐range interactions (LRIs) between metallic centres. This Minireview introduces the key aspects of LRIs and highlights opportunities for regulating electrocatalytic mechanisms, thus presenting guidelines for the targeted usage of LRIs.
Transition metal (TM)‐based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot ...fully explain the efficient TM redox cycling. Here, we discover a critical role of TM−O covalency in governing the intrinsic catalytic activity of Co3−xMnxO4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn−O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh–PMS interaction. With appropriate MnIV/MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1Mn1.9O4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.
The Mn−O covalency was enlarged by the Co sites mainly in the octahedral configuration, which results in a decreased charge transfer energy to favor Mn–PMS interaction and enhance MnIV reduction to boost PMS activation activity of Co‐Mn spinel oxides.
A Mn‐electrocatalytic ring‐opening azidation of tert‐cyclobutanols has been developed. The regioselective method is applicable for the azidation of a diverse array of cyclobutanols to provide ...practical γ‐azido ketones in 23–91% yields under chemical oxidants‐free reaction conditions. Detailed mechanistic studies suggest the process of Mn‐mediated alkoxy radical generation followed by β‐scission to form carbon‐centered radical species is possibly involved in this transformation.
It is still of great difficulty to develop the non‐platinum catalyst with high catalytic efficiency towards hydrogen evolution reaction via the strategies till now. Therefore, it is necessary to ...develop the new methods of catalyst designing. Here, we put forward the catalyst designed by the electronic metal–support interaction (EMSI), which is demonstrated to be a reliable strategy to find out the high‐efficiency catalyst. We carried out the density functional theory calculation first to design the proper EMSI of the catalyst. We applied the model of M1‐M2‐X (X=C, N, O) during the calculation. Among the catalysts we chose, the EMSI of Rh1TiC, with the active sites of Rh1‐Ti2C2, is found to be the most proper one for HER. The electrochemical experiment further demonstrated the feasibility of the EMSI strategy. The single atomic site catalyst of Rh1‐TiC exhibits higher catalytic efficiency than that of state‐of‐art Pt/C. It achieves a small overpotential of 22 mV and 86 mV at the at the current density of 10 mA cm−2 and 100 mA cm−2 in acid media, with a Tafel slope of 25 mV dec−1 and a mass activity of 54403.9 mA cm−2 mgRh−1 (vs. 192.2 mA cm−2 mgPt−1 of Pt/C). Besides, it also shows appealing advantage in energy saving compared with Pt/C (≈20 % electricity consuming decrease at 2 kA m−2) Therefore, we believe that the strategy of regulating EMSI can act as a possible way for achieving the high catalytic efficiency on the next step of SACs.
The electronic metal–support interaction (EMSI) is closely related to the electronic structure of active sites, which determines the catalytic activity. We put forward a method of designing the EMSI of single‐atomic site catalysts (SACs) to achieve high efficiency. The SACs achieve a lower overpotential and higher mass activity than any other SACs towards hydrogen evolution reaction, demonstrating the benefits of this method.
Efficient recruitment and angiogenesis of endothelial progenitor cells (EPCs) are critical during a thrombus event. However, the details of EPC recruitment and the regulation of angiogenesis have not ...been fully determined. The aim of this study was to determine the role of the long noncoding (lnc)RNA Wilms tumor 1 associated protein pseudogene 1 (WTAPP1) in regulation of the migration and angiogenesis of EPCs. EPCs were isolated from human peripheral blood and characterized by flow cytometry, after which lentivirus‐mediated lncRNA WTAPP1 overexpression and knockdown were performed. Scratch assay, Transwell assay, and in vitro and in vivo tube formation assays were performed to measure cell migration, invasion, and angiogenic abilities, respectively. Moreover, a microarray screen, bioinformatic prediction, and quantitative PCR and Western blot of miRNAs interacting with lncRNA WTAPP1 were conducted. Western blot was carried out to elucidate the relationship among WTAPP1, miR‐3120‐5P, and MMP‐1 in the autophagy pathway. WTAPP1 positively regulated migration, invasion, and in vitro and in vivo tube formation in EPCs by increasing MMP‐1 expression and activating PI3K/Akt/mTOR signaling. Furthermore, WTAPP1 contains a putative miR‐3120‐5P binding site. Suppression of WTAPP1 by miR‐3120‐5P decreased the level of MMP‐1. In addition, we demonstrated that suppression of the autophagy pathway is involved in the effects of WTAPP1 on EPC migration and angiogenesis. The lncRNA WTAPP1, a molecular decoy for miR‐3120‐5p, regulates MMP‐1 expression via the PI3K/Akt and autophagy pathways, thereby mediating cell migration and angiogenesis in EPCs. Acting as a potential therapeutic target, the lncRNA WTAPP1 may play an important role in the pathogenesis of DVT. Stem Cells 2018;36:1863–12
The long noncoding RNA Wilms tumor 1 associated protein pseudogene 1, a molecular decoy for miR‐3120‐5p, regulates MMP‐1 expression via the PI3K/Akt and autophagy pathways, thereby mediating cell migration and angiogenesis in endothelial progenitor cells.
Resistance to chemotherapy is a major challenge for the treatment of patients with colorectal cancer (CRC). Previous studies have found that microRNAs (miRNAs) play key roles in drug resistance; ...however, the role of miRNA‐373‐3p (miR‐375‐3p) in CRC remains unclear. The current study aimed to explore the potential function of miR‐375‐3p in 5‐fluorouracil (5‐FU) resistance. MicroRNA‐375‐3p was found to be widely downregulated in human CRC cell lines and tissues and to promote the sensitivity of CRC cells to 5‐FU by inducing colon cancer cell apoptosis and cycle arrest and by inhibiting cell growth, migration, and invasion in vitro. Thymidylate synthase (TYMS) was found to be a direct target of miR‐375‐3p, and TYMS knockdown exerted similar effects as miR‐375‐3p overexpression on the CRC cellular response to 5‐FU. Lipid‐coated calcium carbonate nanoparticles (NPs) were designed to cotransport 5‐FU and miR‐375‐3p into cells efficiently and rapidly and to release the drugs in a weakly acidic tumor microenvironment. The therapeutic effect of combined miR‐375 + 5‐FU/NPs was significantly higher than that of the individual treatments in mouse s.c. xenografts derived from HCT116 cells. Our results suggest that restoring miR‐375‐3p levels could be a future novel therapeutic strategy to enhance chemosensitivity to 5‐FU.
Resistance to chemotherapy is a major challenge for the treatment of patients with colorectal cancer (CRC). Our results suggest that the restoration of microRNA‐375‐3p levels could be a future novel therapeutic strategy to modulate and enhance chemosensitivity to 5‐fluorouracil treatment in CRC.
Hard carbon attracts considerable attention as an anode material for sodium‐ion batteries; however, their poor rate capability and low realistic capacity have motivated intense research effort toward ...exploiting nanostructured carbons in order to boost their comprehensive performance. Ultramicropores are considered essential for attaining high‐rate capacity as well as initial Coulombic efficiency by allowing the rapid diffusion of Na+ and inhibiting the contact of the electrolyte with the inner carbon surfaces. Herein, hard carbon nanosheets with centralized ultramicropores (≈0.5 nm) and easily accessible carbonyl groups (CO)/hydroxy groups (OH) are synthesized via interfacial assembly and carbonization strategies, delivering a large capacity (318 mA h g−1 at 0.02 A g−1), superior rate capability (145 mA h g−1 at 5.00 A g−1), and approximately 95% of reversible capacity below 1.00 V. Notably, a new charge model favoring fast capacitive sodium storage with dual potential plateaus is proposed. That is, the deintercalation of Na+ from graphitic layers is manifested as the low‐potential plateau region (0.01−0.10 V), contributing to stable insertion capacity; meanwhile, the surface desodiation process of the CO and OH groups corresponds to the high‐potential plateau region (0.40−0.70 V), contributing to a fast capacitive storage.
Hard carbon nanosheets with centralized ultramicropores (≈0.5 nm), accessible functional CO/OH groups, and large graphitic layer spacings exhibit excellent sodium‐storage properties. The desodiation process from graphitic layers and CO/OH groups results in a new sodium‐storage characteristic with dual‐potential plateaus during the charge process, which favors a high output of 95%, realistic capacity, and rapidly capacitive sodium storage.
Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, ...the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub‐nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub‐nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single‐atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a ≈20 % decrease of the electricity, ≈98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.
The tip effect (TE) has not been mentioned enough in catalysts designing, having a large space to explore. Based on the model of oxidized sub‐nano clusters, the TE was regulated and found to be efficient in designing catalysts, making TiC perform a high activity during the chlor‐alkali industry. This cluster system exhibits great potential in applying in the practical production and the comprehension of the TE is also pushed to a higher level.
The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity ...storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center.
A catalyst with N‐heterocyclic carbene‐ligated Cu SAS as the active site, accompanied by many micro‐nano reactors, synergistically promotes the electrochemical synthesis of methane.
PDF
