The oxygen evolution reaction (OER) is a key reaction for many electrochemical devices. To date, many OER electrocatalysts function well in alkaline media, but exhibit poor performances in neutral and acidic media, especially the acidic stability. Herein, sodium‐decorated amorphous/crystalline RuO2 with rich oxygen vacancies (a/c‐RuO2) was developed as a pH‐universal OER electrocatalyst. The a/c‐RuO2 shows remarkable resistance to acid corrosion and oxidation during OER, which leads to an extremely high catalytic stability, as confirmed by a negligible overpotential increase after continuously catalyzing OER for 60 h at pH=1. Besides, a/c‐RuO2 also exhibits superior OER activities to commercial RuO2 and most reported OER catalysts under all pH conditions. Theoretical calculations indicated that the introduction of Na dopant and oxygen vacancy in RuO2 weakens the adsorption strength of the OER intermediates by engineering the d‐band center, thereby lowering the energy barrier for OER.
Ru nanoparticles have been demonstrated to be highly active electrocatalysts for the hydrogen evolution reaction (HER). At present, most of Ru nanoparticles-based HER electrocatalysts with high activity are supported by heteroatom-doped carbon substrates. Few metal oxides with large band gap (more than 5 eV) as the substrates of Ru nanoparticles are employed for the HER. By using large band gap metal oxides substrates, we can distinguish the contribution of Ru nanoparticles from the substrates. Here, a highly efficient Ru/HfO2 composite is developed by tuning numbers of Ru-O-Hf bonds and oxygen vacancies, resulting in a 20-fold enhancement in mass activity over commercial Pt/C in an alkaline medium. Density functional theory (DFT) calculations reveal that strong metal-support interaction via Ru-O-Hf bonds and the oxygen vacancies in the supported Ru samples synergistically lower the energy barrier for water dissociation to improve catalytic activities.
Facilitating the dissociation of water and desorption of hydrogen are both crucial challenges for improving the hydrogen evolution reaction (HER) in alkaline media. Herein, we report the synthesis of heterostructure of Ru2P/WO3@NPC (N, P co‐doped carbon) by a simple hydrothermal reaction using ruthenium and tungsten salts as precursors, followed by pyrolyzing under an Ar atmosphere. The Ru2P/WO3@NPC electrocatalyst exhibits an outstanding HER activity with an overpotential of 15 mV at a current density of 10 mA cm−2 and excellent durability in a 1.0 M KOH solution, outperforming state‐of‐the‐art Pt/C and most reported electrocatalysts. Experimental results combined with density functional calculations reveal that the electron density redistribution in Ru2P/WO3@NPC is achieved by electron transfer from NPC to Ru2P/WO3 and from Ru2P to WO3, which directly promotes the dissociation of water on W sites in WO3 and desorption of hydrogen on Ru sites in Ru2P.
The aim of this study was to explore the association of specific microRNAs (miRNAs) with the development of esophageal cancer (EC) and to identify new molecular markers for EC by analyzing the expression profiles of miRNAs in EC tissues. The expression profiles of miRNAs in paired EC and paracancerous normal tissues were detected and bioinformatically analyzed using miRNA assays. The outcomes were validated using real-time polymerase chain reaction. The miRNA assays revealed a total of 60 differentially expressed miRNAs in the EC tissues compared with those in the paracancerous normal tissues. Among them, 51 had doubled or more than doubled their expression levels and 9 had halved their expression levels. The most markedly upregulated miRNAs were hsa-miR-15a, hsa-miR-28-3p, hsa-miR-31, hsa-miR-99b, hsa-miR-101, hsa-miR-130a, hsa-miR-143, hsa-miR-196b, hsa-miR-200a, hsa-miR-210, hsa-miR-452 and hsa-miR-27a, whereas the most markedly downregulated miRNAs included hsa-miR-30b, hsa-miR-223, hsa-miR-454, hsa-miR-486, hsa-miR-574-3p and hsa-miR-126. Specific miRNA expression profiles exist in EC tissues and may serve as novel EC molecular markers.
Experimentally, GeS nanosheets have been successfully synthesized using vapor deposition processes and the one-pot strategy. Quite recently, GeS monolayer, the isoelectronic counterpart of phosphorene, has attracted much attention due to promising properties. By means of comprehensive first-principles calculations, we studied the stability and electronic properties of GeS monolayer. Especially, electric field and in-plane strain were used to tailor its electronic band gap. Upon applying electric field, the band gap of GeS monolayer greatly reduces and a semiconductor-metal transition happens under the application of a certain external electric field. Our calculations reveal that the band gaps of GeS monolayer are rather sensitive to the external electric field. On the other hand, for GeS under external strain, quite interestingly, we found that the band gap presents an approximately linear increase not only under compression strain but also under tensile strain from -10% to 10%. For biaxial compressive and tensile strains, the band gap follows the same trend as that of the uniaxial in the zigzag x direction. The present results provide a simple and effective route to tune the electronic properties of GeS monolayer over a wide range and also facilitate the design of GeS-based two-dimensional devices.
Synergistic optimization of the elementary steps of water dissociation and hydrogen desorption for the hydrogen evolution reaction (HER) in alkaline media is a challenge. Herein, the Ru cluster anchored on a trace P‐doped defective TiO2 substrate (Ru/P‐TiO2) was synthesized as an electrocatalyst for the HER; it exhibited a commercial Pt/C‐like geometric activity and an excellent mass activity of 9984.3 mA mgRu−1 at −0.05 V vs. RHE, which is 34.3 and 18.7 times higher than that of Pt/C and Ru/TiO2, respectively. Experimental and theoretical studies indicated that using a rutile‐TiO2‐crystal‐phase substrate enhanced the HER activity more than the anatase phase. Rich surface oxygen vacancies on rutile‐TiO2 facilitated the adsorption and dissociation of water, while the partial substitution of Ti4+ with P5+ enhanced H2 generation by facilitating hydrogen spillover from the Ru site to the surface P site, synergistically enhancing the HER activity.
Developing highly active, durable, and cost‐effective electrocatalysts for the oxygen evolution reaction (OER) is of prime importance in proton exchange membrane (PEM) water electrolysis techniques. Herein, a surface lanthanum‐deficient (SLD) iridium oxide as a highly efficient OER electrocatalyst is reported (labeled as La3IrO7‐SLD), which is obtained by electrochemical activation, and shows better activity and durability than that of commerically available IrO2 as well as most of the reported Ir‐based OER electrocatalysts. At a current density of 10 mA cm−2, the overpotential of La3IrO7‐SLD is 296 mV, which is lower than that of IrO2 (316 mV). Impressively, the increase of potential is less than 50 mV at a voltage–time chronopotentiometry extending for 60 000 s using a glass carbon electrode that is vastly superior to IrO2. Moreover, the mass activity of the catalyst is approximately five times higher than that of IrO2 at 1.60 V versus reversible hydrogen electrode. Density functional theory calculations suggest that a lattice oxygen participating mechanism with central Ir atoms serving as active sites (LOM‐Ir) rationalizes the high activity and durability for the La3IrO7‐SLD electrocatalyst. The favorable energy level of surface active Ir 5d orbitals relative to coordinated O 2p orbitals makes the La3IrO7‐SLD more active.
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