Molecule-confined modification of graphitic C3N4 to design mesopore-dominated Fe-N-C hybrid electrocatalyst for oxygen reduction reaction

To design inexpensive carbon catalysts and enhance their oxygen reduction reaction (ORR) activity is critical for developing efficient energy-conversion systems. In this work, a novel Fe-N-C hybrid electrocatalyst with carbon nanolayers-encapsulated Fe₃O₄ nanoparticles is synthesized successfully by utilizing the molecular-level confinement of graphitic C₃N₄ structures via hemin biomaterial. Benefiting from the Fe-N structure prevalent on the carbon nanosheets and large mesopore-dominated specific surface area, the synthesized catalyst under optimized conditions shows excellent electrocatalytic performance for ORR with an E_ORR at 1.08 V versus reversible hydrogen electrode (RHE) and an E_1/2 at 0.87 V vs. RHE, and outstanding long-term stability, which is superior to commercial Pt/C catalysts (E_ORR at 1.04 V versus RHE and E_1/2 at 0.84 V versus RHE). Moreover, the low hydrogen peroxide yield (<11%) and average electron transfer number (~3.8) indicate a four-electron ORR pathway. Besides, the maximum power density of the home-made Zn-air battery using the obtained catalyst is 97.6 mW cm⁻². This work provides a practical route for the synthesis of cheap and efficient ORR electrocatalysts in metal-air battery systems.     

Formation of ST12 phase Ge nanoparticles in ZnO thin films

In this work, we focus on the Ge nanoparticles (Ge-np) embedded ZnO multilayered thin films. Effects of reactive and nonreactive growth of ZnO layers on the rapid thermal annealing (RTA) induced formation of Ge-np have been specifically investigated. The samples were deposited by sequential r.f. and d.c. sputtering of ZnO and Ge thin film layers, respectively on Si substrates. As-prepared thin film samples have been exposed to an ex-situ RTA at 600 °C for 60 s under forming gas atmosphere. Structural characterizations have been performed by X-ray Diffraction (XRD), Raman scattering, Secondary Ion Mass Spectroscopy (SIMS), and Scanning Electron Microscopy (SEM) techniques. It has been realized that reactive or nonreactive growth of ZnO layers significantly influences the morphology of the ZnO: Ge samples, most prominently the crystal structure of Ge-np. XRD and Raman analysis have revealed that while reactive growth results in a mixture of diamond cubic (DC) and simple tetragonal (ST12) Ge-np, nonreactive growth leads to the formation of only DC Ge-np upon RTA process. Formation of ST12 Ge-np has been discussed based on structural differences due to reactive and nonreactive growth of ZnO embedding layer.     

Blocked crystallization in capped ultrathin polymer films studied by molecular simulations

The crystallization of capped ultrathin polymer films is closely dependent on film thickness and interfacial interaction. Using dynamic Monte Carlo simulations, the crystallization behaviors of polymer films confined between two substrates were investigated. The crystallization rate of confined polymers is reduced with high interfacial interactions. Above a critical strength of interfacial interaction, polymer crystallization in the thin film is inhibited within the simulation time scales. An increase in film thickness leads to a rise in critical interfacial interaction. In thicker films, the chains have more space to change conformation to form crystal stems. In addition, there are fewer absorbed segments in confined chains for the thicker films, and thus the chains have stronger ability to adjust their conformation. Therefore an increase in film thickness can cause a reduction in the entropic barrier required for the formation of crystals and thus an increase in the critical interfacial interaction. © 2018 Society of Chemical Industry     

Insight into enhanced hydrogen evolution of single-atom Cu1/TiO2 catalysts from first principles

Developing efficient catalysts of low-cost transition metals for hydrogen production is of great importance but remains a huge challenge. Motivated by the idea of engineering local atomic configuration, we propose to focus on single metal atom confined in the lattice oxygen environment, as a class of non-Pt catalysts for hydrogen production. By first principles calculations, we study the characteristics and mechanism of hydrogen evolution reaction of single-atom Cu supported on anatase TiO₂ catalysts, Cu₁/TiO₂. Cu preferentially sits on the bridge-centre site between two 2-fold coordinated O atoms (O_2c) on the surface. Cu and coordinated O_2c function as copper oxide species (-Cu-O-) in the reaction. The reaction starts with two isolated H respectively positioned on Cu and O_2c, proceeds with a transfer of H from O_2c to Cu, and eventually forms a H₂ molecule. The free energy profiles indicate that Cu₁/TiO₂ exhibits excellent hydrogen evolution activity even better than Pt and MoS₂. This study not only shows that single-atom Cu₁/TiO₂ is an excellent hydrogen evolution catalyst, but also expands the understanding of oxide species in single-atom catalysis and proposes an engineering local atomic configuration strategy for optimizing the design of single-atom catalysts for enhanced hydrogen production.     

Combined Effects of Confinement and Macromolecular Crowding on Protein Stability

Confinement and crowding have been shown to affect protein fates, including folding, functional stability, and their interactions with self and other proteins. Using both theoretical and experimental studies, researchers have established the independent effects of confinement or crowding, but only a few studies have explored their effects in combination; therefore, their combined impact on protein fates is still relatively unknown. Here, we investigated the combined effects of confinement and crowding on protein stability using the pores of agarose hydrogels as a confining agent and the biopolymer, dextran, as a crowding agent. The addition of dextran further stabilized the enzymes encapsulated in agarose; moreover, the observed increases in enhancements (due to the addition of dextran) exceeded the sum of the individual enhancements due to confinement and crowding. These results suggest that even though confinement and crowding may behave differently in how they influence protein fates, these conditions may be combined to provide synergistic benefits for protein stabilization. In summary, our study demonstrated the successful use of polymer-based platforms to advance our understanding of how in vivo like environments impact protein function and structure.     

A molecular model for ion dehydration in confined water

Although ion dehydration in confined water is ubiquitous in many important processes concerning ion adsorption, transport and separation, and so forth, few theoretical models have been developed to unravel the mechanism of dehydration in confined space. Herein, a molecular model is proposed by weighing the molecular orientation of surrounding water within the first hydration shell, and then this model is applied to predict the hydration numbers and hydrated radii of simple ions with the help of molecular density functional theory. The predictions are rationalized not only with parallel simulations but also with relevant experimental measurements. We find that the ion hydration in confined water is depressed owing to the confinement, and thus the multilayer hydration shell is disturbed, which results in the decline of hydration number and hydrated radius, favoring the ion dehydration. This work provides an insightful route toward the quantitative understanding and prediction of ion dehydration in confined water.     

配置高强箍筋混凝土框架梁端抗震性能试验研究

进行15个框架梁端试件的低周反复加载试验,其中试件的剪跨比包括1.4、2.5和3.4,试件的受力纵筋为HRB500级钢筋,箍筋为970MPa级PC钢棒和HRB400级钢筋。研究配置高强纵筋和高强箍筋的混凝土框架梁端的破坏特征、滞回曲线、骨架曲线、位移延性和刚度退化等抗震性能和极限承载力,分析平均约束应力（ ）的影响,并利用试验结果对比分析了中国、美国和日本相关标准的受剪承载力计算公式。结果表明：提高 可限制试件裂缝开展,降低破坏程度,使试件滞回曲线饱满,并可提高其抗震性能与极限承载力,但对受弯破坏试件的承载力和位移延性的提高幅度不大,且过大的 会使梁身过强而出现梁端结合面破坏;达到极限承载力时,所有试件的受力纵筋均屈服,受剪破坏试件中PC钢棒箍筋的实测最大应变值为 ;当取 为钢筋实测屈服强度且 ≤3.5MPa时,按《混凝土结构设计规范》（GB 50010-2010）和《高强箍筋混凝土结构技术规程》（CECS 356-2013）计算受剪承载力与试验值之比平均分别为0.91和0.87。     

圆钢管钢纤维活性粉末混凝土短柱轴压性能试验研究

为研究圆钢管钢纤维活性粉末混凝土（RPC）短柱的轴压性能,完成了7根外径219~273mm的圆钢管钢纤维RPC短柱轴压性能试验,分析了套箍系数、径厚比对轴压试件荷载-应变曲线和破坏特征的影响。结果表明：套箍系数ξ在0.63~0.88时,荷载-位移曲线在峰值荷载后出现下降段,短柱呈现剪切破坏模式;当ξ≥1时,在到达峰值荷载后,荷载下降幅度明显减小或出现回升趋势,短柱呈现腰鼓形破坏模式。在达到峰值荷载的85%之前,试件处于弹性阶段,钢管纵向应变大于横向应变;弹塑性阶段,钢管横向应变增加较快,其横向变形系数超过钢管的泊松比并逐渐增大,钢管对RPC的约束作用不断增强。随着混凝土抗压强度提高,其横向变形系数减小,钢管对核心区RPC约束效果降低。     

钢管混凝土核心柱轴压组合性能分析

对于钢管混凝土核心柱,核心钢管混凝土和外围普通混凝土的受压性能存在明显差异,本文分析了外围混凝土体积配箍率等因素对柱协同工作的影响,推导出了临界状态时外围混凝土柱的配箍率,并与试验值进行对比,吻合良好。