Reaction environment self-modification on low-coordination Ni2+ octahedra atomic interface for superior electrocatalytic overall water splitting

Large scale synthesis of high-efficiency bifunctional electrocatalyst based on cost-effective and earth-abundant transition metal for overall water splitting in the alkaline environment is indispensable for renewable energy conversion. In this regard, meticulous design of active sites and probing their catalytic mechanism on both cathode and anode with different reaction environment at molecular-scale are vitally necessary. Herein, a coordination environment inheriting strategy is presented for designing low-coordination Ni²⁺ octahedra (L-Ni-8) atomic interface at a high concentration (4.6 at.%). Advanced spectroscopic techniques and theoretical calculations reveal that the self-matching electron delocalization and localization state at L-Ni-8 atomic interface enable an ideal reaction environment at both cathode and anode. To improve the efficiency of using the self-modification reaction environment at L-Ni-8, all of the structural features, including high atom economy, mass transfer, and electron transfer, are integrated together from atomic-scale to macro-scale. At high current density of 500 mA/cm², the samples synthesized at gram-scale can deliver low hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 262 and 348 mV, respectively.

     

原料丙烯中的杂质对聚合反应的影响

就目前来看,聚丙烯主要采用液相本体生产方式,因原料丙烯内含杂质,对生产聚合反应造成一定不良影响的问题日渐凸显。为从根本上提升聚丙烯生产质量与效率,相关研究工作者需对原料丙烯中杂质种类以及对聚合反应的影响进行深入分析,制定出最佳优化方案。     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Novel high-energy ionic molecules deriving from new monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties

ABSTRACT

In recent years, the exploration of a practical strategy for novel energetic molecules with high energy and low sensitivity is very desirable but highly challenging. Novel ionic energetic molecules have attracted much attention in this area due to their prominent advantages including low sensitivities, high thermal stability, and excellent energy performances. Herein, five different ionic energetic molecules based on new monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties with enhanced oxygen balance have been synthesized, characterized and evaluated as potential high-energy materials. Thermal stability, sensitivities and energy output test were measured and studied in detail. The heats of formation and energetic parameters were calculated by using Gaussian 09 suite of programs and EXPLO 5 code. The results suggest that all as-prepared new molecules exhibit good thermal stability with high decomposition temperature (3, 231°C; 5, 160°C; 6, 185°C; 7, 180°C; 8, 213°C), and relative low sensitivity (IS > 20 J, FS = 324 N). Inheriting the significant oxygen content of monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties, they also possess good energy properties (v _D = 8238 ~ 9208 m s^?1, P = 26.8 ~ 36.7 GPa, V _o = 481.8 ~ 959.4 L kg^?1), which make them competitive high-energy materials.     

Plasmonic coupling-enhanced in situ photothermal nanoreactor with shape selective catalysis for C-C coupling reaction

Carbon-carbon (C-C) coupling reactions represent one of the most powerful tools for the synthesis of complex natural products, bioactive molecules developed as drugs and agrochemicals. In this work, a multifunctional nanoreactor for C-C coupling reaction was successfully fabricated via encapsulating the core-shell Cu@Ni nanocubes into ZIF-8 (Cu@Ni@ZIF-8). In this nanoreactor, Ni shell of the core-shell Cu@Ni nanocubes was the catalytical active center, and Cu core was in situ heating source for the catalyst by absorbing the visible light. Moreover, benefiting from the plasmonic resonance effect between Cu@Ni nanocubes encapsulated in ZIF-8, the absorption range of nanoreactor was widened and the utilization rate of visible light was enhanced. Most importantly, the microporous structure of ZIF-8 provided shape-selective of reactant. This composite was used for the highly shape-selective and stable photocatalysed C-C coupling reaction of boric acid under visible light irradiation. After five cycles, the nanoreactor still remained high catalytical activity. This Cu@Ni@ZIF-8 nanoreactor opens a way for photocatalytic C-C coupling reactions with shape-selectivity.

     

等离子体预处理对解淀粉芽胞杆菌生长和α-淀粉酶分泌的影响

本研究采用低真空室温射频等离子体对解淀粉芽胞杆菌CICC 10035进行预处理，通过改变放电功率、处理时间和工作气压等参数，筛选最佳工艺条件，并使用蛋白质组学技术，对差异蛋白质进行生物信息学分析，探讨等离子体预处理对菌体生长和产酶性能的影响。结果表明，等离子体预处理的最佳工艺条件为：放电功率120 W，处理时间15 s，工作气压135 Pa。在最佳条件下，发酵48 h后，α-淀粉酶酶活超过400 U/mL，与对照样相比提高约20%。蛋白组学分析表明，等离子体预处理对菌体的蛋白合成及代谢产生了较强的正效应，尤其在DNA修复和氨基酸合成上，一方面提高了菌体活性，延缓其衰亡过程；另一方面促进了α-淀粉酶在菌体内的合成和分泌。     

基于热力学的自然风压分析方法

从热力学的角度出发，考虑巷道热力因素对风流的影响，导出自然风压的计算方法。     

石膏矿山顶板破坏机理探讨

近几年来，国内的石膏矿山中，大规模采空区顶板冒落事故频繁发生。目前，对于石膏矿山大规模顶板冒落发生机理研究的还很少。根据近几年对石膏矿山的现场调查，结合岩体力学的相关理论和数值模拟技术，得出石膏矿采场顶板冒落及大规模采空区顶板冒落主要是由于石膏矿柱流变特性使其强度变低及随着采区的扩大，石膏矿柱应力增大等而引起的。     

膨胀石墨的尺寸效应及其对油吸附的影响

用不同粒度的石墨在相同条件下酸化、高温膨胀，可获得膨胀倍数不同的膨胀石墨。通过扫描电镜及X射线衍射等观察膨胀石墨结构，证实在生产条件如酸氧化工艺、膨胀温度等相同时，鳞片石墨的粒度越大则膨胀倍数越高，对油的吸附性能越好。