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51.
针对浅埋隧道开挖后底部隆起变形现象,应用极限分析上限法构造了考虑底部隆起变形的围岩压力计算模型,结合线性Mohr-Coulomb准则等推导出极限围岩压力的理论表达式。通过约束条件将围岩压力的计算转化为数学中的最优化问题,编制程序进行了优化计算。将计算结果与工程实测数据及文献计算结果进行了对比,验证了当前方法的可靠性。同时,指出在运用极限分析法处理浅埋隧道围岩压力问题过程中应将隧道底部一同考虑,对隧道底部支护会对整个围岩压力产生影响,有助于隧道结构的整体稳定。研究可以为浅埋隧道的开挖、支护提供一定的理论指导. 相似文献
52.
A method of syringe-dispersive solid-phase extraction combined with ultrahigh performance liquid chromatography with tandem mass spectrometry for the simultanous determination of 10 macrolides in manurebased fertilizers was developed. After extraction with methanol and acetonitrile,the extracts were purified by insyringe dispersion solid-phase extraction in syringes pre-filled with 60 mg PSA and 30 mg C18. The resulted extracts were further separated by a BEH C18 column,detected by multiple reaction monitoring in electrospray positive ion mode,and quantified by matrix-matched external standard method. The results showed that the recoveries of the target compounds ranged from 70% to 110% at three spiked levels(10,30,and 50 μµg/kg)with the relative standard deviations ranged from 1.4% to 12%. The limits of detection and quantification were 0.57 1.75 and 2.77-5.40 μµg/kg,respectively. This method was suitable for the simultaneous determination of residual macrolides in organic fertilizers. © 2023, Youke Publishing Co.,Ltd. All rights reserved. 相似文献
53.
Pengzhou Li Dr. Meng Liao Dr. Shuquan Cui Jiaxin Li Dr. Lei Ye Yibei Yang Chuang Wang Prof. Bingjie Wang Prof. Huisheng Peng 《Angewandte Chemie (International ed. in English)》2023,62(17):e202300705
Flexible batteries based on gel electrolytes with high safety are promising power solutions for wearable electronics but suffer from vulnerable electrode-electrolyte interfaces especially upon complex deformations, leading to irreversible capacity loss or even battery collapse. Here, a supramolecular sol-gel transition electrolyte (SGTE) that can dynamically accommodate deformations and repair electrode-electrolyte interfaces through its controllable rewetting at low temperatures is designed. Mediated by the micellization of polypropylene oxide blocks in Pluronic and host-guest interactions between α-cyclodextrin (α-CD) and polyethylene oxide blocks, the high ionic conductivity and compatibility with various salts of SGTE afford resettable electrode-electrolyte interfaces and thus constructions of a series of highly durable, flexible aqueous zinc batteries. The design of this novel gel electrolyte provides new insights for the development of flexible batteries. 相似文献
54.
Dr. Jia-Hao Xie Yi-Ming Hou Zuolijun Feng Prof. Dr. Shu-Li You 《Angewandte Chemie (International ed. in English)》2023,62(10):e202216396
Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium-catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction of adjacent stereocenters (1,2-position) reported in the literature, the current reaction can achieve the stereodivergent construction of nonadjacent stereocenters (1,3-position) by a proper combination of two chiral catalysts with different enantiomers. 相似文献
55.
Yanan Chang Zhangyu Ma Xuyun Lu Shasha Wang Prof. Jianchun Bao Prof. Ying Liu Prof. Chao Ma 《Angewandte Chemie (International ed. in English)》2023,62(41):e202310163
The rational design of advanced nanohybrids (NHs) with optimized interface electronic environment and rapid reaction kinetics is pivotal to electrocatalytic schedule. Herein, we developed a multiple heterogeneous Co9S8/Co3S4/Cu2S nanoparticle in which Co3S4 germinates between Co9S8 and Cu2S. Using high-angle annular-dark-field imaging and theoretical calculation, it was found that the integration of Co9S8 and Cu2S tends to trigger the interface phase transition of Co9S8, leading to Co3S4 interlayer due to the low formation energy of Co3S4/Cu2S (−7.61 eV) than Co9S8/Cu2S (−5.86 eV). Such phase transition not only lowers the energy barrier of oxygen evolution reaction (OER, from 0.335 eV to 0.297 eV), but also increases charge carrier density (from 7.76×1014 to 2.09×1015 cm−3), and creates more active sites. Compared to Co9S8 and Cu2S, the Co9S8/Co3S4/Cu2S NHs also demonstrate notable photothermal effect that can heat the catalyst locally, offset the endothermic enthalpy change of OER, and promote carrier migrate, reaction intermediates adsorption/deprotonation to improve reaction kinetics. Profiting from these favorable factors, the Co9S8/Co3S4/Cu2S catalyst only requires an OER overpotential of 181 mV and overall water splitting cell voltage of 1.43 V to driven 10 mA cm−2 under the irradiation of near-infrared light, outperforming those without light irradiation and many reported Co-based catalysts. 相似文献
56.
Prof. Takayuki Nakajima Mizuki Takubo Yurika Komura Yuki Maeda Miwa Sato Maki Zouda Prof. Tomoaki Tanase 《欧洲无机化学杂志》2023,26(9):e202200648
A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso-dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu ( 1 a ); M1=Pd, M2=Rh, R=tBu ( 2 a ), Xyl ( 2 b ); M1=Pt, M2=Rh, R=tBu ( 3 a ), Xyl ( 3 b ); M1=Pd, M2=Ir, R=tBu ( 4 a )), supported by a tetradentate phosphine ligand, meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), were synthesized by stepwise reactions of meso-dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso-dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso-dpmppp)(XylNC)] ( 5 ), was also prepared. The structures of 1 – 5 were determined by X-ray analyses to contain two square planar d8 metal centers with face-to-face arrangement, where meso-dpmppp supports M1 and M2 metal ions in cis/trans-P,P coordination mode, combining cis-{M1P2Cl2} and trans-{M2P2(CNR)2} units. Complexes 1 – 4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a – 4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1 – 5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo- and regioselectivity compared with 2 – 5 . 相似文献
57.
气溶胶中磷(P)的准确测定是评估磷沉降对青藏高原生态效应及磷的生物地球化学循环的重要前提。针对青藏高原气溶胶中磷含量低及滤膜单个样品量有限的特征,本文建立了高压密闭消解-电感耦合等离子体质谱法测定气溶胶中磷及其他元素含量的方法。电感耦合等离子体质谱法(ICP-MS)测得P元素的检出限为3.5 μg/L,优于电感耦合等离子体发射光谱仪(ICP-OES)的检测限(89 μg/L),其他元素检出限均达到μg/L(ppb)级(0.013-36 μg/L),部分元素如Co、Cd、Pb等达到ng/L(ppt)级(2-7 ng/L)。各元素线性关系良好,测定结果的相对标准偏差(RSD) < 5%,磷的加标回收在90-103%, 方法准确度和精密度满足分析要求。该方法成功地测定了青藏高原实际气溶胶样品中磷及其他元素,具有良好的可靠性和实用性。 相似文献
58.
Haodong Nie Kaiqiang Wei Yi Li Yan Liu Yajie Zhao Hui Huang Mingwang Shao Yang Liu Zhenhui Kang 《中国化学快报》2021,32(7):2283-2286
Overall water photo-splitting is a prospective ideal pathway to produce ultra-clean H_2 energy by semiconductors.However,the band structure of many semiconductors cannot satisfy the requirement of H_2 and O_2 production at the same time.Herein,we illustrate that carbon dots(CDs)/Bi_2 WO_6 photocatalyst with compensatory photo-electronic effect has enhanced activity for overall water photo-splitting without any sacrificial agent.In this complex photocatalytic system,the photo-potential provided by CDs makes the CDs/Bi_2 WO6(C-BWO) composite could satisfy the band structure conditions for overall water photo-splitting.The C-BWO composite(3 wt% CDs content) exhibits optimized hydrogen evolution(oxygen evolution) of 0.28 μmol/h(0.12 μmol/h) with an approximate 2:1(H_2:O_2) stoichiometry at normal pressure.We further employed the in-situ transient photovoltage(TPV) technique to study the photoelectron extraction and the interface charge transfer kinetics of this composite catalyst. 相似文献
59.
《中国化学快报》2021,32(9):2597-2616
Electrochemical overall water splitting is attracting a broad focus as a promising strategy for converting the electrical output of renewable resources into chemical fuels, specifically oxygen and hydrogen. However, the urgent challenge in water electrolysis is to search for low-cost, high-efficiency catalysts based on earth-abundant elements as an alternative to the high-cost but effective noble metal-based catalysts. The transition metal-based catalysts are more appealing than the noble metal catalysts because of its low cost, high performance and long stability. Some recent advances for the development in overall water splitting are reviewed in terms of transition metal-based oxides, carbides, phosphides, sulfides, and hybrids of their mixtures as hybrid bifunctional electrocatalysts. Concentrating on different catalytic mechanisms, recent advances in their structural design, controllable synthesis, mechanistic insight, and performance-enhancing strategies are proposed. The challenges and prospects for the future development of transition metal-based bifunctional electrocatalysts are also addressed. 相似文献
60.