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41.
Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand 下载免费PDF全文
Zhengran Wang 《中国物理 B》2022,31(4):48202-048202
Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH2) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S0 and S1 states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH2 can undergo the ESDPT process in the S1 state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules. 相似文献
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QI Yuxue LI Tingting HU Yajie XIANG Jiahong SHAO Wenqian CHEN Wenhua MU Xueqin LIU Suli CHEN Changyun YU Min MU Shichun 《高等学校化学研究》2022,38(5):1282-1286
Constructing atomically dispersed active sites with densely exposed and dispersed double metal-Sx catalytic sites for favorable OER catalytic activity remains rare and challenging. Herein, we design and construct a Fe1Sx@Co3S4 electrocatalyst with Fe single atoms epitaxially confined in Co3S4 nanosheets for catalyzing the sluggish alkaline oxygen evolution reaction(OER). Consequently, in ultralow concentration alkaline solutions(0.1 mol/L KOH), such a catalyst is highly active and robust for OER with low overpotentials of 300 and 333 mV at current densities of 10 and 30 mA/cm2, respectively, accompanying long-term stability without significant degradation even for 350 h. In addition, Fe1Sx@Co3S4 shows a turnover frequency(TOF) value of 0.18 s−1, nearly three times that of Co3S4(0.07 s−1), suggesting the higher atomic utilization of Fe single atoms. Mössbauer and in-situ Raman spectra confirm that the OER activity of Fe1Sx@Co3S4 origins from a thin catalytic layer of Co(Fe)OOH that interacts with trace-level Fe species in the electrolyte, creating dynamically stable active sites. Combined with experimental characterizations, it suggests that the most active S-coordinated dual-metal site configurations are 2S-bridged (Fe-Co)S4, in which Co-S and Fe-S moieties are shared with two S atoms, which can strongly regulate the adsorption energy of reaction intermediates, accelerating the OER reaction kinetics. 相似文献
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Two-dimensional van der Waals magnetic materials are intriguing for applications in the future spintronics devices, so it is crucial to explore strategy to control the magnetic properties. Here, we carried out first-principles calculations and Monte Carlo simulations to investigate the effect of biaxial strain and hydrostatic pressure on the magnetic properties of the bilayer CrI3. We found that the magnetic anisotropy, intralayer and interlayer exchange interactions, and Curie temperature can be tuned by biaxial strain and hydrostatic pressure. Large compressive biaxial strain may induce a ferromagneticto-antiferromagnetic transition of both CrI3 layers. The hydrostatic pressure could enhance the intralayer exchange interaction significantly and hence largely boost the Curie temperature. The effect of the biaxial strain and hydrostatic pressure revealed in the bilayer CrI3 may be generalized to other two-dimensional magnetic materials. 相似文献
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将一种人工合成的无机聚合物——蒙脱石皂石黏土(smectite,Sm)应用于基质辅助激光解吸电离飞行时间质谱分析(matrix-assisted laser desorption/ionization time of flight mass spectrometry, MALDI-TOF-MS),以检测糖类化合物。 将传统的有机基质2,4,6-三羟基苯乙酮(trihydroxyacetophenone, THAP)与阳离子交换后的皂石黏土混合制备成新型复合基质,应用于糖类化合物的检测。通过比较不同的制样方法,测定不同分子直径的糖类化合物,发现由于受复合基质晶面间距的限制,只有小分子糖类化合物能进入晶面间隙充分接触有机基质并被离子化,从而实现对小分子糖类化合物的选择性检测。 相似文献
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采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)2(H2O)2]n·2H2O,其中H3TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力。单晶结构分析表明,该配合物属于三斜晶系,空间群$P \overline{1}$,配合物中心离子Ni(Ⅱ)分别与来自两个水分子上的氧原子及四个不同1,3,5-三(羧基甲氧基)苯配体的羧酸氧原子配位,形成六配位的NiO6八面体构型,并通过与1,3,5-三(羧基甲氧基)苯配体的氧原子配位不断延伸形成具有孔洞结构的一维链状构型。配合物具有良好的荧光性能和热稳定性。Hirshfeld表面作用分析表明配合物分子中O…H/H…O作用占主导且占比为39.0%,而H…H的作用力占比为25.9%,O…O的作用力占比为13.6%。 相似文献
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通过基于密度泛函理论的第一性原理计算,研究了Mg单掺杂、N单掺杂和不同浓度的Mg-N共掺杂β-Ga2O3的结构性质、电子性质和光学性质,以期获得性能比较优异的p型β-Ga2O3材料。建立了五种模型:Mg单掺杂、N单掺杂、1个Mg-N共掺杂、2个Mg-N共掺杂和3个Mg-N共掺杂β-Ga2O3。经过计算,3个Mg-N共掺杂β-Ga2O3体系的结构最稳定。此外,在5种模型中,3个Mg-N共掺杂β-Ga2O3体系的禁带宽度是最小的,并且N 2p和Mg 3s贡献的占据态抑制了氧空位的形成,从而增加了空穴浓度。因此,3个Mg-N共掺杂β-Ga2O3体系表现出优异的p型性质。3个Mg-N共掺杂体系的吸收峰出现明显红移,在太阳盲区的光吸收系数较大,这归因于导带Ga 4s、Ga 4p、Mg 3s向价带O 2p、N 2p的带间电子跃迁。本工作将为p型β-Ga2O3日盲光电材料的研究和应用提供理论指导。 相似文献
49.
High dielectric loss materials have an important application in electromagnetic (EM) absorption fields. In this paper, the ternary nanocomposites: 1T/2H-MoS2/Mo2S3 with heterogeneous interfaces are synthesized by hydrothermal method. XRD, XPS, FTIR, SEM, and TEM measurements are applied to study the structure, morphology, and composition. The frequency spectra of complex permittivity (εr-f) are measured in 2–18 GHz by vector network analyzer. The results show that the nanocomposites have higher dielectric loss angle tangents than the reported 2H-MoS2 absorbers. Based on the εr-f spectra, the reflection loss-frequency curves () are simulated at given thicknesses. An effective absorption bandwidth of 5.2 GHz (12.8–18 GHz) and a peak of −29.49 dB are achieved in a thin thickness of 1.62 mm, which are comparable to the reported 2H-MoS2 absorbers with complex composition, showing that the 1T/2H-MoS2/Mo2S3 nanocomposites have great application potential as an EM wave absorber in the Ku band. 相似文献
50.
This study investigated the effects of different treatment of alkaline pH-shifting on milk protein concentrate (MPC), micellar casein concentrate (MCC) and whey protein isolate (WPI) assisted by the same ultrasound conditions, including changes in the physicochemical properties, solubility and foaming capacity. The solubility of milk proteins had a significant increase with gradual enhancement of ultrasound-assisted alkaline pH-shifting (p < 0.05), especially for MCC up to 99.50 %. Also, treatment made a significant decline in the particle size of MPC and MCC, as well as the turbidity of the proteins (p < 0.05). The foaming capacity of MPC, MCC, and WPI was all improved, especially at pH 11, and at this pH, the milk protein also showed the highest surface hydrophobicity. The best foaming capacity at pH 11 was the result of the combined effect of particle size, potential, protein conformation, solubility, and surface hydrophobicity. In conclusion, ultrasound-assisted pH-shifting treatment was found to be effective in improving the physicochemical properties and solubility and foaming capacity of milk proteins, especially MCC, with promising application prospect in food industry. 相似文献