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1.
《International Journal of Hydrogen Energy》2022,47(9):6217-6226
The development of electrocatalysts with high activity and durability for oxygen reduction reaction (ORR) in acidic electrolyte environments remains a serious challenge for clean and efficient energy conversion. Synergistic effects between Pt and inexpensive metals, the d band center of Pt and catalyst morphology could adjust the adsorption and desorption of oxygen intermediates by the Pt. All the factors affect the catalytic performance of Pt-based nanocrystals. Here, we prepared Cu@PtCu3 NWs with an average diameter of 74.9 nm for Cu and about 10 nm PtCu3 layer. After etching, the Cu@PtCu3 nanowires is transformed into PtCu nanotube structure, due to the removal of copper from the surface and interior. PtCu NTs for ORR shows excellent activities and durability due to the integration of structural advantages and synergistic effects. Notably, the mass activity and specific activity of PtCu NTs (0.105 A mg?1Pt and 0.230 mA cm?2Pt) are 2.0 and 3.8 times higher than that of commercial Pt/C (0.053 A mg?1Pt and 0.06 mA cm?2Pt). The etching process to change the morphology of the catalyst and alter the electronic structure of the catalyst is expected to be useful for the design of future structured Pt-based alloy nanocatalysts. 相似文献
2.
Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry 相似文献
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With the increase of industrialization and urbanization, humankind faces massive oil-based pollution due to tanker accidents, human error, and natural disasters. For this, hydrophobic sorbents are fabricated and their applications for the removal of oil from polluted water sources are investigated. These hydrophobic sorbents are prepared by the condensation reaction of poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]isocyanurate cross-linker via bulk polymerization. The obtained sorbents exhibit high oil sorption capacity, fast absorption–desorption kinetics, and great reusability. Moreover, they can selectively absorb oil from the water surface, thus making them practical for water clean-up applications. 相似文献
5.
目的:探索炎性疾病患者的乳酸林格氏液(Ringer's lactate,RL)液体动力学特征以及炎性生物标记物是否可以作为协变量影响RL分布和排泄。方法:本研究为前瞻性队列研究。选择40例美国麻醉医师分级(ASA)I-II级,腹腔镜下择期胆囊切除术(胆囊炎组,n=20)或者腹腔镜下急诊阑尾切除术(阑尾炎组,n=20)。所有患者麻醉诱导前开始输注RL,按15 mL/kg,35 min内输毕。采用酶联免疫(enzyme-linked immunosorbent assay,ELISA)方法测定血浆炎症(TNF-α,IL-10和CRP)或者内皮损伤生物标记物(syndecan-1,SDC-1);利用血红蛋白(Hb)稀释-时间曲线和尿量,使用Phoenix软件,采用非线性混合效应模型分析计算RL液体动力学参数和协变量的影响。结果:与胆囊炎组相比,阑尾炎组RL从组织间隙到血浆的转运速率常数(k21)显著降低(14×10-3min-1 versus 35×10-3min-1;P=0.012)。阑尾炎组C反应蛋白(CRP)升高[中位数38.1(1.8-143.6) μg/mL versus 1.3(0.1-159.0) μg/mL;P<0.001];与清醒状态相比,麻醉期间(输液开始后30~45 min),液体从中央室中到外周室的转运速率常数(k12)显著增加(57×10-3min-1 versus 32×10-3min-1;P<0.01)。清除速率常数(k10)降低90%(0.6×10-3min-1 versus 5.3×10-3min-1;P<0.001)。无论在清醒状态还是麻醉状态下低血压均能降低液体清除;炎症或者内膜损伤的生物标记物不能作为显著影响RL液体动力学参数的协变量。结论:阑尾炎或者胆囊炎患者术前输入液体后“炎症反应的生物标记物”不是RL的液体动力学的协变量,但是两组患者中,全身麻醉期间输入液体的清除率下降。 相似文献
6.
目的研究热风辅助射频(hot air-assisted radio frequency,HA-RF)干燥过程中维生素C随温度变化的降解动力学模型。方法在6.5 cm极板间距和60℃热风系统条件下进行HA-RF干燥,重点研究胡萝卜丁中维生素C在干燥过程中的降解动力学,包括脱氢抗坏血酸(dehydroascorbic acid,DHAA)和抗坏血酸(ascorbic acid,AA)。总维生素C含量采用2,4-硝基苯肼分光光度法测定,AA采用2,6-二氯吲哚酚滴定法测定。结果HA-RF干燥过程中维生素C的降解规律符合一级可逆模型,其降解活化能为40.54 kJ/mol。DHAA活化能为35.83 kJ/mol,表明DHAA的稳定性低于AA。结论本研究使用的干燥温度为62.5~77.5℃,较高的干燥温度下维生素C降解速率较高,较低处理温度下的降解过程具有更好的模型适应度(R2>0.98)。 相似文献
7.
Zhongyu Qiu Xiaowen Ge Naibao Huang Shixian Zhou Junjie Zhang Jiaping Xuan 《International Journal of Hydrogen Energy》2021,46(3):2952-2959
Polyethylene oxide (PEO)-polypropylene oxide (PPO)-polyethylene oxide block copolymer having different molecular weights are used as precursors of carbon materials to prepare Hollow -Derivatives carbon material as an electrocatalyst through block copolymer self-assembly. The composition and microstructure of the prepared catalysts are shown by Raman spectroscopy, X-ray diffraction (XRD), Test of nitrogen adsorption and desorption curves, High resolution transmission electron microscopy (HR-TEM) and scanning electron microscopy (HR-SEM). Oxygen was passed into alkaline electrolyte solution until the solution reached saturation state. With molecular weight increasing, the obtained sample gradually changed from block to hollow and spherical. When the molecular weight was 12600 g mol?1, the evenly hollow carbon nanocages was acquired (C-12600). In O2 saturated alkaline electrolyte (0.1 M KOH solution), C-12600's limited current density,half-wave potential and initial potential are 5.23 mA cm?2@0.4 V, 0.72 V and 0.81 V, respectively. And most important is that half-wave potential and onset potential have barely change after 2000 cycles of cyclic voltammetry. As a result, the porous carbon materials exhibited excellent electrocatalytic activity while maintaining high stability in alkaline KOH solution. 相似文献
8.
《International Journal of Hydrogen Energy》2021,46(58):30061-30078
A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H2 adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H2 adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion. 相似文献
9.
Manjin Kim Qinfen Gu Tanveer Hussain Yahia Ali Trevor B. Abbott Kazuhiro Nogita 《International Journal of Hydrogen Energy》2021,46(53):27096-27106
With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH2), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H2 compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics. 相似文献
10.
Yilin Yang Siddarth K. Achar John R. Kitchin 《American Institute of Chemical Engineers》2022,68(6):e17653
The degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate-limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady-state and transient kinetics. Furthermore, we illustrate a hybrid local-global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high-quality results efficiently. 相似文献