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1.
A mathematical model of simultaneous cobalt deposition and hydrogen evolution was developed and applied to the electroreduction process of 5 mM Co2+ ions investigated by cyclic voltammetry (CV) technique at different hydrogen ion concentrations (pH=2, 3, 4). The kinetic parameters of such a complex process were determined, and the validity of the model and its sensitivity to changes in individual parameters were verified. The relative value of the approximate standard deviation (ASD%) was used to determine the degree of fit of the model to the experimental data. The catalytic effect of cobalt on the hydrogen evolution process was comprehensively confirmed.  相似文献   
2.
沈荣晨  郝磊  陈晴  郑巧清  张鹏  李鑫 《物理化学学报》2022,38(7):2110014-41
随着化石燃料使用的增加和温室气体排放量持续上升,20世纪以来气温上升得更快。开发环境友好型能源取代传统化石燃料是当务之急。氢能源作为一种清洁、高效的能源,被认为是最有希望取代传统化石燃料的能源。光催化水分解水产氢作为为一种环保型技术被认为是最有前景的氢能生产方法。提高光生电子-空穴对分离效率是构建高效光催化剂的关键。然而,利用高度分散的助催化剂构建高效、稳定的产氢光催化剂仍然是一个挑战。本文首次成功地采用一步原位高温磷化法制备了高度分散的非贵金属三金属过度金属磷化Co0.2Ni1.6Fe0.2P助催化剂(PCNS-CoNiFeP)掺杂P的石墨相氮化碳纳米片(PCNS)。有趣的是,PCNS-CoNiFeP与传统氢氧前驱体磷化法制备的CoNiFeP相比,没有聚集性,分散性高。X射线衍射(XRD)、X射线光电子能谱(XPS)、元素映射图像和高分辨率透射电镜(HRTEM)结果表明,PCNS-CoNiFeP已成功合成。紫外-可见吸收光谱结果表明,PCNS-CoNiFeP在200–800 nm波长范围内较PCNS略有增加。光致发光光谱、电化学阻抗谱(EIS)和光电流分析结果表明,CoNiFeP助催化剂能有效促进光生电子-空穴对的分离,加速载流子的迁移。线性扫描伏安法(LSV)结果还表明,负载CoNiFeP助催化剂可大大降低CNS的过电位。结果表明,以三乙醇胺溶液为牺牲剂的PCNS-CoNiFeP最大产氢速率为1200 μmol·h-1·g-1,是纯CNS-Pt (320 μmol·h-1·g-1)的4倍。在420 nm处的表观量子效率为1.4%。PCNS-CoNiFeP在光催化反应中也表现出良好的稳定性。透射电镜结果表明,6–8 nm的CoNiFeP高度分散在PCNS表面。高度分散的CoNiFeP比聚集的CoNiFeP具有更好的电荷分离能力和更高的电催化析氢活性。由此可见,聚合的CoNiFeP-PCNs (300 μmol·h-1·g-1)的产氢速率远低于PCNS-CoNiFeP。此外,CNS的P掺杂可以改善其电导率和电荷传输。  相似文献   
3.
本文采用有限体积法对激光熔覆过程的温度场分布和熔体流动进行了数值模拟。基于CALPHAD相图法计算了基体和粉末的热物理性质,采用三维热源精确预测了凝固过程和温度分布,研究了Marangoni对流对熔池尺寸的影响。在熔池凝固过程中模拟所得出的温度梯度和凝固速度,预测了熔覆层凝固组织的演变趋势,相应的显微组织与实验结果吻合较好。  相似文献   
4.
Ruppeiner geometry has been successfully applied in the study of the black hole microstructure by combining with the small–large black hole phase transition, and the potential interactions among the molecular-like constituent degrees of freedom are uncovered. In this paper, we will extend the study to the triple point, where three black hole phases coexist acting as a typical feature of black hole systems quite different from the small–large black hole phase transition. For the six-dimensional charged Gauss–Bonnet anti-de Sitter black hole, we thoroughly investigate the swallow tail behaviors of the Gibbs free energy and the equal area laws. After obtaining the black hole triple point in a complete parameter space, we exhibit its phase structures both in the pressure–temperature and temperature–horizon radius diagrams. Quite different from the liquid–vapor phase transition, a double peak behavior is present in the temperature–horizon radius phase diagram. Then we construct the Ruppeiner geometry and calculate the corresponding normalized curvature scalar. Near the triple point, we observe multiple negatively divergent behaviors. Positive curvature scalar is observed for the small black hole with high temperature, which indicates that the repulsive interaction dominates among the microstructure. Furthermore, we consider the variation of the curvature scalar along the coexisting intermediate and large black hole curves. Combining with the observation for different fluids, the result suggests that this black hole system behaves more like the argon or methane. Our study provides a first and preliminary step towards understanding black hole microstructure near the triple point, as well as uncovering the particular properties of the Gauss–Bonnet gravity.  相似文献   
5.
通过熔盐法制备TiB2载体,并采用简单的沉淀-沉积法制备了Co/TiB2磁性可回收纳米催化剂,用于室温催化氨硼烷(NH3BH3)溶液产氢及串联降解对硝基苯酚(4-NP)及偶氮染料酸性橙7(AO7)、酸性红1(AR1)和甲基橙(MO)等有机污染物。采用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、振动样品磁强计等表征方法对催化剂的微观形貌和结构等进行分析。结果表明,Co纳米粒子均匀地分布在TiB2载体表面,晶粒尺寸约为40 nm,并且被TiB2载体包覆,具有典型的金属-载体强相互作用。Co/TiB2表现出优异的室温催化NH3BH3溶液产氢活性,产氢速率为565.8 molH2·molcat-1·h-1。在串联降解有机污染物反应中,Co/TiB2在7 min内催化4-NP氨基化的转化率接近100%,反应速率常数高达0.72 min-1;降解AO7的反应速率常数在3种偶氮染料中最高(0.34 min-1)。通过EPR-DMPO(EPR=电子顺磁共振,DMPO=5,5-二甲基-1-吡咯啉-N-氧化物)自由基捕获实验检测出Co/TiB2+NH3BH3催化体系中产生大量的氢自由基(·H)。得益于·H的强还原性,Co/TiB2+NH3BH3催化体系能够将4-NP氨基化为具有更高价值的对氨基苯酚(4-AP),同时能够还原偶氮染料分子中的显色基团偶氮基(—N=N—)。  相似文献   
6.
This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.  相似文献   
7.
A mere few decades ago, culture was thought a unique human attribute. Evidence to the contrary accumulated through the latter part of the twentieth century and has exploded in the present one, demonstrating the transmission of traditions through social learning across all principal vertebrate taxa and even invertebrates, notably insects. The scope of human culture is nevertheless highly distinctive. What makes our cultural capacities and their cognitive underpinnings so different? In this article I argue that in behavioural scientists' endeavours to answer this question, fruitful research pathways and their ensuing discoveries have come to exist alongside popular, yet in the light of current empirical evidence, highly questionable scenarios and even scientific blind alleys. I particularly re-evaluate theories that rely on the centrality of a supposed uniquely human capacity for imitative copying in explaining the distinctive capacity for massive cumulative cultural evolution (CCE) in our species. The most extreme versions of this perspective suffer logical incoherence and severe limits on scientific testability. By contrast the field has generated a range of rigorous observational and experimental methodologies that have revealed both long-term cultural fidelity and limited forms of CCE in non-human species. Attention now turns to directly investigating the scope, limits and underlying cognition of non-human versus human CCE, with a broader approach to factors additional to cultural transmission, notably the role of invention, innovation and evolved motivational biases underlying the scope of CCE in the species studied.  相似文献   
8.
Modern convection-based supports differ substantially in pore size, porosity, and microstructure topology. Due to such variability, it is challenging to evaluate the contribution of a particular microstructure topology on flow resistance. We demonstrated that the flow resistance parameter (ϕ $\phi $) introduced decades ago can be used as a criterion to evaluate the effect of microstructure topology on a pressure drop when the pore size is used as a characteristic support dimension. Furthermore, the ϕ $\phi $ value of simple cubic packing was calculated over the entire range of open porosity and compared to the ϕ $\phi $ values determined for pressure drop models derived for particular convection-based supports and experimental values of various convection-based supports from the literature. It was shown that different convection-based supports become clustered into distinct groups when plotted according to their ϕ $\phi $ and open porosity values, allowing their discrimination.  相似文献   
9.
Herein, we report a facile method for synthesizing MoCo-layered double hydroxide (LDH) nanosheets employing Prussian blue analog (PBA) as the precursor. The introduction of Mo in Co-LDH modulates the electronic structure, increases the number of active sites and electrochemical surface area to improve the hydrogen evolution, oxygen evolution, and overall water splitting activity. As a result, PBA-derived Mo0.25Co0.75-LDH nanosheets demonstrated 10 mA cm?2 current density at only 220 mV and 115 mV overpotentials for OER and HER, respectively. The overall water splitting was attained at 1.52 V cell voltage for 10 mA cm?2 current density.  相似文献   
10.
The aim of this study is to investigate market depth as a stock market liquidity dimension. A new methodology for market depth measurement exactly based on Shannon information entropy for high-frequency data is introduced and utilized. The proposed entropy-based market depth indicator is supported by an algorithm inferring the initiator of a trade. This new indicator seems to be a promising liquidity measure. Both market entropy and market liquidity can be directly measured by the new indicator. The findings of empirical experiments for real-data with a time stamp rounded to the nearest second from the Warsaw Stock Exchange (WSE) confirm that the new proxy enables us to effectively compare market depth and liquidity for different equities. Robustness tests and statistical analyses are conducted. Furthermore, an intra-day seasonality assessment is provided. Results indicate that the entropy-based approach can be considered as an auspicious market depth and liquidity proxy with an intuitive base for both theoretical and empirical analyses in financial markets.  相似文献   
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