The effect of copper content on the reactivity of Cu/Co6Al2 solids in the catalytic steam reforming of methane reaction

The steam reforming of methane over Cu/Co₆Al₂ mixed oxides with different copper contents was studied. The Co₆Al₂ support was prepared via the hydrotalcite route. It was thermally stabilized at 500 °C, impregnated with 5 wt.%, 15 wt.% or 25 wt.% copper using copper (II) nitrate Cu(NO₃)₂·3H₂O precursor and then calcined again at 500 °C under an air flow. The impregnation of copper enhanced significantly the reactivity of the solids in the considered reaction. The 5Cu/Co₆Al₂ solid was the most reactive one, with a methane conversion of 96% at 650 °C. The selectivities of H₂ and CO₂ were also better for the catalyst containing 5 wt.% copper compared to higher copper loadings. The decrease in the catalytic reactivity with increasing the copper content was attributed to the formation of agglomerated and less reactive CuO species, which were detected by XRD and TPR analyses.     

The Influence of Different Pretreatment Methods on Color and Pigment Change in Beetroot Products

Vegetable processing pomace contains valuable substances such as natural colors that can be reused as functional ingredients. Due to a large amount of water, they are an unstable material. The aim of our research was to assess how the pretreatment method (thermal or nonthermal) affects the properties of powders obtained from beet juice and pomace after the freeze-drying process. The raw material was steamed or sonicated for 10 or 15 min, and then squeezed into juice and pomace. Both squeezed products were freeze-dried. The content of dry substance; L*, a*, and b* color parameters; and the content of betalain pigments were analyzed. Pretreatments increased the proportion of red and yellow in the juices. Steam and ultrasound caused a significant reduction in parameter b* in the dried pomace. A significant increase in betanin in lyophilizates was observed after pretreatment with ultrasound and steam for 15 min. As a result of all experiments, dried juices and pomaces can also be used as a colorant source. However, there is higher potential with pomaces due to their additional internal substances as well as better storage properties. After a few hours, juice was sticky and not ready to use.     

基于Ti3C2-MXene的太阳能界面水汽转换

水资源匮乏是现代化发展中面临的全球性问题,太阳能界面水汽转换(Interfacial Solar Steam Generation, ISSG)是一种高效、绿色、低成本进行海水淡化和废水处理的方法。ISSG使用绿色的太阳能作为热源,通过光热转换并将热限制在水气界面上以高效产生蒸气,然后经过冷凝收集获得清洁水。设计和构筑具有强光吸收的光热转换材料是ISSG的技术核心。Ti₃C₂-MXene是一种新型二维碳化钛材料,具有比表面积大、水分散性好和光热转换效率高等优点,在ISSG领域具有巨大的应用潜力。本文介绍了ISSG技术和MXene,总结了光热转换材料的设计原则,论述了Ti₃C₂-MXene复合材料在ISSG领域的研究进展,其中包括二维MXene薄膜、三维MXene气凝胶和水凝胶、生物基-MXene复合材料的构筑和性能等,并分析了Ti₃C₂-MXene所面临的挑战和发展前景。     

物理化学教学中安全工程教育的融合与内化实例*

如何强化安全工程教育是化学化工类专业高等教育的一个重要课题。通过对蒸汽锅炉爆炸、火灾爆燃事故以及锈蚀危害等3个实例的详细讲述,指出在物理化学的教学中,若适时融入相关的安全工程教育,可以使学生深刻理解安全事故发生及防范所依赖的物理化学原理,从而起到安全意识的内化作用。教学中现代教育技术的引入可以增强这一效果。     

Revelation of ESIPT mechanism for the novel fluorescent system HNIBT in toluene and methanol solvents: A TDDFT study

In this work, we devote to explore excited‐state intramolecular proton transfer (ESIPT) behavior for a novel fluorescent molecule naphthalimide‐based 2‐(2‐hydroxyphenyl)‐benzothiazole (HNIBT) [New J. Chem. 2019, 43, 9152.] in toluene and methanol (MeOH) solvents. Exploring weak interactions, stable HNIBT‐enol, and HNIBT‐MeOH‐enol complex can be found in S₀ state via TDDFT/B3LYP/6‐311+G(d,p) level. Given photoexcitation, intramolecular hydrogen bond O1? H2···N3 of HNIBT‐enol and HNIBT‐MeOH‐enol is dramatically enhanced, which offers impetus for facilitates ESIPT reaction. After repeated comparisons, we verify the unavailability of intermolecular hydrogen bonding effects between HNIBT‐enol and MeOH molecules. In view of excitation, HOMO (π) → LUMO (π*) transition and the changes of electronical densities indeed impulse ESIPT tendency. Via constructing potential energy curves (PECs), for both HNIBT‐enol and HNIBT‐MeOH‐enol complex, the ESIPT could only occur along with intramolecular hydrogen bond O1? H2···N3. Through comparison, the potential barrier falls from 4.124 kcal/mol (HNIBT‐enol) to 2.132 kcal/mol (HNIBT‐MeOH‐enol). Therefore, we confirm that the ESIPT of the HNIBT system happens more easily in the MeOH solvent compared with the toluene solvent.     

改进蚁群PID-神经元解耦的CFB锅炉燃烧系统控制

床温和主汽压都是循环流化床锅炉生产运行中的重要参数,会直接影响机组的安全性和经济性。但由于这两者对象存在非线性、大时延、强耦合等特点,其现场控制效果一直不太理想。本文首先采用自适应神经元将床温和主汽压解耦,再利用具有分工特征的蚁群算法优化参数的PID控制器对两者进行独立控制。采用该算法优化常规PID控制参数,能够实现控制参数的快速寻优。该方案应用于循环流化床锅炉燃烧系统仿真,结果表明能有效实现系统解耦,且具有响应快、超调量小等优点,有效地提高了控制品质。     

基于GA的主汽温系统内模控制研究

主汽温控制系统是典型的大迟延、大惯性、时变控制系统,一直以来都是火电厂自动控制的难点。为此将内模控制引入主汽温控制系统,并提出采用遗传算法对滤波器参数优化整定,该方法简单易行,相较于传统PID参数整定方法具有一定的优越性。并对内模控制为主控制器的IMC-PI控制系统进行SIMULINK仿真,与PID-PI控制系统进行对比,仿真结果表明IMC-PID控制系统相比于传统PID-P串级控制系统过渡时间短、超调量小、鲁棒性好等特点。其控制效果好于常规串级 PID 控制系统,适用于大迟延、大惯性过程的控制,并且易于在工业上实现。     

Photoassisted Selective Steam and Dry Reforming of Methane to Syngas Catalyzed by Rhodium–Vanadium Bimetallic Oxide Cluster Anions at Room Temperature

Photoassisted steam reforming and dry (CO₂) reforming of methane (SRM and DRM) at room temperature with high syngas selectivity have been achieved in the gas-phase catalysis for the first time. The catalysts used are bimetallic rhodium–vanadium oxide cluster anions of Rh₂VO_1–3⁻. Both the oxidation of methane and reduction of H₂O/CO₂ can take place efficiently in the dark while the pivotal step to govern syngas selectivity is photo-excitation of the reaction intermediates Rh₂VO_2,3CH₂⁻ to specific electronically excited states that can selectively produce CO and H₂. Electronic excitation over Rh₂VO_2,3CH₂⁻ to control the syngas selectivity is further confirmed from the comparison with the thermal excitation of Rh₂VO_2,3CH₂⁻, which leads to diversity of products. The atomic-level mechanism obtained from the well-controlled cluster reactions provides insight into the process of selective syngas production from the photocatalytic SRM and DRM reactions over supported metal oxide catalysts.     

A density functional theory-time-dependent density functional theory investigation of photo-induced hydrogen bond and proton transfer for 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid

Given the paramount importance of excited-state relaxation in the photochemical process, excited-state hydrogen bonding interactions and excited-state intramolecular proton transfer (ESIPT) are always hot topics. In this work, we theoretically explore the excited-state dynamical behaviors for a novel 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid (DDPBC) system. As two intramolecular hydrogen bonds (O1 H2⋯N3 and O4 H5⋯O6) exist in the DDPBC structure, we first check if the double proton transfer form cannot be formed in the S1 state. Then, we explore the changes of geometrical parameters involved in hydrogen bonds, based on which we confirm that the dual intramolecular hydrogen bonds are strengthened on photo-excitation. The O1 H2⋯N3 hydrogen bond particularly plays a more important role in excited state. When it comes to the photo-induced excitation, we find charge transfer and electronic density redistribution around O1 H2 and N3 atom moieties. We verify the ESIPT tendency arising from the O1 H2⋯N3 hydrogen bond. In the analysis of the potential energy curves, along with O1 H2⋯N3 and O4 H5⋯O6, we demonstrate that the ESIPT reaction should occur along with O1 H2⋯N3 rather than O4 H5⋯O6. This work not only clarifies the specific ESIPT mechanism for DDPBC system but also paves the way for further novel applications based on DDPBC structure in the future.     

Theoretical investigation of the molecular structure,vibrational spectra,and molecular docking of tramadol using density functional theory

The optimized molecular structures, harmonic vibrational wavenumbers, and the corresponding vibrational assignments of (1S,2S)-tramadol and (1R,2R)-tramadol are computationally examined using the B3LYP density functional theory method together with the standard 6–311++G(d,p) and def2-TVZP basis sets. The optimized structures show that phenolic rings of both 1R,2R and 1S,2S tramadol adopt planar geometry, which are slightly distorted due to the substitution at the meta-position; and the six-membered cyclohexane adopts a slightly distorted chair conformation. The 1S,2S enantiomer is energetically more favorable than 1R,2R with the energy differences of 1.32 and 1.03 kcal/mol obtained at B3LYP/6–311++G(d,p) and B3LYP/Def2-TVZP levels, respectively. The analysis of the binding pocket in the silico molecular docking with the m-opioid receptor shows that it originated two clusters with the 1S,2S enantiomer and one cluster with the 1R,2R enantiomer of tramadol. The results point to a more stable complex of the m-opioid receptor with the 1R,2R enantiomer of tramadol.