改性氧化钛对羟乙基乙二胺水溶液解吸CO2的强化

羟乙基乙二胺（AEE）水溶液的CO₂循环吸收量高（1.2molCO₂/molAEE），吸收速度快，稳定性好，但解吸速度慢、解吸量少（0.8mol CO₂/mol AEE）是限制该技术广泛应用的主要原因。本文通过向AEE水溶液中添加质量分数为0.05%～0.20%的改性氧化钛（TiO₂-MWCNT和TiO₂-OH）强化AEE的解吸能力。CO₂循环吸收（40℃）-解吸（120℃）实验结果表明改性氧化钛的添加比氧化钛强化CO₂解吸效果更好，强化顺序为TiO₂-MWCNT＞TiO₂-OH；其对应的最大解吸速率分别为0.093L/min（质量分数0.15%）和0.083L/min（质量分数0.20%），相对于AEE水溶液，分别提高了32.9%和18.6%；其对应的最大解吸量分别为0.92molCO₂/molAEE（质量分数0.15%）和0.88molCO₂/molAEE（质量分数0.20%），分别提高了12.2%和9.7%；其对应的CO₂循环吸收量分别是0.95molCO₂/molAEE（质量分数0.15%）和0.89molCO₂/molAEE（质量分数0.15%），分别提高了18.75%和11.25%；5次循环吸收解吸实验结果表明改性氧化钛强化CO₂解吸效果稳定，具有较强的化学稳定性。对反应后的改性氧化钛进行XRD、BET、FTIR和SEM表征，结果表明改性氧化钛具有较强的结构稳定性。TiO₂-MWCNT和TiO₂-OH在促进有机胺溶液解吸CO₂方面具有一定的工业应用潜力。     

Plasmonic Oxygen-Deficient TiO2-x Nanocrystals for Dual-Band Electrochromic Smart Windows with Efficient Energy Recycling

Dual-band electrochromic smart windows capable of the spectrally selective modulation of visible (VIS) light and near-infrared (NIR) can regulate solar light and solar heat transmittance to reduce the building energy consumption. The development of these windows is however limited by the number of available dual-band electrochromic materials. Here, plasmonic oxygen-deficient TiO_2-x nanocrystals (NCs) are discovered to be an effective single-component dual-band electrochromic material, and that oxygen-vacancy creation is more effective than aliovalent substitutional doping to introduce dual-band properties to TiO₂ NCs. Oxygen vacancies not only confer good near-infrared (NIR)-selective modulation, but also improve the Li⁺ diffusion in the TiO_2-x host, circumventing the disadvantage of aliovalent substitutional doping with ion diffusion. Consequently optimized TiO_2-x NC films are able to modulate the NIR and visible light transmittance independently and effectively in three distinct modes with high optical modulation (95.5% at 633 nm and 90.5% at 1200 nm), fast switching speed, high bistability, and long cycle life. An impressive dual-band electrochromic performance is also demonstrated in prototype devices. The use of TiO_2-x NCs enables the assembled windows to recycle a large fraction of energy consumed in the coloration process (“energy recycling”) to reduce the energy consumption in a round-trip electrochromic operation.     

烟气CO2捕集热能梯级利用节能工艺耦合优化

醇胺法捕集CO₂技术是一种较成熟的CO₂捕集技术，具有吸收速度快、脱除效果好等显著优点，但其操作费用高、解吸能耗大。本文以降低醇胺法捕集烟气中CO₂系统再生能耗为出发点，对常规醇胺法捕集CO₂工艺统进行了节能优化研究。在常规工艺流程基础上引入压缩式热泵节能技术，并利用Aspen Plus软件建立了基于压缩式热泵技术的CO₂捕集工艺流程模型。研究了压缩式热泵与机械蒸汽压缩回收（MVR）热泵、分流解吸、分布式换热、级间冷却4种节能工艺耦合，通过模拟计算与优化，结果说明了最佳节能工艺组合为“解吸塔压缩式热泵+贫液MVR热泵+分流解吸+级间冷却”耦合的CO₂捕集工艺流程，当解吸塔顶气体分流比为0.25∶0.75、冷富液分流比为0.05∶0.95、级间冷却器位于吸收塔17块塔板位置、吸收塔输入冷量为-3.0GJ/h时，系统再生能耗最低，为2.533 GJ/tCO₂，相比常规有机胺工艺（再生能耗4.204GJ/tCO₂）节能率39.748%。     

Pure CuBi2O4 Photoelectrodes with Increased Stability by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition

A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.     

酸改性CoPd/TiO2催化CH4-CO2直接合成C2含氧化合物

采用酸处理方法对CoPd/TiO₂催化剂进行改性，并将酸改性催化剂用于温和条件下CH₄-CO₂梯阶转化直接合成C₂含氧化合物（乙酸和乙醇）的反应。在150～300℃考察了浸酸方式和不同种类酸处理对催化剂活性和选择性的影响。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、NH₃程序升温脱附（NH₃-TPD）和N₂吸附对催化剂进行了表征。结果表明，酸改性明显提高了CoPd/TiO₂上C₂含氧化合物的生成速率和选择性。浸酸方式对催化剂性能和结构有显著影响，先用酸浸渍载体然后再浸渍活性金属所得催化剂具有更高的活性。在H₃PO₄、HNO₃和HCl中，H₃PO₄浸渍的催化剂活性最佳，在150℃时C₂含氧化合物（乙酸和乙醇）的生成速率为3365 μg/(g·h)，选择性达到91%。     

铜吡啶配合物催化合成1-甲氧基-2,2,6,6-四甲基哌啶-4-醇

目前1-烷氧基-2,2,6,6-四甲基哌啶基化合物的合成主要是以醛酮法为主。醇法合成虽然醇价格便宜，但合成效率很低。为解决这一问题，本文对醇法合成工艺进行了深入探讨，并以乙醇和4-羟基-2,2,6,6-四甲基哌啶氮氧自由基（ZJ-701）为原料，30%过氧化氢为氧化剂，氯化铜和吡啶配合物为催化剂，通过氧化和自由基偶合合成了1-甲氧基-2,2,6,6-四甲基哌啶-4-醇，通过红外光谱、核磁共振谱和质谱表征了其结构。通过实验进一步优化了反应时间、温度等一系列合成条件。研究结果表明：当反应时间为12h，反应温度为78℃，n(ZJ-701)∶n(乙醇)∶n(H₂O₂)∶n(CuCl₂)∶n(吡啶)=1∶39.25∶17.01∶0.034∶0.36时，产品产率最高，为60.6%，质量分数为98.8%，熔点为87～90℃。该方法具有原料乙醇便宜易得、反应条件温和、产品提纯容易等优点。     

不同晶相结构ZrO2负载铜基催化剂用于二乙醇胺脱氢反应

通过制备不同晶相结构〔单斜相(m-ZrO_2)、四方相(t-ZrO_2)和无定型(a-ZrO_2)〕ZrO_2载体,再通过沉积沉淀法制得Cu/m-ZrO_2、Cu/t-ZrO_2和Cu/a-ZrO_2催化剂,分别用于催化二乙醇胺脱氢合成亚氨基二乙酸反应。采用XRD、氮气物理吸附脱附、XPS、H_2-TPR、CO_2-TPD对催化剂的结构进行了表征。结果表明,Cu/m-ZrO_2催化剂界面更加有利于Cu~+/Cu~0稳定存在,具有更多的碱性位点,且抗氧化性较好。在二乙醇胺脱氢反应中,Cu/m-ZrO_2催化剂性能最好,反应时间为2.5 h,亚氨基二乙酸收率为97.64%。     

Ultrasensitive electrocatalytic detection of COX-2 rs20417: relying on 3D interconnected architecture of Pt-LSSUs@PAA nanostructures for sensor interface modification

Mutated COX-2 has become the new molecular marker of aspirin resistance. However, there is still a technical ‘bottleneck’ for direct and sensitive detection of circulating COX-2 mutant gene. In this work, we reported a simple and ultrasensitive electrochemical method for COX-2–765G/C (rs20417) detection for the first time. Polyallylamine (PAA) functionalised Pt nanostructures with long-spined sea urchin-like morphology (Pt-LSSUs@PAA) was synthesised by a simple chemical method for the construction of nano-sensing interface. Ru(NH₃)₆³⁺ is used as a primary electron acceptor that is electrostatically attracted to peptide nucleic acid modified electrodes and Fe(CN)₆^3? is introduced into the redox system as secondary electron acceptor to regenerate Ru³⁺ after electrochemical reduction for multiple redox cycles. Different pulse voltammetry was applied to record the electrochemical signals. Under optimal conditions, the DNA sensors showed a wide linear relationship, from 10?fM to 1?nM, with detection limits of 3.3?fM (S/N?=?3). This study will provide the basis for the precise use of aspirin, and it has important guiding value for individual drug testing of cardiovascular disease.     

Cable tray FIRE tests simulations in open atmosphere and in confined and mechanically ventilated compartments with the CALIF3S/ISIS CFD software

Fire hazard in nuclear power plants (NPPs) is particularly often investigated as potential cause of safety equipment failure and confinement loss. Many fire events recorded in NPPs involve electric cables, widely used throughout facilities. IRSN is developing the CALIF3S/ISIS computational fluid dynamics software devoted to fire simulation in large‐scale confined and mechanically ventilated compartments. This paper presents two aspects of the CALIF3S/ISIS code ability to simulate fires. The first one concerns vertical and horizontal spreading of a cable tray fire in open atmosphere using an approach based on the FLASH‐CAT cable fire spread model. Resorting to the suitable parameters of the FLASH‐CAT model based on video fire analyses of tests enables to properly compute the heat release rate of the fire. The second aspect concerns the ability to simulate the evolution and consequences of fires in confined and mechanically ventilated compartments. For these cases, the heat release rate measured during the corresponding experiment is used as input data for the calculations. The predicted evolutions of pressure or gas temperatures are in relatively good accordance with the experiments. The major discrepancy concerns gas concentrations in the fire room which is attributed to a lack of information about the properties of the fuel material.