固态氧化物电解池中碳-分子电化学转化为可再生燃料

近年来,随着社会环保意识的迅速提高以及对可再生能源利用能力的大幅增强,以燃料电池和电解池为代表的电化学技术已经逐渐在能源的存储、转化和利用方面发挥着不可或缺的独特作用.其中,固态氧化物电解池经过多年的发展,在装置成本和工作效率上取得了长足的进步,在储能转化方面具有重要的潜力.与此同时,伴随着《巴黎协定》签订以来各国的“碳中和”路线图逐渐出台,利用相对廉价易得的可再生电能,将二氧化碳(CO₂)和甲烷(CH₄)等碳-(C1)分子电解转化为高附加值的可再生燃料(如水煤气、乙烯等),对于碳中和目标的实现具有重要的意义.因此,C1分子电化学转化的研究成为了当下重点关注的研究领域,许多重要的研究成果和技术进步在过去几年中不断涌现.固态氧化物电解池作为一种代表性的C1分子电解和转化平台,也日渐引起相关领域研究人员的关注和兴趣.与传统的C1分子催化转化方法相比,基于固态氧化物电解池的电解转化技术具有两个重要优点:高能量转换效率与体系抗中毒能力.这两个特性作为体系稳健性的基石,保障了C1分子转化为可再生燃料的反应过程的长期可持续性.本文首先简要回顾了固态氧化物电解池的前沿技术与发展,并从电解池系统分类、反应体系的特征和反应体系发展的前景与挑战这三个方面,简要介绍了近年来基于固态氧化物电解池体系的C1分子电化学转化的代表性工作.CO₂与CH₄作为廉价易得的C1分子的代表,其转化因其反应分子惰性及反应过程不可控性而广受研究者关注,本文重点关注了在固态氧化物电解池中CO₂,CO₂/H₂O和CH₄三个体系的电化学反应过程和近期研究进展,希望可为相关研究人员未来设计更合适的催化剂和构建更优的电解池结构提供有益的参考.本文还针对目前固态氧化物电解池体系在C1分子转化领域所面临的挑战,提出了未来的一些可能的研究方向,以期助力研究者在不远的将来实现C1分子电解生产可再生燃料的实用化.     

Optimizing the Photovoltaic Performance of Organic Solar Cells for Indoor Light Harvesting

Organic solar cells (OSCs) harvesting indoor light are highly promising for emerging technologies, such as internet of things. Herein, the photovoltaic performance of PTB7-Th:PC₇₁BM solar cells constructed using “optimized (with 1,8-diiodooctane (DIO))” and “non-optimized (without DIO)” processing conditions are compared for indoor and outdoor applications. We find that in comparison to the “optimized” solar cell, the “non-optimized” solar cell is less efficient under simulated solar light illumination (100 mW cm⁻², spectral range 350–1100 nm), owing to significant bimolecular charge carrier recombination losses. However, under simulated indoor illumination (3.28 mW cm⁻², spectral range 400–700 nm), bimolecular recombination losses are effective suppressed, thus the power conversion efficiency of the solar cell without DIO was increased to 14.7 %, higher than that of the solar cell with DIO (14.2 %). These results suggest that the common strategy used to optimize the OSCs could be undesired for indoor OSCs. We demonstrate that the efforts for realizing the desired “morphology” of the active layer for the outdoor OSCs may be unnecessary for indoor OSCs, allowing us to realize high-efficiency indoor OSCs using a non-halogenated solvent.     

还原-氧化协同降解全/多卤代有机污染物

全/多卤代有机污染物大多具有生态毒性、生物蓄积性、环境持久性及长距离迁移性,不仅危害环境与生态安全,而且可经食物链传递威胁人类健康。由于卤原子是吸电子基团且取代数目多,这类物质的最高占据分子轨道能较低,难于被氧化降解,相反较易被还原法脱卤降解。随卤原子取代数减少,脱卤产物难被进一步还原,而其毒性甚至高于母体污染物。注意到低卤代有机物更容易发生氧化降解,一些研究构建了还原-氧化接力降解体系,即先利用还原法将全/多卤代有机污染物还原为低卤代产物,再利用氧化法降解这些中间产物,从而实现深度/完全脱卤和矿化。本文根据催化反应类型对还原-氧化联用法进行了归纳,分类介绍了基于传统化学催化、光催化、电化学、光电化学及机械化学等构建还原-氧化协同降解体系的原理及应用,以期为开发高效的处置技术提供思路和建议。     

Enhanced stability designs of cell membrane chromatography for screening drug leads

Cell membrane chromatography is an effective method for screening bioactive components acting on specific receptors in complex systems, which maintains the biological activity of the membrane receptors and improves screening efficiency. However, traditional cell membrane chromatography suffers from poor stability, resulting in a limited life span and low reproducibility, greatly limiting the application of this method. To address this problem, cyanuric chloride-decorated silica gel was used for the covalent immobilization of the cell membranes. Cyanuric chloride reacts with amino groups on the cell membranes and membrane receptors to form covalent bonds. In this way, the cell membranes are not easy to fall off. The column life of the cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography column was extended to more than 8 days, whereas the column life of the normal cell membrane chromatography column dropped sharply in the first 3 days. A cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography online HPLC-IT-TOF-MSn system was applied for screening drug leads from Trifolium pratense L. One potential drug lead, formononetin, which acts on the epidermal growth factor receptor, was screened. Our strategy of covalently immobilizing cell membrane receptors also improved the stability of cell membrane chromatography.     

Targeted isolation of 1,1-diphenyl-2-picrylhydrazyl inhibitors from Saxifraga atrata and their antioxidant activities

Saxifraga atrata is an important traditional Tibetan medicine used to treat cough and pneumonia, and has tremendous medicinal potential. In this study, we devised a technique to separate 1,1-diphenyl-2-picrylhydrazyl inhibitors from a methanol extract of S. atrata. The material was first processed using MCI GEL CHP20P medium-pressure liquid chromatography, yielding 1.1 g of the target fraction Fr2. Subsequently, online hydrophilic interaction liquid chromatography-1,1-diphenyl-2-picrylhydrazyl assay was used to identify prospective 1,1-diphenyl-2-picrylhydrazyl inhibitors, and two 1,1-diphenyl-2-picrylhydrazyl inhibitor fractions (Fr24 and Fr25) were identified from Fr2. Then, medium-pressure preparation was continued using an XIon column to separate two 1,1-diphenyl-2-picrylhydrazyl inhibitor fractions (Fr24 and Fr25). The target compound was concentrated in fractions Fr24 and Fr25 using reverse-phase liquid chromatography during further separation procedures. Finally, the purity, structure, and 1,1-diphenyl-2-picrylhydrazyl inhibitory activity of the isolated 1,1-diphenyl-2-picrylhydrazyl inhibitors were determined. Two 1,1-diphenyl-2-picrylhydrazyl inhibitors (adenosine with the half maximal inhibitory concentration of 66.87 ± 14.33 μM and (-)-4-O-(E)-caffeoyl-l -threonic acid with the half maximal inhibitory concentration of 59.06 ± 5.02 μM) were isolated with purities exceeding 95%. The results showed that this technology is effective in the targeted separation of antioxidants from natural products.     

Water-in-salt widens the electrochemical stability window: Thermodynamic and kinetic factors

Originating from the 1.23 V potential window of pure water, the narrow electrochemical stability window (ESW) has always been the most stubborn problem for aqueous battery systems. However, the water-in-salt system magically widens the ESW of aqueous electrolyte from 1.23 V to above 3 V by the super-concentrated LiTFSI solution. The mechanisms of widening aqueous battery ESW have been a crucial topic, in which the significant factors, including unique solid–electrolyte interface, solvation structure, and others, have been highlighted. Here, we specify the concept of ESW in detail and review the influence factors of ESW in the water-in-salt system from both thermodynamic and kinetic perspectives to explore the importance of each factor.     

Biocomputing Based on DNA Strand Displacement Reactions

The high sequence specificity and precise base complementary pairing principle of DNA provides a rich orthogonal molecular library for molecular programming, making it one of the most promising materials for developing bio-compatible intelligence. In recent years, DNA has been extensively studied and applied in the field of biological computing. Among them, the toehold-mediated strand displacement reaction (SDR) with properties including enzyme free, flexible design and precise control, have been extensively used to construct biological computing circuits. This review provides a systemic overview of SDR design principles and the applications. Strategies for designing DNA-only, enzymes-assisted, other molecules-involved and external stimuli-controlled SDRs are described. The recently realized computing functions and the application of DNA computing in other fields are introduced. Finally, the advantages and challenges of SDR-based computing are discussed.     

Reduction of Dimerization Tendency Due to the Decrease in Hybridization Index by Inclusion of 4s and 4p Semicore States as Valence States in Mon (n=2-18) Clusters: A First-Principles Study

Owing to the unique structural, electronic, and physico-chemical properties, molybdenum clusters are expected to play an important role in future nanotechnologies. However, their ground states are still under debate. In this study, the crystal structure analysis by particle swarm optimization (CALYPSO) approach is used for the global minimum search, which is followed by first-principles calculations, to detect an obvious dimerization tendency in Mo\begin{document}$ _n $\end{document} (\begin{document}$ n $\end{document} = 2\begin{document}$ - $\end{document}18) clusters when the 4s and 4p semicore states are not regarded as the valence states. Further, the clusters with even number of atoms are usually magic clusters with high stability. However, after including the 4s and 4p electrons as valence electrons, the dimerization tendency exhibits a drastic reduction because the average hybridization indices \begin{document}$ H_{ \rm{sp}} $\end{document}, \begin{document}$ H_{ \rm{sd}} $\end{document}, and \begin{document}$ H_{ \rm{pd}} $\end{document} are reduced significantly. Overall, this work reports new ground states of Mo\begin{document}$ _n $\end{document} (\begin{document}$ n $\end{document} = 11, 14, 15) clusters and proves that semicore states are essential for Mo\begin{document}$ _n $\end{document}     

Form-stable and tough paraffin-Al2O3/high density polyethylene composites as environment-friendly thermal energy storage materials: preparation,characterization and analysis

Journal of Thermal Analysis and Calorimetry - In this study, we focus on important global issue containing both environmental pollution control and energy saving. High density polyethylene (HDPE)...     

Dithienylmaleimide-based D-A Conjugated Polymer Film: Photo-Responsive Behavior and Application in Electrical Memory and Logic Gates

Solid-stated smart polymers responsive to external stimuli have attracted much attention for potential application in the field of photoelectron devices, logic gates, sensor, data storage and security. However, it is a bigger challenge for polymers than that for small molecules in solid state to acquire stimuli-responsive properties, because polymers with high molecular weight are not as easy to change the packing structure as small molecules under external stimulation. Here, a D-A type alternating copolymer PTMF-o containing 3,4-bisthienylmaleimide(A unit) and fluorene(D unit) is designed and synthesized. Upon irradiation of sunlight, PTMF-o film exhibits a photo-response with the color altering from purple to colorless. It is attributed to the structure of copolymer transformed from ring-opening form(PTMF-o) to ring-closure form(PTMF-c), resulting from the oxidative photocyclization of 3,4-bisthienylmaleimide unit. Consequently, the ability of charge transfer(CT) from fluorene to 3,4-bisthienylmaleimide unit in PTMF-o can be easily weakened by light stimuli. PTMF-o film displays a WORM-type resistive storage performance for the strong CT. Interestingly, after exposure, the electrical memory behavior in situ transfers into FLASH type, due to weak CT in PTMF-c. PTMF-o film can also be employed as smart material to construct NAND and NOR logic gates by using light as input condition. The work provides a simple way to modify the electronic properties of polymers and realize stimuli-response in solid states.