基于共轭聚合物的近红外光传感器

近红外光(NIR)传感器在军事警戒、空间勘探、科研检测、医疗诊断等领域有着极为重要的应用价值。传统的NIR传感材料主要是基于半金属的无机材料,借助窄带隙来吸收低能量的NIR而改变材料自身的电导率,继而实现检测。无机传感材料由于加工繁琐、不具备柔性、成本高昂以及难降解等因素致其进一步发展受到限制。新兴的共轭聚合物材料通过光热转换或者能级可调的光电效应实现对NIR的高灵敏传感,同时能够实现快速响应。该类聚合物材料具有π电子离域的共轭结构,同样具有较窄的带隙,在NIR照射下能够通过自身电导率的改变或光热转换作用将热量传递至其他超热敏材料来实现对光的检测。借助柔性、环境友好、制备简单、便于掺杂、灵敏度高等优势,共轭聚合物材料为新一代NIR传感器的应用与普及开辟了新的前景。     

钙钛矿基近红外光电探测器

近年来,具有ABX₃晶体结构的金属卤化物钙钛矿材料因其可调带隙、高吸收系数、长载流子传输距离等光电学特性而在光电探测领域表现出良好应用前景,尤其是基于纯Sn或者Sn/Pb混合阳离子制备的杂化钙钛矿在760～1050nm范围的近红外光电响应性能非常优异,展现出高灵敏度、低暗电流和高探测率等多方面优势。为进一步拓宽钙钛矿的近红外以及红外响应波长范围,研究人员探索了将有机材料、晶体硅/锗、Ⅲ-Ⅴ族化合物、Ⅳ-Ⅵ族化合物、上转换荧光材料等作为互补光吸收层与钙钛矿结合制备异质结来构筑出宽谱响应的近红外光电探测器。基于以上研究,本文总结了当前拓宽钙钛矿光电探测器的光谱范围的有效途径。同时,对钙钛矿材料的近红外光电探测器的未来发展前景作出了展望。     

高效钙钛矿缺陷态钝化材料及其钝化机理

正有机金属卤化物钙钛矿材料具有可调的直接带隙、高摩尔吸光系数和高载流子迁移率等优异的光电性质~1。基于该类钙钛矿材料的太阳能电池经过短短几年的发展,其能量转换效率几乎能够和传统晶体硅太阳能电池的效率相媲美~2。因此,钙钛矿太阳能电池被研究者们寄予厚望。在电池制备过程中所形成的钙钛矿多晶薄膜往往具有大量的晶界,处于晶界中配位不饱和的卤离子和金属离子会诱导缺陷态的形成~3,从而大     

基于碳纳米管的光伏电池

碳纳米管具有独特的一维结构和优异的光电特性,是构建光伏电池的理想材料。本文主要综述了近年来碳纳米管基光伏电池的结构设计、制备方法以及碳纳米管在器件中的不同功能应用。首先概述了碳纳米管的结构和光电特性,重点讨论了碳纳米管作为光电转换材料、导电电极和载流子传输层等功能层时器件的原理、制作方法及优缺点,介绍了碳纳米管在微型光伏电池、碳纳米管/硅异质结光伏电池、染料敏化光伏电池、钙钛矿光伏电池、有机光伏电池以及柔性光伏电池中的应用,最后总结了碳纳米管基光伏电池的优势和挑战,以期为新型碳基光伏电池的设计和制作提供思路和参考。     

气敏新材料MXenes在呼出气体传感器中的应用

电子鼻结合人工智能对呼出气进行检测、分析和识别已成为非侵入性医疗检测领域的研究热点。然而,目前已报道的气体传感材料尚不能同时满足高灵敏度、高选择性和稳定的室温检测,阻碍了气体传感器在医疗健康领域的应用及发展,寻找合适的传感材料具有重要的意义和挑战。新型二维层状纳米材料MXenes具有种类多、比表面积大、导电性能强、表面含有丰富的官能团以及能带宽度可调等优异性能,是高灵敏、低能耗气体传感器的明星候选材料。本综述针对MXenes基材料的特殊结构,总结梳理了MXenes基材料在气体传感中的最新研究成果,聚焦于MXenes材料的气体传感机理和改性方法,对MXenes材料用于气体传感依然存在的问题和挑战进行深入探讨。     

共价有机骨架的设计、制备及应用

共价有机骨架(COF)材料是一类由共价键连接有机构筑单元而形成的结晶型有机多孔材料。COF因其长程有序的结晶结构,以及具有可设计性、可剪裁性和易功能化的特点,因而表现出优异的物理化学性质,被科学家们广泛关注和研究。基于COF材料特定的拓扑结构、多样的单元组成、可调的孔道性质和灵活的功能开发,COF材料在气体存储、非均相催化、传感检测、光电转换、质子传导、储能等方面体现出重要的应用价值。本文从COF材料的设计、制备以及应用等方面,综述了COF材料领域的发展和现状,并对其研究和应用前景进行展望。     

光电化学传感器的构建及应用

光电化学分析是基于光电化学过程和化学/生物识别过程建立起来的一种新的分析方法。该方法以光作为激发信号,以光电流作为检测信号,具有灵敏度高、响应快速、设备简单和易微型化等优点,在生物和环境等分析领域受到了广泛关注。电极表面修饰的光电层在吸收光子后被激发,所产生的载流子发生电荷分离和电子迁移,进而产生光电流。通过在光电层上进一步修饰传感识别单元,利用直接氧化还原、分子识别与结合、酶催化等方法所导致的光电流的变化与待测分子之间的数量关系,可实现对目标物的定量分析。因此,光电化学传感器在功能结构上包括光电转换单元和传感识别单元两部分,光电层的材料选择和传感识别策略是光电化学传感器构建的两大关键点。本文在对光电化学传感器基本原理及应用领域总结的基础上,对光电化学传感器的材料选择和传感模式进行了分析和综述。     

手性钙钛矿的结构维度与光电特性

近十年,有机无机杂化钙钛矿凭借其新颖优异的光电特性而引起广泛关注。最近,手性钙钛矿由于结合了钙钛矿材料和手性材料各自独特性能,在三维显示、光学信息处理、量子光学、生物探测、自旋电子等方面具有重要应用价值。根据有机、无机组分的空间分布,可以对手性钙钛矿的结构维度进行分类。本文以手性钙钛矿的不同结构维度为出发点,分别阐述了一维、二维和三维手性钙钛矿的晶体结构、光学和光电特性,包括圆二色性、圆偏振光致发光和光电探测等特性。考虑到二维手性钙钛矿具有独特的范德华层状晶体结构,重点介绍了其与其它二维材料组合成二维异质结构方面的工作。最后,分别从材料制备和器件应用的角度,总结了手性钙钛矿的重点挑战问题和未来发展方向。     

钙钛矿阵列化组装及其多功能探测器的应用

钙钛矿材料优异的光电性能使其在高集成、 高性能、 多功能光电探测领域具有广泛的应用前景. 近年来, 科研人员致力于钙钛矿阵列化探测器的研究, 并取得了一系列重要的成果. 本文重点评述了钙钛矿材料的阵列化及其多功能探测器的制备和应用, 介绍了钙钛矿材料的结构分类、 阵列化集成方法及光电探测器的基本器件类型和性能指标, 并进一步阐述了基于钙钛矿一维阵列的高性能光电探测器及其多功能探测器的相关应用研究进展. 最后, 对该研究领域未来的发展方向进行了总结和展望.     

脑内三磷酸腺苷的光电化学活体分析北大核心CSCD

神经化学信号传递是实现大脑复杂功能的基础,因此发展神经化学信号的活体原位检测方法,对于探索脑功能和脑疾病的神经化学分子机制具有重要意义。光电化学传感技术具有灵敏度高、背景信号低和易于微型化等优点,是活体原位分析的潜在有力工具。然而,常见的光电活性材料需要短波长的光激发,其组织穿透深度不足,限制了在活体分析中的应用。基于此,本文构建了一种可近红外激发的光电化学微传感器,用于脑内三磷酸腺苷(ATP)的原位检测。将稀土掺杂的上转换纳米颗粒(UCNPs)引入传感界面,用UCNPs的发光激发电极表面的光电活体材料产生光电流信号,通过荧光染料(TAMRA)标记的核酸适配体调节UCNPs的发光,发展一种基于光学调控策略检测脑内ATP的光电化学传感新方法。所制备的微传感器成功用于炎症模型中小鼠脑内ATP的原位检测,初步探索了脑部炎症与ATP水平变化的关系。     

微波热冲快速制备二维多孔La0.2Sr0.8CoO3钙钛矿用于高效电催化析氧反应

析氧反应(OER)被认为是电解水的关键限制步骤,已被广泛作为清洁能源方式用于解决能源和环境问题。钙钛矿氧化物(ABO₃)具有可调的电子结构、高灵活性的元素组成,能在OER中表现出良好的催化活性。然而,钙钛矿氧化物的合成通常需要经历长时间的高温,极易导致金属的聚集和影响材料的本征活性。气相微波技术可以显著缩短热处理时间,从而减少相关的碳排放。这项技术不仅解决了对碳中性过程日益增长的需求,而且还增加了对合成的控制,以避免产品的不良团聚。本文采用微波热冲法快速制备了二维(2D)多孔La_0.2Sr_0.8CoO₃钙钛矿。伴随微波过程的快速熵增可以有效地暴露La_0.2Sr_0.8CoO₃结构中丰富的活性位点。此外,高能微波冲击过程可以精准地将Sr²⁺引入到LaCoO₃的晶格中,通过增加Co的氧化态来增加氧空位量。这种锶元素取代镧引入的氧空位能极大提高催化剂的本征催化活性。对于碱性电解液中的OER应用,制备的La_0.2Sr_0.8CoO₃在10 mA∙cm⁻²下展现出了360 mV的过电位,Tafel斜率为76.6 mV∙dec⁻¹。且在经历30000秒的长时间循环测试后仍能维持初始电流密度的97%。这项研究为高活性二维钙钛矿的合成提供了一种简便、快速的策略。     

溶剂工程调控钙钛矿薄膜中PbI2和PbI2(DMSO)的形成

钙钛矿太阳能电池以其高效、低成本的特点备受关注。到目前为止,钙钛矿太阳能电池的最高光电转换效率已经超过25%,显示出良好的应用前景。钙钛矿薄膜的结晶性能是决定器件性能的关键,因此,调控钙钛矿薄膜的生长过程至关重要。本工作中,我们发现通过简单调节前驱体溶剂,即调节二甲基亚砜：1, 4-丁内酯: N, N-二甲基甲酰胺(DMSO : GBL : DMF)的三种混合溶剂的比例,可实现钙钛矿薄膜中PbI₂和PbI₂(DMSO)含量的调节,从而调节电池的器件性能。此外,本工作系统研究了PbI₂和PbI₂(DMSO)的含量对器件性能的影响。结果表明,PbI₂(DMSO)的形成会导致300–425 nm波长范围内电池的外量子效率(EQE)降低,从而导致器件性能下降。相反,通过在前驱体溶液中添加额外的碘化亚甲基铵(MAI),可以抑制PbI₂和PbI₂(DMSO)的形成。     

La掺杂BiOI微球可见光下光催化氧化NO性能研究

Photocatalytic oxidation has been widely acknowledged as an economical and effective technology for the treatment of low-concentration NO. Three-dimensional (3D) BiOI microspheres, which are typical visible-light responsive semiconductor photocatalysts, often suffer from quick recombination of photogenerated carriers and unsatisfactory electrical conductivity when applied in NO photocatalytic oxidation reactions. However, owing to their micro-sized structures, they are usually difficult to couple with other semiconductors and co-catalysts because of their incompact interfaces that provide insufficient contact. In this study, a rare-earth metal (La) doping strategy was first adopted to modify BiOI microspheres via a simple one-step solvothermal method; subsequently, the photocatalytic NO oxidation performance under visible light illumination was systematically investigated. Further, the La precursors and doping contents were optimized. It was found that La(NO₃)₂ was the best precursor when compared to LaCl₃ and La(AC)₃. Moreover, 0.3%La/BiOI exhibited the best NO photocatalytic conversion efficiency of up to 74%, which was significantly higher than that of the pure BiOI benchmark (44%). It also exhibited excellent stability during the continuous 5-cycle experiments. Analysis of the physicochemical properties revealed that La doping facilitated the crystallization of BiOI without altering its morphology and structure. La³⁺ may enter the BiOI lattice by substituting Bi³⁺ or forming La₂O₃ nanoclusters that homogeneously scatter in the mesopores of BiOI microspheres. The analysis of the underlying mechanism further revealed that La doping not only enhanced the light harvesting properties by decreasing the bandgaps of BiOI and accelerating the charge separation and transfer dynamics, but also introduced more oxygen vacancies and facilitated the formation of more OH radicals by dissociating the water molecules. All these factors co-contributed to the promotion of NO photocatalytic oxidation activities. Furthermore, NO was mainly oxidized to NO₂ over La/BiOI, and the formed NO₂ tended to desorb from the catalyst surface, which not only maintained the intactness of active sites and facilitated the sustainable occurrence of NO photocatalytic oxidation reactions, but also prevented the photocatalysts from frequent washing-regeneration; therefore, these factors account for the superior photocatalytic stability of La/BiOI and its long-term operation. The formed NO₂ could be easily and totally absorbed by the tail alkaline liquid, thereby effectively avoiding secondary pollution. Therefore, this study elucidates that doping is indeed a feasible and effective approach for the modification of 3D BiOI microspheres, while providing inspiration for the rational design and modification of other 3D semiconductor materials for various photocatalytic applications.      

石墨烯三维结构组装体制备及光热水蒸发和水处理研究进展

水资源短缺是世界长期面临的问题,当前全球80多个国家的约15亿人口面临淡水不足,其中26个国家的3亿人口完全生活在缺水状态。近年来,人们开发了新型太阳能界面水蒸发材料和技术,能够利用高效光热材料吸收太阳能转化为热能,实现大量的、快速的水蒸发,冷凝后收集便得到洁净水,是一种高效、绿色、低成本水处理和解决水资源短缺的方法。石墨烯三维组装体材料的物理和化学性质优异,光热转化效率高,同时其太阳光吸收率高,内部微纳孔道丰富,具有良好的水传输通道,表面水蒸发面积大,在太阳光照射下能够实现超高的水蒸发速率,在光热水处理方面展现了巨大的科学研究意义和实用价值。本文将综述石墨烯三维组装体的制备及光热水处理方面的研究进展,包括石墨烯三维结构组装体制备方法,其光热水蒸发性能,总结了石墨烯三维结构组装体在光热水蒸发及水处理方面的应用,最后分析了石墨烯三维结构组装体光热水处理面临的问题及展望。     

Lewis酸催化纤维素制乳酸机理研究

乳酸是制备可降解聚合物聚乳酸的主要单体。利用秸秆等原生生物质为原料经过化学催化转化制备乳酸对于碳减排具有重要意义。本工作利用同位素核磁和质谱详细探究了不同Lewis酸(Y³⁺,Sc³⁺,Al³⁺)催化纤维素制乳酸的反应选择性和机理。发现葡萄糖异构化为果糖的过程是决定纤维素制乳酸多步串联反应最终选择性的关键步骤,并明确了1, 3-二羟基丙酮生成乳酸经历了烯醇互变异构过程而非经典的1, 2-shift机理。     

Lewis酸催化纤维素制乳酸机理研究

Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y³⁺, Sc³⁺, and Al³⁺) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y³⁺ > Al³⁺ > Sc³⁺. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y³⁺ > Al³⁺, Y³⁺ > Sc³⁺), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc³⁺ > Y³⁺ > Al³⁺), and the conversion of DHA or GLY to the final product lactic acid (Al³⁺ > Y³⁺ > Sc³⁺). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.      

湿空气下制备稳定的CsPbI2Br钙钛矿太阳电池

无机钙钛矿太阳能电池由于具有良好的热稳定性,高吸光系数等优点发展迅速。但无机钙钛矿材料对水分极其敏感,一般在惰性环境下中进行制备,操作复杂。本文通过简单的一步旋涂工艺,在无手套箱空气湿度条件下制备CsPbI₂Br无机钙钛矿薄膜,通过介孔TiO₂厚度的优化,对钙钛矿薄膜的结晶、成膜及稳定性进行了分析,发现在较厚基底介孔层上制备的钙钛矿晶粒大、无孔隙;随着基底厚度的减小,其上所形成的CsPbI₂Br薄膜禁带宽度(E_g)增大;电化学阻抗测试表明在较厚基底介孔层上制备的CsPbI₂Br钙钛矿具有更好的载流子提取与传输能力。对不同厚度介孔层上沉积的钙钛矿薄膜稳定性进行测试,发现CsPbI₂Br钙钛矿的稳定性随着介孔层厚度的增加而提高,在空气中做放置144 h后无明显变化。在空气湿度条件下组装成器件,获得到了8.16%的最佳光电转换效率,并且对器件无任何修饰及封装的情况下,在相对湿地低于35%的空气中放置72 h后保持最初效率的73%。     

金属硫化物基钾离子电池负极：储存机制和合成策略

Rechargeable potassium-ion batteries (PIBs), with their low cost and the abundant K reserves, have been promising candidates for energy storage and conversion. Among all anode materials for PIBs, metal sulfides (MSs) show superiority owing to their high theoretical capacity and variety of material species. Nevertheless, the battery performance of MSs is hindered by many factors such as poor conductivity, low ion diffusivity, sluggish interfacial/surface transfer kinetics, and drastic volume changes. In this review, the electrochemical reaction mechanisms, challenges, and synthesis methods of MSs for PIBs are summarized and discussed. In particular, the most common synthesis methods of MSs for PIBs are highlighted, including template synthesis, hydro/solvothermal synthesis, solid-phase chemical synthesis, electrospinning synthesis, and ion-exchange synthesis. During the potassium storage process, the two-dimensional layered MSs follow the intercalation/extraction mechanism, and the MSs with inactive metal undergo the conversion reaction, whereas the metal-active MSs follow the conversion-alloying reaction mechanism. Given the inherent properties of MSs and the reactions they undergo during cycling, when used as anodes for PIBs, such materials experience a series of problems, including poor ion-/electron-transport kinetics, structural instability, and loss of active material caused by the dissolution of discharged polysulfide products and the occurrence of side reactions. These problems can be solved by optimizing the methods for synthesizing MSs with an ideal composition and structure. The template method can precisely prepare porous or hollow-structured materials, the hydro/solvothermal method can alter the thickness or size of the material by adjusting certain synthesis parameters, and the one-dimensional-structured material obtained via electrospinning often has a large specific surface area, all of which can shorten the transport pathway for potassium ions, thereby improving the performance of the battery. The ion-exchange method affords difficult-to-synthesize MSs via anion- or cation-exchange, in which the product inherits the structure of the starting material. The solid-phase synthesis method makes it possible to combine MSs with other materials. Combinations with materials such as carbon or other MSs helps to provide sufficient buffer space for the volume expansion of MSs during cycling, while promoting electron transport and improving the potassium-storage properties of the anodes. Therefore, this review aims to highlight the current defects of MS anodes and explore the construction of their ideal architecture for high-performance PIBs by optimizing the synthesis methods. Ultimately, we propose the possible future advancement of MSs for PIBs.      

金属硫化物基钾离子电池负极：储存机制和合成策略

钾离子电池由于其低成本和丰富的钾矿产资源,在能量存储和转化领域极具应用潜力。金属硫化物理论容量高且材料种类丰富,在众多钾离子电池负极材料中表现突出。然而,金属硫化物存在的缺点,如导电性差、离子扩散率低、界面/表面传输动力学缓慢等,限制了其在储钾过程中的性能表现。在这篇综述中,我们系统的讨论和总结了金属硫化物作为钾离子电池负极的电化学反应机制、所面临的挑战和合成方法。其中,重点讨论了其常见的合成方法,包括模板法、溶剂热/水热法、固相反应法、静电纺丝法和离子交换法。这篇综述意在通过优化合成策略设计合成理想的组分和结构,来解决钾电负极材料存在的问题,最终得到高性能的钾离子电池负极材料。最后我们还对基于金属硫化物的钾离子电池负极的发展方向进行了展望。     

银纳米粒子修饰的二维金属-有机框架纳米片用于光热增强银离子释放抗菌

近年来,二维(2D)金属-有机框架(MOF)纳米复合材料被广泛的应用于生物医学领域,尤其是在抗菌方面。在此,我们通过光照诱导还银离子成功在二维MOF纳米片上生长银纳米粒子,得到了一种银纳米粒子(Ag NPs)修饰的二维Zr-Fc-MOF (MOF-Ag)纳米片,并将其用于光热增强Ag⁺释放抗菌治疗。通过水热法和超声处理合成MOF纳米片,然后通过原位光辐照诱导还原在MOF纳米片上生长Ag NPs。系列表征结果表明Ag NPs成功负载到MOF纳米片上。聚乙烯吡咯烷酮(PVP)的修饰不仅可以增强MOF-Ag在溶液中的稳定性,还可以增强它的生物相容性。在近红外激光(NIR)照射下,MOF纳米片可以在短时间升温,而温度的升高可以加速Ag NPs在溶液中氧化为银离子。通过细菌生长曲线、菌落相对数和细菌形态变化等实验表明PVP@MOF-Ag纳米片具有优异的广谱杀菌性能。此外,2D MOF纳米片良好的光热性能不仅可以增强Ag⁺的释放,还可以增强细胞膜的通透性,随后进入细菌中的Ag⁺可以诱导内源性活性氧的产生,从而引发细菌的氧化应激,实现高效抗菌。基于良好的体外抗菌性能,进一步将PVP@MOF-Ag纳米片用于小鼠伤口愈合,在此期间PVP@MOF-Ag纳米片表现出良好的治疗效果和生物安全性。我们的研究结果表明,PVP@MOF-Ag纳米片可以作为光热增强Ag⁺释放抗菌治疗和伤口愈合的有效平台。