visible light

可见光
  • 文章类型: Journal Article
    TiO2是研究最多的光电化学水分解制氢的半导体材料之一,但它只对紫外线有反应。有机化合物的引入是扩大TiO2可见光响应的常用手段之一。在这项工作中,采用改进的溶剂热法,以油酸为关键添加剂,在导电玻璃上生长金红石型TiO2纳米线阵列(NWs)。使用X射线衍射对获得的TiO2NWs进行表征,X射线光电子能谱,红外光谱和电化学表征。结果表明,油酸产生的羧基以螯合二齿的形式与TiO2NWs化学键合,这增加了TiO2的可见光吸收范围和活性位点,并降低了光电极与电解质之间的转移电阻。光电流密度在1.23V时增加一倍,达到0.17mAcm-2RHE.这项工作为通过吸附有机化合物来设计金属氧化物半导体光电阳极提供了新的思路。
    TiO2 is one of the most studied semiconductor materials for the photoelectrochemical water splitting to hydrogen production, but it only responds to ultraviolet light. The introduction of organic compound is one of the common means to expand the visible light response of TiO2. In this work, rutile TiO2 nanowire arrays (NWs) were grown on conductive glass by a modified solvothermal method using oleic acid as the key additive. The obtained TiO2 NWs are characterized using X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and electrochemical characterization. The results show that the carboxyl groups arising from oleic acid are chemically bonded with the TiO2 NWs in the form of chelating bidentate, which increases the visible light absorption range and active sites of TiO2, and reduces the transfer resistance between the photoelectrode and the electrolyte. The photocurrent density is doubled to 0.17 mA cm-2 at 1.23 V vs. RHE. This work provides a novel idea for the design of metal oxide semiconductor photoanodes by adsorbing organic compounds.
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  • 文章类型: Journal Article
    由于烯烃的两个邻键交叉π键的同时构建,烯烃的双官能化代表了建立分子复杂性的最直接的方案之一。控制该事件的立体化学结果是非常有吸引力但具有挑战性的。在过去的几年里,可见光和Ni催化的烯烃不对称双官能化为控制区域和对映选择性的饱和碳中心的构建提供了环境良性且有前途的解决方案。在这个概念中,总结了通过可见光和镍催化实现的烯烃的区域和对映选择性双官能化的主动性和进展。此外,已经讨论了发展可见光介导的Ni催化的烯烃不对称双官能化的进一步努力和方向。
    Difunctionalizations of alkenes represent one of the most straightforward protocols to build molecular complexity due to the simultaneous construction of two vicinal bonds cross π-bond of alkenes. It is extremely attractive yet challenging to control the stereochemistry outcome of this event. Over the past years, visible-light and Ni-catalyzed asymmetric difunctionalizations of alkenes provide an environmental benign and promising solution for the construction of saturated carbon centers with the control of regio- and enantioselectivity. In this Concept, the initiative and progress of regio- and enantioselective difunctionalizations of alkenes enabled by visible-light and nickel catalysis has been summarized. Moreover, further efforts and directions for the development of visible-light mediated Ni-catalyzed asymmetric difunctionalizations of alkenes has been discussed.
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  • 文章类型: Journal Article
    全氟烷基物质(PFASs)是典型的持久性有机污染物,他们的移除是迫切需要的,但具有挑战性。由于光诱导电荷载体在光催化剂中的氧化还原能力,光催化已显示出PFAS降解的潜力。在这里,六方ZnIn2S4(ZIS)纳米片是通过一锅油浴法合成的,并通过一系列技术进行了良好的表征。在对全氟壬烯氧基苯磺酸钠(OBS)的降解中,一种代表性的PFAS,合成的ZIS在模拟阳光和可见光照射下的活性均优于P25TiO2。良好的光催化性能归因于增强的光吸收和促进的电荷分离。通过影响OBS在ZIS表面的吸附,发现pH条件在光催化过程中至关重要。光生e和h是ZIS系统中OBS降解的主要活性物种。这项工作证实了可行性,并可以为可见光光催化对PFAS的降解和脱氟提供机理见解。
    Perfluoroalkyl substances (PFASs) are typical persistent organic pollutants, and their removal is urgently required but challenging. Photocatalysis has shown potential in PFASs degradation due to the redox capabilities of photoinduced charge carriers in photocatalysts. Herein, hexagonal ZnIn2S4 (ZIS) nanosheets were synthesized by a one-pot oil bath method and were well characterized by a series of techniques. In the degradation of sodium p-perfluorous nonenoxybenzenesulfonate (OBS), one kind of representative PFASs, the as-synthesized ZIS showed activity superior to P25 TiO2 under both simulated sunlight and visible-light irradiation. The good photocatalytic performance was attributed to the enhanced light absorption and facilitated charge separation. The pH conditions were found crucial in the photocatalytic process by influencing the OBS adsorption on the ZIS surface. Photogenerated e- and h+ were the main active species involved in OBS degradation in the ZIS system. This work confirmed the feasibility and could provide mechanistic insights into the degradation and defluorination of PFASs by visible-light photocatalysis.
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  • 文章类型: Journal Article
    在水介质中光捕获和光响应超分子系统的设计中,两亲性光开关的制造能够通过光照射实现非侵入性功能响应。尽管大多数水性超分子组装体是由高能和生物损伤的紫外光驱动的,我们先前已经报道了由白光控制的两亲性供体-受体Stenhouse加合物(DASAs)的设计。在这里,我们提出了一系列DASA两亲物(DAs),在连接DASA基序与亲水部分的烷基连接链长度上具有较小的结构修饰。有机介质中优异的光开关性能和水性介质中的光响应性,由可见光驱动,通过紫外-可见吸收光谱进行了研究。组装的超分子纳米结构通过电子显微镜证实,而X射线衍射分析揭示了超分子堆积。在可见光照射下,DA几何结构的显著转变使得超分子组装体在微观尺度上的转变成为可能,随后拆卸DA的宏观软支架。目前的工作显示出有望用于制造可见光控制的宏观支架,为下一代生物医学材料提供可见光控制的微环境和未来的软机器人系统。
    In the design of photoharvesting and photoresponsive supramolecular systems in aqueous medium, the fabrication of amphiphilic photoswitches enables a noninvasive functional response through photoirradiation. Although most aqueous supramolecular assemblies are driven by high-energy and biodamaging UV light, we have previously reported a design of amphiphilic donor-acceptor Stenhouse adducts (DASAs) controlled by white light. Herein, we present a series of DASA amphiphiles (DAs) with minor structural modifications on the alkyl linker chain length connecting the DASA motif with the hydrophilic moiety. The excellent photoswitchability in organic medium and the photoresponsiveness in aqueous medium, driven by visible light, were investigated by UV-vis absorption spectroscopy. The assembled supramolecular nanostructures were confirmed by electron microscopy, while the supramolecular packing was revealed by X-ray diffraction analysis. Upon visible-light irradiation, significant transformations of the DA geometry enabled transformations of the supramolecular assemblies on a microscopic scale, subsequently disassembling macroscopic soft scaffolds of DAs. The current work shows promising use for the fabrication of visible-light-controlled macroscopic scaffolds, offering the next generation of biomedical materials with visible-light-controlled microenvironments and future soft-robotic systems.
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  • 文章类型: Journal Article
    纳米TiO2光催化技术因其安全性受到广泛关注,无毒和持久的性能。然而,传统的纳米TiO2由于其宽禁带只能被紫外光(λ<387nm)激活,极大地限制了其应用。在本文中,采用自掺杂法制备了纳米TiO2。合成的纳米TiO2是单一的锐钛矿晶型,粒径为10nm,尺寸均匀。此外,纳米TiO2具有较高的稳定性和良好的分散性。更重要的是,纳米TiO2表现出优异的可见光(400-780nm)活性,由于带隙从3.20eV降低到1.80eV(小于2.0eV),并且在纳米颗粒的表面上存在大量的羟基。在抗菌试验中,在家用低功率LED灯照射下,大肠杆菌和金黄色葡萄球菌的抗菌率接近100%,表现出优异的抗菌性能,表明所制备的纳米TiO2在杀菌和抑菌领域具有广阔的应用前景。
    Nano-TiO2 photocatalysis technology has attracted wide attention because of its safety, nontoxicity and long-lasting performance. However, traditional nano-TiO2 has been greatly limited in its application because its wide band gap can only be activated by ultraviolet light (λ < 387 nm). In this paper, nano-TiO2 was prepared by self-doping method. The synthesized nano-TiO2 was a single anatase crystal type with a particle size of 10 nm and uniform size. In addition, nano-TiO2 has high stability and good dispersion. More importantly, nano-TiO2 exhibits excellent visible light (400-780 nm) activity due to the decrease of bandgap from 3.20 eV to 1.80 eV (less than 2.0 eV) and the presence of a large number of hydroxyl groups on the surface of the nanoparticles. In the antibacterial test, the antibacterial rate of both E.coli and S.aureus was close to 100 % under the irradiation of household low-power LED lamps, showing excellent antibacterial performance, indicating that the prepared nano-TiO2 has broad application prospects in the field of bactericidal and bacteriostatic.
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  • 文章类型: Journal Article
    颗粒物表面上存在的硝基酚在大气中普遍存在。然而,其大气光化学转化途径仍然未知,可见光的关键影响在很大程度上被忽视了,导致对硝基酚在大气环境中的影响的不完全理解。本研究探讨了4-硝基苯酚(4NP)的光解机理,大气中最丰富的硝基苯酚化合物之一,在可见光照射下光活性颗粒的表面。出乎意料的是,非自由基物种(单线态氧,1O2)被确定为驱动4NP可见光解的主导因子。通过获得4NP的硝基(-NO2)和羟基(-OH)基团中C-N和O-H键断裂的直接证据,阐明了HONO和对苯醌(C6H4O2)产生的途径。HONO的进一步分解导致NO和羟基自由基的产生,这可能直接导致大气氧化能力,并使PM2.5成分复杂化。重要的是,1O2诱导的4NP可见光解行为在大气中常见颗粒物表面具有普遍性,如A1粉尘和Fe2O3。这项工作促进了对颗粒相大气硝基苯酚的光化学转化机理的理解,这对于阐明硝基酚在大气化学中的作用是必不可少的。
    Nitrophenols present on the surface of particulates are ubiquitous in the atmosphere. However, its atmospheric photochemical transformation pathway remains unknown, for which the crucial effect of visible light is largely overlooked, resulting in an incomplete understanding of the effects of nitrophenols in the atmospheric environment. This study delves into the photolysis mechanism of 4-nitrophenol (4NP), one of the most abundant atmospheric nitrophenol compounds, on the surface of photoactive particulates under visible light irradiation. Unexpectedly, the nonradical species (singlet oxygen, 1O2) was identified as a dominant factor in driving the visible photolysis of 4NP. The pathways of HONO and p-benzoquinone (C6H4O2) generation were clarified by acquiring direct evidence of C-N and O-H bond breakage in the nitro (-NO2) and hydroxyl (-OH) groups of 4NP. The further decomposition of HONO results in the generation of NO and hydroxyl radicals, which could directly contribute to atmospheric oxidizing capacity and complicate the PM2.5 composition. Significantly, the behavior of 1O2-induced visible photolysis of 4NP was universal on the surface of common particulates in the atmosphere, such as A1 dust and Fe2O3. This work advances the understanding of the photochemical transformation mechanism of particulate-phase atmospheric nitrophenols, which is indispensable in elucidating the role of nitrophenols in atmospheric chemistry.
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  • 文章类型: Journal Article
    通过热缩聚和共沉淀法制备了FeOOH/g-C3N4复合光催化剂,其次是XRD,SEM和UV-vis表征。通过回收试验探索了FeOOH/g-C3N4的稳定性。通过捕获实验研究了反应体系中的活性物种。结果表明,g-C3N4的最佳制备条件是在600°C下煅烧4h。XRD分析表明,g-C3N4具有高纯度相,FeOOH/g-C3N4中的Fe以高度分散的非晶态存在。SEM分析表明,FeOOH/g-C3N4具有粗糙的表面,具有不规则的层状结构。元素组成分析证实制备的催化剂中元素含量与理论计算相符。FeOOH/g-C3N4具有143.2m2/g的最大比表面积和合适的孔分布。UV-visDRS分析表明,FeOOH/g-C3N4的吸收强度强于g-C3N4。当催化剂用量为1.0g/L时,H2O2用量为4mmol/L,PNP初始浓度为10mg/L,初始pH值为5时,PNP去除率在120min内可达到92%。即使经过5个周期,FeOOH/g-C3N4对PNP的去除效率保持近80%。捕获实验表明,·OH和·O2-都在PNP的光催化降解中起作用,·OH更重要。这些发现证实了FeOOH已成功掺入g-C3N4中,从而在可见光辅助的类Fenton反应中对PNP的降解产生了显着的催化作用。
    The composite photocatalyst FeOOH/g-C3N4 was prepared through thermal polycondensation and co-precipitation methods, followed by XRD, SEM and UV-vis characterization. The stability of FeOOH/g-C3N4 was explored by the recycling test. The active species in the reaction system were investigated by the capture experiment. The results indicated that the optimal preparation condition for g-C3N4 involved calcination at 600 °C for 4 h. XRD analysis revealed that g-C3N4 exhibits a high-purity phase, and Fe in FeOOH/g-C3N4 exists in a highly dispersed amorphous state. SEM analysis showed that FeOOH/g-C3N4 has a rough surface with an irregular layered structure. Element composition analysis confirmed that the content of elements in the prepared catalyst is consistent with the theoretical calculation. FeOOH/g-C3N4 possesses the largest specific surface area of 143.2 m2/g and a suitable pore distribution. UV-vis DRS analysis showed that the absorption intensity of FeOOH/g-C3N4 is stronger than that of g-C3N4. When the catalyst dosage was 1.0 g/L, the H2O2 dosage was 4 mmol/L, the PNP initial concentration was 10 mg/L and the initial pH value was 5, the PNP removal could reach 92% in 120 min. Even after 5 cycles, the efficiency of PNP removal by FeOOH/g-C3N4 remains nearly 80%. The capture experiment indicated that both •OH and •O2- play roles in the photocatalytic degradation of PNP, with •OH being more significant. These findings affirm that FeOOH has been successfully incorporated into g-C3N4, resulting in a conspicuous catalytic effect on the degradation of PNP in the visible light-assisted Fenton-like reaction.
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  • 文章类型: Journal Article
    在室温下操作的NO2传感器的不良恢复特性的持续挑战仍然是显著的。然而,基于In2O3的气敏材料的开发提供了一种有希望的方法来加速室温下NO2亚ppm检测的响应和恢复。在这里,我们提出了一种简单的两步法来合成具有中空微管的一维(1D)In2O3@ZnO异质结构材料,通过偶联金属-有机骨架(MOFs)(MIL-68(In))和锌离子。同时,基于In2O3@ZnO复合材料的气体传感器在可见光激活下对NO2表现出优异的灵敏度性能。室温下对5ppmNO2的响应值高达1800,是纯In2O3基传感器的35倍。此外,与基于纯In2O3的传感器(74s/235s)相比,基于In2O3@ZnO异质结构的气体传感器显着减少了30s/67s的响应/恢复时间。In2O3@ZnO异质结构传感器的出色气敏特性可归因于异质结构效应导致的光生电荷分离效率提高,并改善了对NO2的受体功能,这可以增加反应位点和气体吸附能力。总之,这项工作提出了一种低成本,高效的方法来合成具有微管结构的一维异质结构材料,它可以作为开发高性能室温气体传感器的基本技术。
    The persistent challenge of poor recovery characteristics of NO2 sensors operated at room temperature remains significant. However, the development of In2O3-based gas sensing materials provides a promising approach to accelerate response and recovery for sub-ppm of NO2 detection at room temperature. Herein, we propose a simple two-step method to synthesize a one-dimensional (1D) In2O3@ZnO heterostructure material with hollow microtubes, by coupling metal-organic frameworks (MOFs) (MIL-68 (In)) and zinc ions. Meanwhile, the In2O3@ZnO composite-based gas sensor exhibits superior sensitivity performance to NO2 under visible light activation. The response value to 5 ppm of NO2 at room temperature is as high as 1800, which is 35 times higher than that of the pure In2O3-based sensor. Additionally, the gas sensor based on the In2O3@ZnO heterostructure demonstrates a significantly reduced response/recovery time of 30 s/67 s compared to the sensor based on pure In2O3 (74 s/235 s). The outstanding gas sensing properties of the In2O3@ZnO heterostructure-based sensors can be attributed to the enhanced photogenerated charge separation efficiency resulting from the heterostructure effect, and the improved receptor function toward NO2, which can increase the reactive sites and gas adsorption capacity. In summary, this work proposes a low-cost and efficient method to synthesize a 1D heterostructure material with microtube structures, which can serve as a fundamental technique for developing high-performance room-temperature gas sensors.
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  • 文章类型: Journal Article
    激发光活性电子供体-受体(EDA)络合物以产生自由基是自由基化学中的一种有前途的方法。在这项研究中,我们介绍了一种新的H键EDA配合物模型,用于在可见光条件下羰基活化的烯烃与多种硫醇的选择性氢硫醇化和羟基亚磺酰化。这种H键EDA复杂模型的可靠性已通过细致的实验和理论计算得到证实。机理研究表明,溶剂在确定光敏H键EDA复合物的激发是否会导致电荷转移(CT)或能量-电荷转移(En-CT)方面具有重大影响,从而控制Markovnikov和反Markovnikov选择性。值得注意的是,分子中原子的量子理论(QTAIM)分析清楚地表明,C=O---H-SEDA复合物的激发态涉及闭壳部分共价相互作用。
    Excitation of photoactive electron donor-acceptor (EDA) complexes to generate radical is a promising approach in radical chemistry. In this study, we introduce a new model of H-bonding EDA complexes for the selective hydrothiolation and hydroxysulfenylation of carbonyl-activated alkenes with diverse thiols under visible light conditions. The reliability of this H-bonding EDA complex model has been confirmed by meticulous experimental and theoretical calculations. Mechanistic investigations have revealed the significant influence of the solvent in determining whether the excitation of photoactive H-bonding EDA complex leads to charge transfer (CT) or energy-charge transfer (En-CT), thereby controlling Markovnikov and anti-Markovnikov selectivity. Notably, the Quantum Theory of Atoms in Molecules (QTAIM) analysis clearly shows that the excited state of the C=O-H-S EDA complex involves closed-shell partially covalent interactions.
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  • 文章类型: Journal Article
    通过光控可逆失活自由基聚合(photoRDRP)技术的光诱导3D打印已经成为一种用于制造聚合物材料的强大技术。然而,精确调整这些材料的机械性能的方法仍然有限。在这项研究中,我们提出了一种简单的方法,通过在基于NorrishI型光引发可逆加成-断裂链转移(NTI-RAFT)聚合的3D打印过程中调节聚合物分散性来调节3D打印物体的机械性能。我们研究了改变三硫代碳酸酯(BTPA)和黄原酸酯(EXEP)的浓度和摩尔比对印刷材料机械性能的影响。我们的研究结果表明,增加RAFT剂的浓度或更高比例的更活性的BTPA导致杨氏模量和玻璃化转变温度的降低,随着断裂伸长率的增加,这可以归因于聚合物网络的均匀性增强。使用商用液晶打印机,基于NTI-RAFT的3D打印系统有效地生产了具有定制机械性能的材料,突出其实际应用的潜力。
    Photoinduced 3D printing via photocontrolled reversible-deactivation radical polymerization (photoRDRP) techniques has emerged as a robust technique for creating polymeric materials. However, methods for precisely adjusting the mechanical properties of these materials remain limited. In this study, we present a facile approach for adjusting the mechanical properties of 3D-printed objects by adjusting the polymer dispersity within a Norrish type I photoinitiated reversible addition-fragmentation chain transfer (NTI-RAFT) polymerization-based 3D printing process. We investigated the effects of varying the concentrations and molar ratios of trithiocarbonate (BTPA) and xanthate (EXEP) on the mechanical properties of the printed materials. Our findings demonstrate that increased concentrations of RAFT agents or higher proportions of the more active BTPA lead to a decrease in Young\'s modulus and glass transition temperatures, along with an increase in elongation at break, which can be attributed to the enhanced homogeneity of the polymer network. Using a commercial LCD printer, the NTI-RAFT-based 3D printing system effectively produced materials with tailored mechanical properties, highlighting its potential for practical applications.
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