Visible‐Light‐Induced Generation of H2 by Nanocomposites of Few‐Layer TiS2 and TaS2 with CdS Nanoparticles

Graphene analogues of TaS₂ and TiS₂ (3–4 layers), prepared by Li intercalation followed by exfoliation in water, were characterized. Nanocomposites of CdS with few‐layer TiS₂ and TaS₂ were employed for the visible‐light‐induced H₂ evolution reaction (HER). Benzyl alcohol was used as the sacrificial electron donor, which was oxidized to benzaldehyde during the reaction. Few‐layer TiS₂ is a semiconductor with a band gap of 0.7 eV, and its nanocomposite with CdS showed an activity of 1000 μmol h^?1 g^?1_. The nanocomposite of few‐layer TaS₂, in contrast, gave rise to higher activity of 2320 μmol h^?1 g^?1, which was attributed to the metallic nature of few‐layer TaS₂. The amount of hydrogen evolved after 20 and 16 h for the CdS/TiS₂ and CdS/TaS₂ nanocomposites was 14833 and 28132 μmol, respectively, with turnover frequencies of 0.24 and 0.57 h^?1, respectively.     

UV/Vis-LED激发的香豆素吡啶鎓盐光引发剂的合成及性能

设计合成了3种基于香豆素骨架的紫外-可见发光二极管(UV/Vis-LED)可激发的新型吡啶鎓盐光引发剂, 并研究了这3种香豆素吡啶鎓盐的构效关系及其作为单组分自由基光引发剂在丙烯酸酯体系中的光引发活性. 紫外-可见吸收光谱分析表明, 这3种香豆素吡啶鎓盐在300~400 nm区域有较强吸收. 在LED@365 nm和LED@405 nm光源辐照下, 研究了3种光引发剂的稳态光解和光聚合动力学. 研究表明, 这3种香豆素吡啶鎓盐光引发剂在相应光辐照下都具有较好的光解速率. 此外, 3种光引发剂对丙烯酸酯都具有较好的引发活性. 构效关系研究表明, 吡啶环4号位引入推电子的甲氧基会使其引发丙烯酸酯单体聚合的活性降低; 而引入吸电子的乙酰基会使其引发丙烯酸酯单体聚合的活性增加. 差示扫描量热(DSC)实验表明, 此类吡啶鎓盐光引发剂具有较好的热稳定性. 当3种光引发剂与丙烯酸单体混合时可提升体系的热稳定性; 通过电子自旋共振(ESR)证明了活性物种的产生, 并对该类引发剂的引发机理进行了探讨.     

Microwave-assisted sol-gel synthesis of CeO2–NiO nanocomposite based NO2 gas sensor for selective detection at lower operating temperature

The progress in the development of gas sensors has considerably grown using some novel nanomaterials of metal, metal oxide and composite. In the current study, we intended and evaluated the properties of nanomaterials like CeO₂, NiO, and CeO₂–NiO composite and its application as NO₂ gas sensor. Sensing of low concentration of NO₂ gas at optimum functional temperature was succeeded using CeO₂–NiO nanocomposites (NCs) film. The working temperature ranges in between 100 and 225 ?°C. Highly crystalline nanomaterials (CeO₂, NiO and CeO₂–NiO) have been prepared by applying microwave-assisted sol-gel route. The as-prepared nanomaterials are characterized for their structure, size, morphology and constitution by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis. XRD studies of nanoparticles reveal the formation of nanoscale CeO₂ and NiO with crystallite size 26, 23 ?nm, respectively. Both are having a face centered cubic structure. The nanocomposite (NC) Ce:Ni ?= ?60:40 has crystallite size of 13 ?nm. XRD study of NCs shows assimilation of Ni metal into the ceria and proves physical similarities of two phases. It can be observed from SEM that prepared NC has a porous surface which enables more surface active sites for adsorbing oxygen. The optical properties are measured with the help of UV–Vis. Spectroscopy. Optical band gaps of 3.19, 3.41 and 2.9 ?eV were observed for CeO_2, NiO nanoparticles (NPs) and CeO₂–NiO NC, respectively. Gas sensing properties state that the NC material shows a higher gas response % of 67.34% for NO₂ gas (25 ?ppm) at comparatively low operating temperature (125 ?°C). It gives response time as (～28 ?s) and the recovery (～54 ?s). NiO incorporation in CeO₂ results in a decline of operating temperature of NC and improves the sensing features.     

CdS基纳米管光催化氧化5-羟甲基糠醛选择性生成2,5-呋喃二甲醛

将生物质转化为高附加值化学品以替代传统化石能源衍生的碳资源不可再生能源已经引起了人们的广泛关注. 本工作制备了内部中空的ZnS@CdS/Ni纳米管催化剂用于光催化氧化5-羟甲基糠醛(HMF). 通过X射线光电子能谱表征了催化剂内部存在ZnS缺陷态使得ZnS能带带隙降低. 光照条件下, 光生空穴能够从CdS迁移至ZnS缺陷态, 抑制了ZnS@CdS内部的载流子复合, 提高了光催化性能. 中空的纳米管表面负载Ni催化剂可以参与质子还原产氢的反应, 而ZnS@CdS内部产生的空穴可以催化氧化HMF选择性生成2,5-呋喃二甲醛(DFF). 光反应1 h后, HMF的转化率达到36%, 产物DFF选择性为99%, 并且催化剂可以重复利用三次而不降低催化效果.     

太阳能光催化分解水制氢※

利用太阳能光催化分解水制氢是解决能源环境问题并实现太阳能有效转化和储存最有前途的技术之一, 这一“圣杯”式反应经过几十年不懈努力取得了诸多重要研究进展. 本文将综述光催化分解水制氢体系的基本概念、活性测试方法与注意事项、光催化材料种类等; 并从光催化分解水制氢的光吸收、光生电荷分离和表面催化反应等基本过程和关键科学问题的角度总结其重要研究进展, 最后对于太阳能光催化分解水制氢的挑战和潜在的发展方向进行分析和展望. 希望通过本综述的简要介绍能让刚从事光催化分解水制氢研究的青年科技人员清晰地了解掌握该领域的一些基本概念、操作规范、研究总体进展和现状等.     

Tuning Deazaflavins Towards Highly Potent Reducing Photocatalysts Guided by Mechanistic Understanding – Enhancement of the Key Step by the Internal Heavy Atom Effect

Deazaflavins are well suited for reductive chemistry acting via a consecutive photo-induced electron transfer, in which their triplet state and semiquinone – the latter is formed from the former after electron transfer from a sacrificial electron donor – are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5-aryldeazaflavins with Br or Cl substituents on different structural positions via a three-component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo-instability and enhances unproductive side reactions. Bromine on the 5-phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo- and chloroarenes with electron-donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved.     

Boosting Hydrogen Evolution at Visible Light Wavelengths by Using a Photocathode with Modal Strong Coupling between Plasmons and a Fabry-Pérot Nanocavity

Hot-hole injection from plasmonic metal nanoparticles to the valence band of p-type semiconductors and reduction by hot electrons should be improved for efficient and tuneable reduction to obtain beneficial chemical compounds. We employed the concept of modal strong coupling between plasmons and a Fabry-Pérot (FP) nanocavity to enhance the hot-hole injection efficiency. We fabricated a photocathode composed of gold nanoparticles (Au−NPs), p-type nickel oxide (NiO), and a platinum film (Pt film) (ANP). The ANP structure absorbs visible light over a broad wavelength range from 500 nm to 850 nm via hybrid modes based on the modal strong coupling between the plasmons of Au−NPs and the FP nanocavity of NiO on a Pt film. All wavelength regions of the hybrid modes of the modal strong coupling system promoted hot-hole injection from the Au−NPs to NiO and proton/water reduction by hot electrons. The incident photon-to-current efficiency based on H₂ evolution through water/proton reduction by hot electrons reached 0.2 % at 650 nm and 0.04 % at 800 nm.     

Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity

Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N₂ and the resulting reactive species initiate C−H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C−H activation reactions. The sulfonyl nitrene radical anion is the least reactive and its reactivity is governed by the proton coupled electron transfer mechanism. In contrast, sulfonyl nitrene and sulfonyl amidyl radicals react via hydrogen atom transfer pathways. These reactivities and detailed characterization of the radicals with vibrational spectroscopy and with DFT calculations provide information necessary for taking control over the reactivity of these intermediates.     

Solar Driven Gas Phase Advanced Oxidation Processes for Methane Removal - Challenges and Perspectives

Methane (CH₄) is a potent greenhouse gas and the second highest contributor to global warming. CH₄ emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH₄ emissions by developing large-scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH₄ (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar-driven gas phase advanced oxidation processes for CH₄ removal. And (3) to propose some ideas, which may help to develop solar-driven gas phase advanced oxidation processes and make them deployable at a climate significant scale.     

Photocatalytic Reduction of Nicotinamide Co-factor by Perylene Sensitized RhIII Complexes**

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene-based light-harvesting moiety and a catalytic rhodium center ( Rh^IIIphenPer ). The excited-state dynamics were investigated by means of steady-state and time-resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of Rh^IIIphenPer yields the formation of a charge-separated intermediate, namely Rh^IIphenPer ⋅ ⁺ , that results in a catalytically active species in the presence of protons.