ChemPhotoChem

Abstract Having identified inconsistencies when repeating literature examples of photochemical transformations and difficulties recreating experimental setups, we devised several criteria that an ideal lab‐scale reactor should achieve. Herein, we introduce a versatile photoreactor for high‐throughput screening, preparative‐scale batch reactions and continuous processing, all with a single light source. The reactor utilizes interchangeable arrays of pseudo‐monochromatic high‐power LEDs in a range of synthetically useful wavelengths, combined with excellent temperature control. Moreover, light intensity can be modulated in an accurate and straightforward manner. This system has subsequently been tested on a range of literature methodologies.

Holly E. Bonfield

Kayleigh Mercer

Alba Diaz‐Rodriguez

Gemma C. Cook

Blandine S. J. McKay

Pawel Slade

George M. Taylor

Wei Xiang Ooi

Jason D. Williams

Jack P. M. Roberts

John A. Murphy

Luca Schmermund

Wolfgang Kroutil

Tamara Mielke

Jared Cartwright

Gideon Grogan

Lee J. Edwards

The Right Light: De Novo Design of a Robust Modular Photochemical Reactor for Optimum Batch and Flow Chemistry

正确的光源：新型设计的高效模块化光化学反应器，适用于最佳批次和流动化学

Abstract In this study, we investigate the effect of terminal benzene derivatives in triphenylamine‐based oxime esters on their photoreactivity. Five novel oxime esters ( Miko series) that containing different benzene derivatives as terminal groups, were synthesized. The electronic properties of the substituents on the benzene ring range from electron‐donating to electron‐withdrawing. Specifically, a methoxy benzene for Miko‐MOB , tert ‐butyl benezene for Miko‐ t ‐Bu , chloro benzene for Miko‐CB , trifluoromethyl benzene for Miko‐TFM , and nitro benzene for Miko‐NB . Additionally, a compound with benzene only as the terminal substituent ( TP‐1 ) was selected for comparision. All the new compounds exhibited higher molar extinction coefficients than TP‐1 . Additionally, the steady‐state photolysis and electron spin resonance (ESR) properties would decrease from the electron‐donating substitutes to electron‐withdrawing substitutes. Finally, these oxime esters are utilized in Type I photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) under UV or LED@405 nm light irradiation conditions. Among all formulations, Miko‐MOB demonstrated the highest double bond conversion efficiency under both UV and LED@405 nm light irradiation. Thus, terminal benzene derivatives in oxime esters play an important role in tuning the optical and photochemical reaction performance, offering significant value for the design strategy of such photoinitiators.

Jyun‐Bin Hsieh

Yung‐Chung Chen

The role of the terminal benzene derivatives in triphenylamine‐based oxime esters for free radical photopolymerization

三苯胺基肟酯中末端苯衍生物在自由基光聚合中的作用

The increasing number of devastating environmental disasters in recent years is ascribed to a changing climate due to the steady increase in the concentration of carbon dioxide in the atmosphere. With this in mind, the search for ways to recycle and transform CO2 into more useful products has received significant attention and has become an issue of global concern. The activation of CO2 is, however, a very energy intensive endeavor and the use of a renewable energy source, such as sunlight, is a basic requirement. Strategies that aim at harnessing sunlight to produce fuels or chemicals are often assigned to the large research field of "artificial photosynthesis". Within this field it was realized that direct utilization of sunlight to produce electrical energy is often impractical because of its intrinsic intermittency and fluctuating intensity. Thus, converting light into chemical bond energy is highly desirable for a sustainable future fuel economy. The transformation of CO2 into different C1 building blocks, such as carbon monoxide, formic acid, methanol or methane, or compounds with a higher number of carbon atoms, all have their significance for industrial applications. Sunlight can either be applied directly or indirectly via a photovoltaic device to activate CO2. While indirect sunlight application is actually reducing the topic to a problem of electrocatalysis, direct application of sunlight can be roughly divided into homogeneous or heterogenous catalytic methods with some very interesting recent developments in the field of hybrid systems. Molecular compounds, with their well-defined structure, enable in-depth mechanistic studies and the deduction of structure–activity relationships, of which several are presented in this Special Collection. On the other hand, solid-state materials stand out with higher robustness and stability, although they usually show poor product selectivity. Nevertheless, the products obtained from systems incorporating solid-state materials are usually higher reduced forms of CO2 and Cn compounds (with n>1), which is attractive for further downstream industrial processes. As a novel synthetic development, hybrid systems, in which a molecular catalyst is fixed on a (most often) semiconducting surface, aim to merge the advantages of both worlds, and some interesting examples are also provided within this collection. In summary, in this Special Collection different developments to transform CO2 into value-added chemicals by using light as a clean energy source are presented. The research articles and reviews provide insight into existing state-of-the-art molecular, solid-state and hybrid systems. We hope that interested readers will take the presented work as stimulation and inspiration for the design of future photocatalytic or photoelectrochemical systems as well as other systems for solar energy conversion and storage. There is still the need to improve catalyst stability and selectivity, which will ensure continuation of research efforts to achieve a sustainable circular process. Any achievements will undoubtedly play an important role for the global society, economy and science in the future. Matthias Schwalbe studied chemistry in Jena (Germany) and Glasgow (UK). After a postdoctoral stay at MIT, Cambridge (USA), he started his independent career at the Humboldt-Universität zu Berlin (Germany) in 2010. His major research interest is in the design of metal complexes for the activation of small molecules, in particular CO2 and O2, for testing in electro- and photocatalytic applications. Hongwei Huang is a Professor at School of Materials Science and Technology, China University of Geosciences (Beijing, China). His current research mainly focuses on preparation of polar semiconductor photocatalysts for energy and environmental applications. Gonghu Li is currently a Professor of Chemistry at the University of New Hampshire (USA). His research involves the applications of surface chemistry and catalysis in solar energy conversion. Recent projects in his group include hybrid photocatalysts and single atom catalysts for solar CO2 reduction.

Matthias Schwalbe

Hongwei Huang

Gonghu Li

Photocatalytic and Photoelectrochemical Carbon Dioxide Reduction

光催化与光电化学二氧化碳还原

Tim Silies

Nikos L. Doltsinis

Constantin G. Daniliuc

Fabio Rizzo

Front Cover: Fluorene vs. Spirobifluorene: Effect of the <i>π</i>‐System on TADF Properties (ChemPhotoChem 12/2024)

封面：芴与螺二芴：π系统对热激活延迟荧光性质的影响（《化学光化学》2024年第12期）

The photolysis of the gold nanoclusters Au25(SR)18z (z = 1‐, 0 and 1+, R=C2H4Ph and C12H25) NCs in halogenated solvents such as dichloromethane leads to changes in the charged states of the Au25(SR)18z observed using UV‐Visible and 1H NMR spectroscopic techniques. Matrix assisted laser desorption mass spectrometry results proved that during charge transformation, from anion to neutral and eventually cation forms, the size of nanoclusters remains intact. Electrochemistry of Au25(SR)18 has enabled us to monitor changes by cyclic voltammetry, indicating decay in the redox peak current upon irradiation. In the absence of light and/or in a non‐halogenated solvent, e.g., tetrahydrofuran, no substantial change in the photophysical signatures of Au25 nanoclusters was observed. These observations highlight (i) the importance on selecting appropriate solvent(s) in the synthesis and photochemical studies of atomically precise metal nanoclusters and (ii) possibility of using photochemistry in halogenated solvents to synthesize different charge state of atomically precise metal nanoclusters. Thus, we envision that other monodispersed molecule‐like nanoclusters, with various size and charges can be achieved via this photosynthetic protocol under controlled conditions, e.g., solvent, light, and photolysis duration.

Johanna A. de-Jong

Mark Steven Workentin

Mahdi Hesari

Charge State Tuning and Photochemical Stability of Au25(SR)18 Nanoclusters

Au25(SR)18纳米团簇的电荷态调控与光化学稳定性

Hole‐scavengers are a crucial part of particulate photocatalytic systems. The use of hole‐scavengers increases the photocatalytic activity by preventing electron‐hole recombination. The holes are used in photo‐oxidation of the hole‐scavenger molecules increasing the probability of electrons involved in photoreduction of water. In this study, different hole‐scavengers utilized in photocatalytic water splitting reaction were tested. The impact of different hole scavengers on photocatalytic reactions were investigated on [Ca2Nb3O10]‐ 2D nanosheets mechanistically. Cyclic voltammetry and chronoamperometry tests were employed to assess the impact of hole scavengers on photocatalytic efficiency. The photoelectrochemical tests agree with the results of the photocatalytic reactions. Methanol and EDTA give the largest oxidation photocurrent and the best photocatalytic activity.

Bengisu Yilmaz

Ugur Unal

Photoelectrochemical investigation of Hole Scavengers for Photocatalytic Hydrogen Evolution Reaction on Perovskite‐type Niobate Nanosheets

钙钛矿型铌酸盐纳米片光催化析氢反应中空穴清除剂的光电化学研究

Artificial photosynthesis, encompassing the photocatalytic generation of H2 and CO2 reduction innovations, seems to be a highly promising approach. This is due to its ability to efficiently transform CO2 into hydrocarbon fuel and valuable chemical products using solar energy as a direct energy source. This will simultaneously help to mitigate global warming and energy shortage issues. Chalcogenide‐based semiconductors have recently gotten a lot of attention as an important area of research for photocatalytic H2 production and CO2 conversion, owing to their low band gap energy, suitable band structures, and a great photoresponsivity spectrum. Modifying chalcogenides into their heterostructures could be a great way to solve problems like photo corrosion and carrier recombination. Therefore, this review summarized a series of different modifications of chalcogenides and recent developments in their photocatalytic and photo electrocatalytic performance, particularly in H2 production and CO2 conversion. Lastly, we discussed the challenges, limitations, areas for development, and future prospects of chalcogenides and their heterostructures capable of utilizing visible light to produce H2 gas and reduce CO2.

Ashmalina Rahman

Shaikh Parwaiz

Youngku Sohn

Mohammad Mansoob Khan

Advances in Artificial Photosynthesis: The Role of Chalcogenides and Chalcogenide‐based Heterostructures

人工光合作用的进展：硫属化物及其硫属化物基异质结构的作用

Triplet pairs (TT) in crystalline molecular semiconductors have unique spin properties of interest for quantum information or enhancing solar photoconversion. The population and diffusion dynamics of TT have been the subject of recent studies, both in covalent dimers and in crystalline systems. Here, we monitor the triplet population in neat polycrystalline and amorphous films of a heteroacene with known TT spectral properties and tunable spin polarization depending on the intermolecular geometry. Transient measurements reveal an anomalous power dependence in polycrystalline films that we attribute to the fast diffusion and interaction of dissociated triplet pairs confined to one‐dimensional stacks of strongly coupled molecules. The nongeminate triplet interaction after dephasing facilitates conversion to the triplet 3TT and eventually T1+S0. Amorphous films have no power dependence and proceed directly from 1TT to 3TT and subsequently T1+S0 via state mixing facilitated by nonparallel geometries and weak exchange coupling.

Brandon K. Rugg

Angana De

Sarath Santhakumar

Qiushi Ma

Brian Fluegel

Karl J. Thorley

John E. Anthony

Libai Huang

Justin Johnson

Distinct Mechanisms of Triplet‐Pair Decay in Amorphous and Crystalline Heteroacene Thin Films

无定形和结晶并五苯薄膜中三重态对衰减的不同机制

Abbreviation
Journal Impact	3.04
Quartiles(Global)	CHEMISTRY, PHYSICAL(Q3)

ISSN	2367-0932
h-index	36

Publication Information	Publisher: Wiley-VCH Verlag，Publishing cycle: ，Journal Type: journal，Open Access Journals: No
Basic data	Year of publication: 2017，Proportion of original research papers: 95.77%，Self Citation Rate:3.30%， Gold OA Rate: 30.40%

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The Right Light: De Novo Design of a Robust Modular Photochemical Reactor for Optimum Batch and Flow Chemistry

The role of the terminal benzene derivatives in triphenylamine‐based oxime esters for free radical photopolymerization

Photocatalytic and Photoelectrochemical Carbon Dioxide Reduction

Front Cover: Fluorene vs. Spirobifluorene: Effect of the π‐System on TADF Properties (ChemPhotoChem 12/2024)

Charge State Tuning and Photochemical Stability of Au25(SR)18 Nanoclusters

Photoelectrochemical investigation of Hole Scavengers for Photocatalytic Hydrogen Evolution Reaction on Perovskite‐type Niobate Nanosheets

Advances in Artificial Photosynthesis: The Role of Chalcogenides and Chalcogenide‐based Heterostructures

Charge State Tuning and Photochemical Stability of Au25(SR)18 Nanoclusters

Distinct Mechanisms of Triplet‐Pair Decay in Amorphous and Crystalline Heteroacene Thin Films

Front Cover: Fluorene vs. Spirobifluorene: Effect of the π‐System on TADF Properties (ChemPhotoChem 12/2024)