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The overlooked role of adsorption isotherms in electrocatalysis 吸附等温线在电催化中被忽视的作用
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01461-z
Nitish Govindarajan, An T. Chu, Christopher Hahn, Yogesh Surendranath
Electrocatalysts enable the efficient interconversion of electrical and chemical energy for the sustainable production of fuels and chemicals. Here we highlight the importance of developing electrochemical adsorption isotherms to demystify complex reaction mechanisms and rationalize catalytic activity.
电催化剂使电能和化学能有效地相互转换,以实现燃料和化学品的可持续生产。在这里,我们强调了开发电化学吸附等温线对揭开复杂反应机理和合理化催化活性的重要性。
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引用次数: 0
Nitroarenes as energy transfer catalysts 硝基芳烃作为能量转移催化剂
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01458-8
Cong Xiao, Wen-Jing Xiao
Energy transfer photocatalysis typically requires expensive metal complexes or specific synthetic photosensitizers with particular triplet energies. Nitroarenes now emerge as powerful, sustainable alternatives, with their catalytic efficiency governed by excited-state geometry rather than only by energy matching, enabling efficient alkene isomerizations and cycloadditions.
能量转移光催化通常需要昂贵的金属配合物或具有特定三重态能量的特定合成光敏剂。硝基芳烃现在成为一种强大的、可持续的替代品,其催化效率受激发态几何形状而不仅仅是能量匹配的控制,从而实现了高效的烯烃异构化和环加成。
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引用次数: 0
Illuminating the transformation of photocatalysts in light-driven organic synthesis 阐明光催化剂在光驱动有机合成中的转化
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01457-9
Jianbin Li, Ding Zhang, Zhennan Hu, Zehao Yuan
Photocatalysis has become a cornerstone in modern organic synthesis due to its ability to generate and manage reactive radical intermediates, thus facilitating diverse chemical processes under mild conditions. A critical yet often overlooked aspect of photocatalysis is the dynamic transformation of photocatalysts into their active forms during reactions, which fundamentally governs their reactivity, selectivity and reaction outcome. Here we term this class of catalysts ‘transformer photocatalysts’, which undergo various activation pathways such as reductive activation, acid coordination, radical substitution and deconstructive processes. By categorizing selected examples based on these activation mechanisms, we aim to highlight the typical activation modes of some common photocatalysts and elucidate the underlying principles that guide the formation and behaviour of these active species. We hope that these mechanistic insights will provide a foundation for broadening the horizon of photocatalysis and developing photocatalysts tailored to organic transformations, thus inspiring further research in photochemistry and beyond. Photocatalysis enables many appealing synthetic reactions to proceed under mild conditions. This Review focuses on structural and electronic changes of photocatalysts, potentially resulting in frequently neglected active species that facilitate catalysis.
光催化已成为现代有机合成的基石,因为它能够产生和管理活性自由基中间体,从而在温和的条件下促进多种化学过程。光催化的一个关键但经常被忽视的方面是光催化剂在反应过程中向活性形式的动态转化,这从根本上决定了它们的反应活性、选择性和反应结果。本文将这类催化剂称为“变形光催化剂”,它们经历多种活化途径,如还原活化、酸配位、自由基取代和解构过程。通过对这些活化机制进行分类,我们的目标是突出一些常见光催化剂的典型活化模式,并阐明指导这些活性物质形成和行为的基本原理。我们希望这些机制的见解将为拓宽光催化的视野和开发适合有机转化的光催化剂提供基础,从而激发光化学等领域的进一步研究。光催化使许多有吸引力的合成反应在温和的条件下进行。本文综述了光催化剂的结构和电子变化,这些变化可能导致经常被忽视的催化活性物质的产生。
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引用次数: 0
Growing the carbon chain 生长碳链
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01455-x
Boon Siang Yeo
Electrocatalytic CO2 reduction on Cu is typically studied at room temperature and pressure, producing mostly C1 and C2 products (short carbon chains). High-temperature experiments above 125 °C now reveal a carbon-chain growth mechanism akin to the thermally driven Fischer–Tropsch reaction, resulting in the production of C1–C5 hydrocarbons.
通常在室温常压下研究Cu上的电催化CO2还原,主要产生C1和C2产物(短碳链)。125°C以上的高温实验揭示了类似于热驱动的费托反应的碳链生长机制,导致C1-C5碳氢化合物的产生。
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引用次数: 0
Shifting both ways on ceria 在二氧化铈上,两种方法都可以转换
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01468-6
Marcal Capdevila-Cortada
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引用次数: 0
Deracemization by recombination 重组脱羧
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01467-7
Jan-Stefan Völler
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引用次数: 0
Practical conversion of carboxylic acids to nitriles 羧酸到腈的实际转化
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01459-7
Christina N. Wiswell, David K. Tanas, Mitchell P. Croatt
Direct conversion of carboxylic acids to nitriles is desirable but thermodynamically uphill. Here, a bioinspired process utilizes magnesium and palladium co-catalysts and urea as a nitrogen source.
羧酸直接转化为腈是可取的,但热力学上是上坡的。在这里,一个生物启发的过程利用镁和钯共催化剂和尿素作为氮源。
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引用次数: 0
Shining light using the dark 利用黑暗发出光亮
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-22 DOI: 10.1038/s41929-025-01469-5
Benjamin Martindale
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引用次数: 0
Near-infrared plasmonic activation of molecular oxygen for selective oxidation of biomass derivatives 近红外等离子体活化分子氧选择性氧化生物质衍生物
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-18 DOI: 10.1038/s41929-025-01454-y
Manpreet Kaur, Sourav Rej, Jan Navrátil, Eva Yazmin Santiago, Michal Otyepka, Stefano Livraghi, Lorenzo Mino, Štěpán Kment, Zhikang Xu, Haibo Zhu, Paolo Fornasiero, Alexander O. Govorov, Piotr Błoński, Alberto Naldoni
Upgrading biomass feedstock into higher-value chemicals is central to improve the sustainability of the chemical industry and to reduce its dependence on fossil raw materials. Heterogeneous photocatalysts are promising for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a biomass-derived molecular platform for biopolymers, but their FDCA selectivity is negligible without the aid of a base. Here we present a plasmonic photocatalyst integrating TiN nanocubes and bimetallic RuPt nanoparticles that in base-free conditions exhibits complete HMF conversion and selective FDCA formation due to an unconventional mechanism of molecular oxygen activation. This unique reactivity is enhanced by both photothermal heating and hot electrons, whose contribution is confirmed by kinetic isotopic effect experiments. Density functional theory calculations support a scenario in which the activated nanoparticle–oxygen complex facilitates the rate-determining step and enables an improved FDCA selectivity. Our results demonstrate the potential of plasmonic photocatalysts in the catalytic transformation of biomass. Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O2 and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.
将生物质原料升级为价值更高的化学品,对于提高化学工业的可持续性和减少其对化石原料的依赖至关重要。非均相光催化剂在将5-羟甲基糠醛(HMF)氧化为2,5-呋喃二羧酸(FDCA)这一生物质衍生的生物聚合物分子平台上很有前景,但在没有碱的帮助下,它们的FDCA选择性可以忽略不计。在这里,我们提出了一种集成了TiN纳米立方体和双金属稀土纳米颗粒的等离子体光催化剂,在无碱条件下,由于一种非常规的分子氧活化机制,它表现出完全的HMF转化和选择性的FDCA形成。这种独特的反应性被光热加热和热电子增强,其贡献被动力学同位素效应实验证实。密度泛函理论计算支持这样一种情况,即活化的纳米颗粒-氧配合物促进了速率决定步骤,并使FDCA选择性得到改善。我们的研究结果证明了等离子体光催化剂在生物质催化转化中的潜力。
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引用次数: 0
Excited-state configuration controls the ability of nitroarenes to act as energy transfer catalysts 激发态结构控制硝基芳烃作为能量转移催化剂的能力
IF 44.6 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-12-17 DOI: 10.1038/s41929-025-01453-z
Martin Rihtaršič, Byeongseok Kweon, Piotr T. Błyszczyk, Alessandro Ruffoni, Enrique M. Arpa, Daniele Leonori
Energy transfer (EnT) catalysis enables the selective population of triplet excited states without previous singlet excitation, thus eliminating the need for high-energy irradiation. Traditionally, EnT catalysis has been approached by developing specific photosensitizers with triplet energies (ET) that match those of the targeted substrates. Here we introduce an alternative approach to EnT using widely available nitroarenes as photocatalysts. Our findings reveal that their catalytic efficiency is governed by the localization of their excited state rather than ET. Specifically, 3π,π* nitroarenes, where the excitation is centred on the aromatic core rather than the nitro group, exhibit superior catalytic performance compared with their 3n,π* counterparts. We have demonstrated the utility of this concept for nitroarene photocatalysis in contra-thermodynamic E-to-Z alkene isomerization and [2 + 2] cycloadditions. Additionally, we use the energetic descriptor ΔETT as easy tool to distinguish the preferential population of 3n,π* versus 3π,π* triplet states and therefore accelerate the identification of novel photosensitizers. Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.
能量转移(EnT)催化使三重态激发态的选择性人口没有先前的单线态激发,从而消除了对高能辐照的需要。传统上,通过开发具有与目标底物相匹配的三重态能量(ET)的特定光敏剂来接近EnT催化。在这里,我们介绍了一种使用广泛使用的硝基芳烃作为光催化剂的替代方法。我们的研究结果表明,它们的催化效率取决于它们激发态的定位,而不是ET。具体来说,3n,π*硝基芳烃的激发集中在芳香核而不是硝基上,与3n,π*硝基芳烃相比,它们表现出更好的催化性能。我们已经证明了这一概念在反热力学E-to-Z烯烃异构化和[2 + 2]环加成中对硝基芳烃光催化的效用。此外,我们使用能量描述符ΔETT作为简单的工具来区分3n,π*与3π,π*三重态的优先居群,从而加快了新型光敏剂的鉴定。
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引用次数: 0
期刊
Nature Catalysis
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