Angewandte Chemie最新文献

Electrocatalytic reductive dehydroxylation is a promising strategy for sustainable synthesis of commodity and high-value-added chemicals but remains a formidable challenge due to the high dissociation energy of C─OH bond. Here, we report a selectively electrocatalytic reductive dehydroxylation of 1,4-butenediol (BED) to produce 3-buten-1-ol (BTO) over Cu nanowire arrays (Cu NWAs) under ambient conditions. A high BED conversion of ∼90.5% and a BTO selectivity of ∼80.2% are achieved at –0.9 V versus RHE. Even in a large-scale two-electrode H-type elecrolyser (1 L), the Cu NWAs stably exhibit a BED conversion of ≥ 92.3%, a BTO selectivity of ≥ 82.7%, and a BTO production rate of 190.8 mmol_·g_cat⁻¹_·h⁻¹ at an industrial current density of 200 mA cm⁻². Experimental and theoretical investigations reveal that the Cu surface facilitates the dissociation of C─OH bond in BED and the desorption of BTO, which thus promotes the selective dehydroxylation of BED to BTO. This work highlights a sustainable and efficient strategy for producing high-value-added chemicals.

Das synergistische Zusammenspiel von Elektrizität, Licht und leicht erhältlichen, ungiftigen Eisenkatalysatoren ermöglichte das effiziente Recycling von Polymerabfällen zu wertschöpfenden Produkten. Diese robuste Depolymerisationsstrategie war im Multigramm-Maßstab realisierbar, wobei die kathodische Wasserstoffentwicklungsreaktion eine attraktive Möglichkeit für eine umweltfreundliche Wasserstoffproduktion darstellt.

Das synergistische Zusammenspiel von Elektrizität, Licht und leicht erhältlichen, ungiftigen Eisenkatalysatoren ermöglichte das effiziente Recycling von Polymerabfällen zu wertschöpfenden Produkten. Diese robuste Depolymerisationsstrategie war im Multigramm-Maßstab realisierbar, wobei die kathodische Wasserstoffentwicklungsreaktion eine attraktive Möglichkeit für eine umweltfreundliche Wasserstoffproduktion darstellt.

Conjugated n-type polymers have long been explored as organic cathodes for lithium-ion batteries (LIBs), yet the widely studied P(NDI2OD-T2) has received limited attention as a practical cathode because of its modest capacity (∼55 mAh g⁻¹). Here, we report the first systematic effort to re-engineer this prototypical polymer through side-chain shortening and donor simplification. Replacing bulky 2-octyldodecyl (2OD) chains with 2-butyloctyl (2BO) and simplifying the bithiophene (T2) donor to a vinylene (V) produced P(NDI2BO-V), which delivers a 1.51-fold higher capacity (56.9→86.0 mAh g⁻¹) while retaining excellent cycling stability. Crucially, we show that n-type polymers can achieve remarkable cycling stability at elevated temperatures: both polymers remained stable at 60 °C, where small molecules fail, with P(NDI2OD-T2) keeping 97% after 1000 cycles and P(NDI2BO-V) 80% after 600 cycles. Mechanistic studies combining electrochemical analysis with density functional theory and molecular dynamics simulations reveal how donor linker units dictate structure and transport. Crystalline P(NDI2OD-T2) exhibits higher electronic conductivity and undergoes a one-step two-electron redox process, whereas amorphous P(NDI2BO-V) offers enhanced Li⁺ diffusivity but follows a stepwise pathway. This work establishes a molecular design framework for conjugated polymer cathodes that combine high capacity, efficient charge transport, and long-term thermal stability, advancing their potential for practical LIB applications.

The inverted perovskite solar cell (PSC), featuring self-assembled monolayers (SAMs) as the hole transport layer, has achieved a power conversion efficiency (PCE) exceeding 27%. However, the non-uniformity of SAMs and intrinsic defects within the perovskite film continue to constrain further enhancements in device performance. Herein, we developed a strategy for the synchronous modification of SAMs and perovskite by incorporating an ionic liquid of 1-butyl-3-methylimidazole-hexafluorophosphate (BM) to enhance the uniformity of SAMs and passivate defects in perovskite. Specifically, BM was incorporated into the perovskite precursor solution to effectively occupy halide vacancies and passivate the uncoordinated Pb²⁺. Meanwhile, owing to its ionic properties and the interaction between its functional groups and SAM, BM can effectively regulate the colloidal properties and reduce surface roughness, achieving a more uniform SAM layer. By employing this dual modification strategy, BM significantly modulates the crystallization kinetics, thereby facilitating the formation of highly crystalline perovskite films characterized by substantially enlarged grain sizes and a markedly reduced defect density. Consequently, the device incorporating dual modification of BM achieved a champion PCE of 26.59%, demonstrating exceptional operational stability with no observable PCE degradation after continuous power output at maximum power point (MPP) for 1000 h.

Die Austauschreaktion von Ameisensäure an Meersalz-Aerosolen, bei der HCl freigesetzt wird, fordert die herkömmliche Säure-Base-Chemie heraus. Unsere Gasphasenversuche zeigen, dass diese Reaktion an reinen NaCl-Clusterionen in Abwesenheit von Wasser stattfindet. Oberflächendefekte der NaCl-Clusterionen ermöglichen diese Reaktion durch verstärkte elektrostatische Wechselwirkungen der Salzionen mit dem Formiat, die den Unterschied in der Gasphasen-Acidität zwischen HCl und Ameisensäure mehr als ausgleichen.

Anti-inflammatory colchicine therapy has emerged as a new era for atherosclerotic cardiovascular diseases. However, the therapeutic benefit of colchicine has not been clearly defined. Herein, we present a double coordination-driven approach to fabricate a stable metal-organic nano-assembly of colchicine (COL-TA-Zn) by uniting the tropolone ring of colchicine (COL), phenolic groups of tannic acid (TA), and Zn²⁺ ions. This design leverages the antioxidant and anti-inflammatory properties of COL and TA to create a nanoscale platform capable of scavenging radicals and modulating inflammatory pathways. Through robust Zn²⁺ coordination, the resulting COL-TA-Zn nanocomplexes exhibit enhanced stability under physiological conditions, ensuring efficient delivery and sustained bioactivity. In vitro assays confirm suppression of foam cell formation and multiple inflammatory mediators, suggesting significant potential for managing atherosclerosis by targeting both oxidative stress and inflammation. Intravenous administration of COL-TA-Zn in Apoe^−/− mice significantly reduces atherosclerotic plaque area, MMP-9, TNF-α, and reactive oxygen species (ROS) levels, thereby illustrating its superior anti-atherosclerotic efficacy compared to COL alone. These findings highlight the promise of the dual coordination-driven nanoplatform in cardiovascular disease treatment.

Upcycling of waste plastics into commodity chemicals such as amino acids represents a promising route toward achieving negative carbon emissions and enabling a circular carbon economy. However, existing thermocatalytic methods typically require harsh conditions. While photocatalytic upcycling operates under mild conditions, its dependence on a high-temperature hydrolysis step for plastic pretreatment undermines its overall practicality. Here we report a bio-photocatalytic hybrid system that converts polylactic acid (PLA) plastics into alanine under ambient conditions. The integrated system begins with enzymatic depolymerization of PLA to lactic acid (LA) with 92% conversion at 55°C and pH 10, catalyzed by an engineered peptidase derived from the Micromonospora sp. strain. Without any purification, the resulting hydrolysate is fed directly to the photosynthesis system, where the LA monomers are converted to alanine over a Ni/ZnIn₂S₄ catalyst using ammonia as a nitrogen source. This photocatalytic process, which proceeds via an oxygen-centered radical intermediate pathway, achieves an alanine production rate of 61.91 mmol g⁻¹ h⁻¹ and an overall yield of 60%. Life cycle assessment demonstrates that our tandem bio-photoconversion system substantially reduces the carbon footprint compared to single-step thermocatalytic and photocatalytic systems. This work thus establishes a sustainable route for valued chemicals production from low-cost feedstocks.

Reactive intermediates, including radicals and other short-lived molecules, are ubiquitous in pure chemical processes and often highly difficult to isolate. Recently, we found that energetic, reactive radical species can be trapped through electroprecipitation, where the precipitate contains a reactive intermediate. The principle is straight-forward: If a solubility equilibrium can be exceeded before the reactive intermediate lifetime, the intermediate can be precipitated. Classically, electrochemiluminescence (ECL) is a process where electrical energy is transferred to chemical energy, and then the chemical energy is released in the form of light emission (often in the presence of an electroactive luminophore). The apparent luminescence lifetime, limited by radical lifetimes, of ECL reactions in solution is short (sub-microsecond), and thus can hinder the performance of the technique as light emission is confined to the electrode surface and occurs only when the electrical potential to the system is applied. Here, we show that with a high concentration (10–250 mM) of benzoyl peroxide (BPO) being co-reduced with a tris(2,2′-bipyridyl)ruthenium(II) complex, we can achieve an ECL emission that lasts for hundreds of seconds after potential arrest, corresponding to a thousand-fold (10³) increase in apparent afterglow chemiluminescence lifetimes. This electroprecipitation process occurs at an aqueous|organic multiphase boundary, which are present all through nature and are arguably more representative of natural chemical processes. Furthermore, experimental parameters, including BPO concentration, applied potential, and electrode material, were investigated. Competitive and parasitic processes, such as the hydrogen evolution reaction and decarboxylation, diminish the electroprecipitation of reactive intermediates, and we detail mitigation and optimization efforts. Overall, this work reveals that multiphase interfaces can be used to electroprecipitate reactive radicals, separating their use in space and time.

Für die nichtoxidative Ethandehydrierung zu Ethen wurden Katalysatoren mit isolierten Co²⁺-Spezies in den 6MR- (Co²⁺-Z₂) und 8MR-Fenstern ([Co(OH)]⁺-Z) eines SSZ-13-Zeolithen hergestellt. Die Co²⁺-Z₂-Spezies zeigten im Vergleich zu den [Co(OH)]⁺-Spezies eine unerwartet hohe Ethenbildungsgeschwindikeit. Der aktivste der entwickelten Katalysatoren, der Co²⁺-Z₂ enthält, übertrifft Analoga der kommerziellen K-CrO_x/Al₂O₃- und PtSn/Al₂O₃-Katalysatoren in Bezug auf die Ethenbildung.