Latest ArticlesFunctionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO2 reduction reaction (CO2RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO2 than H2O on Pd NPs surface, and induced more CO linear configuration intermediate (*COL), indicative of ease CO2 transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FECO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FECO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
Given the emerging demand to “escape from flatland” for modern medicinal chemistry, both the catalytic construction of complex three-dimensional molecular architectures from planar aromatics and the bioisosteric substitution of aromatic ring with bicyclo[2.1.1]hexanes (BCHs) become increasingly valuable. Despite notable advancements in the cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) and 2π-components, the application of easily accessible aromatic compounds in these transformations, particularly in an asymmetric manner, is still relatively unexplored. Herein, we report a nickel-catalyzed enantioselective polar dearomative (3 + 2) cycloaddition of BCBs with benzazoles and indoles. This protocol offers an efficient route for the synthesis of N,S- or N,N-heterocycles decorated fused aza-BCHs bearing two quaternary carbon centers. This approach stands out for its practicality and appeal due to the utilization of easily accessible starting materials and catalysts, broad substrate scope, easy scalability, and the employment of mild reaction conditions. Density functional theory (DFT) calculations offer crucial insights into the reaction mechanism and elucidate the factors governing the enantioselectivity within the dearomative cycloaddition process.
A novel method for carbonylation of tertiary C(sp3)–H bonds in 2-aminophenyl-alkyl methanones with CO2 has been developed, enabling the synthesis of 2,4-quinolinediones featuring quaternary carbon centres. Building on this approach, a promising iridium(Ⅲ) complex involving carbon from CO2 was designed and synthesized. This complex, exhibiting a high photoluminescent quantum yield, was successfully applied in organic light-emitting diodes (OLEDs), achieving a high maximum luminance up to 12,010 cd/m2 and a maximum external quantum efficiency (EQE) of 13.95%.
The α,β-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of γ-butyrolactones—a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of α,β-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing γ-butyrolactone moiety.
The hydrogen evolution reaction (HER) is a pivotal process for clean energy conversion, yet the development of efficient and cost-effective electrocatalysts remains a major challenge. Alloy catalysts, with their tunable electronic properties and promising catalytic performance, have shown great potential for HER. However, the design of component types and ratios, along with structural optimization, has largely relied on traditional trial-and-error approaches, which are very complex and time-consuming. The rise of machine learning (ML) provides an efficient strategy for discovering and optimizing alloy catalysts by enabling rapid analysis of extensive experimental and simulation datasets. This review highlights the recent advances in applying ML techniques for the design and optimization of alloy electrocatalysts for HER, covering binary and multinary (ternary, quaternary and high-entropy alloys). In particular, by employing supervised learning and deep learning techniques, ML has achieved remarkable success in the rapid screening of alloy catalysts and in improving prediction accuracy. It also demonstrates the merit and capability of ML in accelerating this process. In the end, we discuss current challenges and future prospects for integrating ML into advanced HER catalysis, highlighting its potential to revolutionize catalyst development and promote sustainable hydrogen energy solutions.
Transforming sunlight into renewable energy sources like hydrogen and methane through photocatalytic water splitting and the CO2 conversion presents a promising prospect to tackle energy scarcity and environmental pollution caused by burning fossil fuels. As the core of the photocatalytic technique, photocatalysts design is most significant for acquiring the desirable catalytic performance and target products. Photonic crystals, also denoted as inverse opals and three-dimensionally ordered macroporous materials (3DOM), have been extensively applied in photocatalytic fields due to their distinct advantages. Specifically, photonic crystal possesses slow photons effect, rich reactive sites, and well-interconnected inner channels. Among the above advantages, the slow photons effect contributes the most essential role for accelerating photocatalytic reaction. However, how to design materials with maximized slow photons effect upon specific wavelength illumination is still in the infancy. Although some reviews about 3DOM photocatalysts have been published, a critical review focusing on tunable slow photons effects for efficient photocatalysis is still lacking. In this review, we highlighted recent advances in slow photons effect in boosting solar energy conversion. Meanwhile, the relevant mechanism and fundamentals of the slow photons effect are discussed. Finally, we present our vision of the future developments and challenges in this exciting research field.
Organic electrochemical transistor (OECT)-based inverters hold great promise for neural-machine interfaces due to their low operating voltage and compatibility with aqueous environments. However, unbalanced p-/n-channel characteristics hinder the inverter's voltage gain and fast switching. Here, a rational inverter design is presented, leveraging ion concentration to equilibrate p-n channel conductivity and kinetic doping in the OECT inverter, achieving an extremely high gain value of over 370 V/V under optimized driving conditions. Furthermore, a 3-stage ring oscillator constructed from these ion-equilibrated OECT inverters exhibits a rapid response time (stage delay < 0.6 ms) and a broad frequency response exceeding 300 Hz, matching the mechanoreceptor signals in human skin. The biocompatible output displays a sublinear reaction to static pressure pulses, indicating successful tactile recognition in live neurons. This work presents a practical strategy for constructing neural-compatible artificial logics through ion-concentration engineering, providing a platform for seamless neural-machine integration.
Essential oils (EOs) are widely present in aromatic plants and possess a wide range of significant pharmacological activities such as antibacterial, antioxidant and anti-tumor properties. They have broad application prospects in medical care, food, agriculture and other fields. However, their poor stability poses substantial challenges that significantly hinder their development and practical application. Metal-organic framework materials (MOFs), characterized by highly controllable structures, large specific surface areas, and stimuli-responsive release properties, have been extensively utilized in various fields such as drug delivery and food preservation. Due to their capacity to encapsulate and deliver EOs, MOFs have garnered considerable attention. In this review, we systematically summarize the structural features, types, and characteristics of MOFs, as well as the recent advancements in their application for controlled EO release. Furthermore, we focus on discussing engineering strategies aimed at enhancing the encapsulation, release, and delivery of EOs using MOFs. Finally, we briefly outline the existing challenges in the delivery of EOs using MOFs and present well-reasoned insights into prospective directions for future research.
Supported noble‐metal catalysts often suffer from nanoparticle sintering, resulting in rapid deactivation under high‐temperature conditions. We report hierarchically porous spinel type high-entropy oxide (S-HEO) nanofibers, (CrMnFeCoMg)3O4, as robust supports for Pt nanoparticles. The porous structure (38.5 m2/g) endows thermal stability, preserving porosity after 880 ℃ calcination. The porous Pt/S-HEO-500 exhibits exceptional sinter-resistance. Under 500 ℃ calcination, Pt exhibits only a 0.2 nm growth increment, owing to the physical confinement and strong metal–support interactions. For Pt/S-HEO-500, the T50 (50% conversion temperature) for CO oxidation was merely 9 ℃ higher than that without calcination, with 100% conversion retained over 100 h of steady-state operation. These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in high-temperature applications.
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