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Hierarchical porous covalent organic framework nanosheets with adjustable large mesopores 具有可调大介孔的分层多孔共价有机框架纳米片

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.022

Synchronous manipulation of meso-structure and architecture of covalent organic frameworks (COFs) is vital for customized applications but still remains challenging. Here, we develop a polymerization-induced co-assembly approach to construct hierarchical porous COF-based nanosheets with adjustable large mesopores (7–40 nm), intrinsic micropores (∼1.2 nm), ultra-thin thickness (∼24 nm), and a crystalline wall. Furthermore, density functional theory calculations and adsorption experiments indicated that the complementarity of the two-dimensional architecture and intrinsic micropores of COFs can effectively confine iodine molecules. Meanwhile, the exposed nitrogen-containing active sites created by the unique mesoporous structure can strongly anchor iodine species, thereby greatly inhibiting their dissolution and shuttling. Therefore, as a cathode for zinc-iodine battery, they delivered an outstanding rate capability (191.2 mAh g⁻¹ at 0.5 A g⁻¹) and stable long-term cyclability (154.8 mAh g⁻¹ at 3 A g⁻¹ after 20,000 cycles). This approach sheds light on the precise fabrication of crystalline porous materials for diverse applications.

同步操纵共价有机框架（COFs）的中层结构和体系结构对定制应用至关重要，但仍然具有挑战性。在这里，我们开发了一种聚合诱导的共组装方法，以构建具有可调节的大中孔（7-40 nm）、本征微孔（∼1.2 nm）、超薄厚度（∼24 nm）和晶壁的分层多孔 COF 基纳米片。此外，密度泛函理论计算和吸附实验表明，COFs 的二维结构和固有微孔的互补性可有效禁锢碘分子。同时，独特的介孔结构所形成的外露含氮活性位点可以强力锚定碘物种，从而极大地抑制其溶解和穿梭。因此，作为锌碘电池的阴极，它们具有出色的速率能力（0.5 A g-1 时为 191.2 mAh g-1）和稳定的长期循环能力（20,000 次循环后，3 A g-1 时为 154.8 mAh g-1）。这种方法为精确制造晶体多孔材料的各种应用提供了启示。

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引用次数: 0

Terpenoid-based high-performance polyester with tacticity-independent crystallinity and chemical circularity 萜类高性能聚酯，具有与触觉无关的结晶性和化学循环性

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.024

The development of chemically circular, bio-based polymers is an urgently needed solution to combat the plastic waste crisis. However, the most prominent, commercially implemented bio-based aliphatic polyester, poly(lactic acid) (PLA), is brittle, therefore largely limiting its broad applications. Herein, we introduce a class of aliphatic polyesters produced through the ring-opening polymerization (ROP) of (1R,5S)-8,8-dimethyl-3-oxabicyclo[3.2.1]octan-2-one (D-CamL) and the racemic mixture (rac-CamL), which exhibit superior material properties relative to PLA. A metal-based or organic catalyst was used for the modulation of polymer tacticity. Notably, regardless of tacticity, poly(CamL) exhibits intrinsic crystallinity, resulting in polyesters with high yield stress (24–39 MPa), high Young’s modulus (1.36–2.00 GPa), tunable fracture strains (6%–218%), and high melting temperatures (161°C–225°C). Importantly, poly(CamL) can be chemically recycled to monomer in high yield, and virgin-quality poly(CamL) is obtained after repolymerization. Overall, poly(CamL) represents a new class of bio-derived and chemically circular high-performance polyesters.

开发化学循环型生物基聚合物是应对塑料废弃物危机急需的解决方案。然而，最著名的商业化生物基脂肪族聚酯--聚乳酸（PLA）却很脆，因此在很大程度上限制了它的广泛应用。在本文中，我们介绍了通过 (1R,5S)-8,8-二甲基-3-氧杂双环[3.2.1]辛烷-2-酮（D-CamL）和外消旋混合物（rac-CamL）的开环聚合（ROP）生产的一类脂肪族聚酯，与聚乳酸相比，这种聚酯表现出更优越的材料特性。金属催化剂或有机催化剂可用于调节聚合物的触变性。值得注意的是，无论触变性如何，聚（CamL）都表现出固有的结晶性，因此聚酯具有高屈服应力（24-39 兆帕）、高杨氏模量（1.36-2.00 GPa）、可调断裂应变（6%-218%）和高熔化温度（161°C-225°C）。重要的是，聚（CamL）可以通过化学方法高产率地回收为单体，并在重新聚合后获得原生质量的聚（CamL）。总之，聚（CamL）是一类新型的生物衍生和化学循环高性能聚酯。

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引用次数: 0

Ribosomal peptides with polycyclic isoprenoid moieties 具有多环异戊二烯分子的核糖体肽

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.026

Florian Hubrich , Sanath K. Kandy , Clara Chepkirui , Chandrashekhar Padhi , Silja Mordhorst , Philipp Moosmann , Tao Zhu , Muriel Gugger , Jonathan R. Chekan , Jörn Piel

Isoprenoid modifications of proteins and peptides serve fundamental biological functions and are of therapeutic interest. While C₁₅ (farnesyl) and C₂₀ (geranylgeranyl) moieties are prevalent among proteins, known ribosomal peptide prenylations involve shorter-chain units not exceeding farnesyl in size. To our knowledge, cyclized terpene moieties have not been reported from either biomolecule class. Here, we used targeted genome mining and heterologous pathway reconstitution to identify ribosomally synthesized and post-translationally modified peptides (RiPPs) with elaborate, cyclized geranylgeranyl modifications. The installing maturases commonly feature fused prenyltransferase-terpene cyclase architectures. We characterized two bifunctional maturases with distinct prenyltransferase folds and identified the terminal product of a cyanobacterial proteusin as an exceptionally complex pseudosteroid-annelated polycyclic peptide. Bioassays suggest modest anti-cyanobacterial activity with the modification being crucial for activity. Genome data predict cyclic isoprenoid units for various RiPP families, including proteusin, Nif11, and lasso peptides, and thus the broader natural and biotechnological compatibility of the maturase system.

蛋白质和肽的异戊烯基修饰具有基本的生物学功能和治疗意义。虽然 C15（法呢基）和 C20（香叶基）分子在蛋白质中很普遍，但已知的核糖体肽前炔基化涉及的短链单位大小不超过法呢基。据我们所知，这两类生物大分子中都没有环化萜烯分子的报道。在这里，我们利用有针对性的基因组挖掘和异源途径重组来鉴定核糖体合成和翻译后修饰肽（RiPPs），这些肽具有精细的环化香叶基萜烯修饰。安装的成熟酶通常具有融合的前酰基转移酶-萜烯环化酶结构。我们对两种具有不同前炔基转移酶折叠的双功能成熟酶进行了鉴定，并发现蓝藻蛋白苷的末端产物是一种异常复杂的假甾醇-通道化多环肽。生物测定表明，这种酶具有适度的抗蓝藻活性，而修饰是其活性的关键。基因组数据预测了各种 RiPP 家族的环状异戊二烯单元，包括蛋白肽、Nif11 和拉索肽，从而使成熟酶系统具有更广泛的自然和生物技术兼容性。

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引用次数: 0

The legacy of Professor Li-Xin Dai: Organometallic and asymmetric catalysis 戴立新教授的遗产：有机金属催化和不对称催化

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.003

Tao Tu , Yong-Gui Zhou , Yong Tang , Boliang Lou , Shu-Li You

Prof. Li-Xin Dai will always be remembered for his development of organometallic chemistry and asymmetric synthesis, especially for the refining and synthesis of aureomycin, organoboron chemistry, and the development of novel chiral ligands for transition-metal-catalyzed asymmetric reactions. In addition to making significant contributions to science, Prof. Dai has also made a profound impact as an esteemed educator and mentor, imparting his knowledge and work ethic to future generations of chemists and fostering fruitful collaborations with his colleagues.

人们将永远铭记戴立新教授在有机金属化学和不对称合成方面的发展，尤其是在金霉素的提纯和合成、有机硼化学以及开发用于过渡金属催化不对称反应的新型手性配体方面。除了对科学做出重大贡献外，戴教授还作为一位受人尊敬的教育家和导师产生了深远的影响，他将自己的知识和职业道德传授给后代化学家，并与同事们建立了富有成效的合作关系。

引用次数: 0

Kinetic sieving separation of a gating macrocyclic crystal for purification of propylene 用于提纯丙烯的门控大环晶体的动力学筛分分离技术

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.007

Finding an energy-efficient alternative to cryogenic distillation for the room temperature, pressure-swing-adsorptive separation of propylene/propane (C₃H₆/C₃H₈) is challenging due to their physiochemical similarity. Herein, we report a gating macrocyclic crystal facilely prepared by the recrystallization of a macrocyclic arene (i.e., naphthyl-hexnutarene), which exhibits outstanding separation capabilities for C₃H₆/C₃H₈, with a remarkable kinetic selectivity of 76.7 and fast C₃H₆ adsorption kinetics with a diffusional time constant of 0.1727 min⁻¹. The achievement is attributed to the transient motions of a gating methoxy group on the macrocycle that extend toward the contracted pore apertures, effectively amplifying the subtle distinction in guest transport. Furthermore, this crystal demonstrates great potential in actual pressure swing adsorption processes, showcasing energy-saving and efficient regeneration, as evidenced by a low heat of adsorption of 15.4 kJ mol⁻¹ for C₃H₆ and full recovery of adsorption capacity through dynamic vacuum at room temperature, together with merited exclusions of co-present C₂H₆/C₂H₄/CH₄/CO₂/N₂ for C₃H₆ purification.

由于丙烯/丙烷（C3H6/C3H8）具有相似的物理化学性质，因此寻找一种替代低温蒸馏的高能效室温压力摆动吸附分离技术具有挑战性。在此，我们报告了一种通过重结晶大环芳烃（即萘六烯）而方便制备的门控大环晶体，该晶体对 C3H6/C3H8 具有出色的分离能力，其动力学选择性高达 76.7，对 C3H6 的吸附动力学速度极快，扩散时间常数为 0.1727 min-1。这一成果归功于大循环上的门控甲氧基向收缩孔径延伸的瞬态运动，有效地放大了客体传输中的微妙差异。此外，这种晶体在实际变压吸附过程中表现出巨大的潜力，展示了节能和高效的再生能力，这体现在它对 C3H6 的吸附热低至 15.4 kJ mol-1，并且在室温下通过动态真空完全恢复了吸附能力，同时还排除了共存的 C2H6/C2H4/CH4/CO2/N2，有利于 C3H6 的提纯。

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引用次数: 0

Enhancing backbone organization and photovoltaic performance of M-series acceptors by using partially fluorinated side chains 通过使用部分氟化侧链增强 M 系列受体的骨架组织和光伏性能

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.005

Side-chain fluorination of nonfullerene acceptors (NFAs) has been rarely reported to enhance their photovoltaic performance, although it may improve their backbone organization and carrier mobilities. Here, we design new partially fluorinated side chains and incorporate them into M-series NFAs, which are featured with a ladder-type heteroheptacene-cored skeleton without sp³-hybridized carbons. Compared with the traditional M-series acceptor with non-fluorinated side chains (MC7F0), the NFA with partially fluorinated side chains (MC7F3) shows down-shifted energy levels, reduced miscibility, and more importantly, improved backbone organization, thereby leading to the formation of a 3D network packing structure with enhanced carrier transport. Consequently, the MC7F3-based device exhibits a power conversion efficiency of 17.61% and an excellent fill factor of 79.48%, both of which are among the best values for all A-D-A-type NFAs reported so far. The results highlight that side-chain fluorination can efficiently enhance π-conjugated backbone organization, improve intermolecular interaction, increase electron mobilities, and boost photovoltaic performance of NFAs.

非富勒烯受体（NFAs）的侧链氟化可改善其骨架组织和载流子迁移率，但很少有报道称氟化可提高其光伏性能。在这里，我们设计了新的部分氟化侧链，并将其加入到 M 系列非富勒烯受体中，这种受体具有梯形杂七烯芯骨架，没有 sp3 杂化碳。与传统的带有非氟化侧链的 M 系列受体（MC7F0）相比，带有部分氟化侧链的 NFA（MC7F3）能级下移，混溶性降低，更重要的是骨架组织得到改善，从而形成了三维网络堆积结构，载流子传输能力增强。因此，基于 MC7F3 的器件显示出 17.61% 的功率转换效率和 79.48% 的出色填充因子，这两项指标都是迄今所报道的所有 A-D-A 型 NFA 的最佳值之一。研究结果表明，侧链氟化可有效增强π-共轭骨架组织，改善分子间相互作用，提高电子迁移率，从而提高 NFA 的光伏性能。

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引用次数: 0

Electroreduction of alkaline/natural seawater: Self-cleaning Pt/carbon cathode and on-site co-synthesis of H2 and Mg hydroxide nanoflakes 碱性/天然海水的电还原：自清洁铂/碳阴极和 H2 与氢氧化镁纳米片的现场共合成

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.018

Distributed coastal/offshore seawater splitting plants can facilitate H₂-based economy’s global deployment. Increasingly, studies emerge mostly focusing on inhibiting anodic oxidation of halide ions. Equally tricky cathodic precipitation in natural seawater reduction (NSR) is neglected due to the use of alkaline seawater in most studies. Herein, we explore possible strategies (introducing a proton sponge to change cathodic microenvironments, breaking local OH⁻ gradients, employing self-cleaning cathodes) to alleviate surface precipitation. We introduce a famous H₂ evolution-active metal, Pt, onto a self-cleaning carbon support with H₂ gas evacuation capability. Our proposed binder-free Pt/carbon cathode is more robust than many previous Pt/C cathodes for NSR. Moreover, we highlight possibilities of co-electrosynthesizing nano-sized Mg hydroxides and H₂ from natural seawater. This work suggests that designs of local environments, pH gradient disruption, and/or cathode architecture-based gas/liquid flows may suppress surface precipitation. We demonstrate in detail the various issues in NSR and possible solutions.

分布式沿海/近海海水分离厂可促进基于 H2 的经济在全球范围内的应用。越来越多的研究主要集中于抑制卤化离子的阳极氧化。同样，由于大多数研究都使用碱性海水，自然海水还原（NSR）中棘手的阴极沉淀问题也被忽视了。在此，我们探讨了减轻表面沉淀的可能策略（引入质子海绵以改变阴极微环境、打破局部 OH- 梯度、采用自清洁阴极）。我们将一种著名的具有 H2 演化活性的金属--铂--引入到具有 H2 气体排空能力的自清洁碳支持物中。我们提出的无粘结剂铂/碳阴极比以前许多用于 NSR 的铂/碳阴极更坚固。此外，我们还强调了从天然海水中共同电合成纳米级氢氧化镁和 H2 的可能性。这项工作表明，局部环境设计、pH 梯度破坏和/或基于阴极结构的气体/液体流动可以抑制表面沉淀。我们详细展示了 NSR 中的各种问题和可能的解决方案。

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引用次数: 0

Operando electrochemical NMR spectroscopy reveals a water-assisted formate formation mechanism 操作电化学核磁共振光谱揭示了水辅助甲酸盐形成机制

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.001

The affinity of oxygen (O)-bound species is a key factor in CO₂ reduction (CO₂R) reactions (including C₁ and C₂₊ products), although existing experimental methods cannot quantitatively track the O atoms active within CO₂R reactions in real time. Among the diversified products from CO₂R reactions, the formate (HCOO⁻) possesses the highest profit per mole of electrons. Here, we report an operando electrochemical nuclear magnetic resonance (NMR) method, which allows to quantitatively describe the complex species containing O atoms during the electrochemical CO₂R reactions. Based on Cu and bimetallic Cu-based materials (Bi₂CuO₄ and In₂Cu₂O₅) systems, we found that by introducing Bi and In metal adsorption sites, the O atoms of adsorbed H₂O can directly involve in the formation of HCOO⁻ through a water-assisted mechanism (∗COOH⁻ regeneration), thereby improving the selectivity of liquid HCOO⁻ product mostly from 34.2% to 98%. This strategy gives valuable insights into the design of HCOO⁻-favored catalysts.

与氧（O）结合的物种的亲和力是二氧化碳还原（CO2R）反应（包括 C1 和 C2+ 产物）中的一个关键因素，尽管现有的实验方法无法实时定量跟踪在 CO2R 反应中活跃的 O 原子。在 CO2R 反应的多种产物中，甲酸盐（HCOO-）每摩尔电子的利润最高。在此，我们报告了一种操作电化学核磁共振（NMR）方法，该方法可定量描述电化学 CO2R 反应过程中含有 O 原子的复杂物种。基于铜和双金属铜基材料（Bi2CuO4 和 In2Cu2O5）体系，我们发现通过引入 Bi 和 In 金属吸附位点，吸附 H2O 的 O 原子可通过水辅助机制（∗COOH- 再生）直接参与 HCOO- 的形成，从而将液态 HCOO- 产物的选择性从 34.2% 提高到 98%。这一策略为设计 HCOO 偏好催化剂提供了宝贵的启示。

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引用次数: 0

Elucidating the role of cathode identity: Voltage-dependent reversibility of anode-free batteries 阐明阴极特性的作用：无阳极电池的电压可逆性

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.008

The cathode material in a lithium (Li) battery determines the system cost, energy density, and thermal stability. In anode-free batteries, the cathode also serves as the source of Li for electrodeposition, thus impacting the reversibility of plating and stripping. Here, we show that the reason LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) cathodes deliver lower Coulombic efficiencies than LiFePO₄ (LFP) is the formation of tortuous Li deposits, acidic species in the electrolyte, and accumulation of “dead” Li⁰. Batteries containing an LFP cathode generate dense Li deposits that can be reversibly stripped, but Li is lost to the solid electrolyte interphase (SEI) and corrosion according to operando ⁷Li NMR, which seemingly “revives” dead Li⁰. X-ray photoelectron spectroscopy (XPS) and in situ ¹⁹F/¹H NMR indicate that these differences arise because upper cutoff voltage alters electrolyte decomposition, where low-voltage LFP cells prevent anodic decomposition, ultimately mitigating the formation of protic species that proliferate upon charging NMC811.

锂（Li）电池中的阴极材料决定了系统成本、能量密度和热稳定性。在无阳极电池中，阴极也是电沉积锂的来源，从而影响电镀和剥离的可逆性。在这里，我们发现 LiNi0.8Mn0.1Co0.1O2 (NMC811) 阴极的库仑效率低于 LiFePO4 (LFP)的原因是畸形锂沉积的形成、电解质中的酸性物质以及 "死 "锂的积累。含有 LFP 阴极的电池会产生可逆剥离的致密锂沉积物，但根据操作性 7Li NMR，锂会流失到固体电解质相间层（SEI）和腐蚀中，这似乎会 "复活 "死亡的 Li0。X 射线光电子能谱 (XPS) 和原位 19F/1H NMR 显示，出现这些差异的原因是上限截止电压改变了电解质分解，低电压 LFP 电池阻止了阳极分解，最终减轻了 NMC811 充电时增殖的原生物种的形成。

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引用次数: 0

Electrocatalytic reduction of nitrogen oxide species to ammonia 电催化氧化氮还原成氨

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.006

Huimin Liu , Lichen Bai , Arno Bergmann , Beatriz Roldan Cuenya , Jingshan Luo

The nitrogen cycle is one of the most important biochemical cycles. However, the development of human society has led to a substantial release of nitrogen oxide species, both as ions (NO_x⁻) and gases (NO_x), into the environment, causing a considerable burden on the natural denitrification processes. Electrocatalytic reduction of NO_x⁻ and NO_x emerges as a promising approach to transform these waste products into valuable ammonia, thereby contributing to the restoration of the nitrogen cycle. This review provides a concise overview of recent advances in electrocatalytic NO_x⁻ and NO_x reduction to ammonia, including detailed reaction mechanisms, catalyst development strategies based on both theoretical and experimental results, and the design and selection of electrolytic cells. Furthermore, it highlights key challenges associated with scaling up the reaction from laboratory-scale to practical industrial-scale application and explores potential opportunities to upgrade this reaction.

氮循环是最重要的生化循环之一。然而，人类社会的发展导致大量氮氧化物以离子（NOx-）和气体（NOx）的形式释放到环境中，给自然脱氮过程造成了相当大的负担。电催化还原氮氧化物和氮氧化物是一种很有前景的方法，可将这些废物转化为有价值的氨，从而促进氮循环的恢复。本综述简要概述了电催化一氧化氮和氮氧化物还原成氨的最新进展，包括详细的反应机理、基于理论和实验结果的催化剂开发策略，以及电解槽的设计和选择。此外，该书还强调了将该反应从实验室规模扩大到实际工业规模应用所面临的关键挑战，并探讨了升级该反应的潜在机会。

引用次数: 0

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