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Artificial synthesis of carbohydrates from electrochemically fixed carbon dioxide 由电化学固定二氧化碳人工合成碳水化合物
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-02 DOI: 10.1038/s44160-025-00961-x
Jing Li, Kedang Chen, Nathan E. Soland, Jindou Yang, Yuanzuo Gao, Seonjeong Cheon, Yuming Su, Peidong Yang, Hailiang Wang
Sustainable synthesis of C5+ carbohydrates from CO2 remains challenging due to the complexity of controlled CO2 reduction and carbon–carbon coupling. Biochemical approaches can convert primary CO2 reduction products into C5+ carbohydrates, but are often constrained by lengthy reaction periods, low production rates and system complexity. Here we present a two-step electrochemical reduction–formose reaction method that uses hydroxymethanesulfonate (HMS) as a more stable surrogate for formaldehyde to facilitate the direct synthesis of C5+ carbohydrates from electrochemically fixed CO2. Using cobalt tetraaminophthalocyanine molecules supported on multiwalled carbon nanotubes as an electrocatalyst, we achieve an HMS Faradaic efficiency of ~12% at a total current density of 150 mA cm−2. Employing direct CO reduction increases the Faradaic efficiency to ~25% with over 63% carbon efficiency. The produced HMS enables an efficient formose reaction under mild conditions reaching a yield of 20.4% for C5+ carbohydrates. The CO2-derived HMS also demonstrates its versatility as a formaldehyde surrogate in other reactions for synthesizing various valuable chemical products, promising a new approach for feeding advanced chemical synthesis with electrochemically fixed CO2 via the intercepted formaldehyde intermediate.
由于可控CO2还原和碳-碳耦合的复杂性,从CO2中可持续合成C5+碳水化合物仍然具有挑战性。生物化学方法可以将初级CO2还原产物转化为C5+碳水化合物,但往往受到反应周期长、生产率低和系统复杂性的限制。本文提出了一种两步电化学还原-福尔摩斯反应方法,该方法使用羟基甲烷磺酸盐(HMS)作为更稳定的甲醛替代物,促进了由电化学固定CO2直接合成C5+碳水化合物。利用负载在多壁碳纳米管上的四氨基酞菁钴分子作为电催化剂,在总电流密度为150 mA cm−2时,我们实现了约12%的HMS法拉第效率。采用直接CO还原法可使法拉第效率提高到25%,碳效率超过63%。所制备的HMS能在温和条件下对C5+碳水化合物进行高效的福尔斯反应,产率达20.4%。二氧化碳衍生的HMS还证明了其作为甲醛替代品的多功能性,可以在其他反应中合成各种有价值的化学产品,这为通过截获的甲醛中间体进行电化学固定CO2的高级化学合成提供了新的途径。
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引用次数: 0
Synthesis of discrete oligoethylenes towards chemically recyclable polyolefins 用化学可回收聚烯烃合成离散型低聚乙烯
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-02 DOI: 10.1038/s44160-025-00955-9
Rui Tan, Yanru An, Yuxin Liu, Xiaojie Yang, Qinmeng Zhong, Xinyue Yan, Yuxiao Hu, Minglong Chen, Jie Cen, Xiaoman Huang, Gefei Wang, Jinming Hu, Shiyong Liu, Zhengbiao Zhang
Polyethylene-like materials consist of long-chain oligoethylene blocks and chemically cleavable linkages, providing a promising alternative to chemically inert polyethylene while retaining comparable properties. Larger and uniform chain lengths of oligoethylene blocks are preferred to retain polyethylene crystallinity; however, the efficient synthesis of uniform ultralong oligoethylenes with guaranteed purity remains challenging. Here we report the precision synthesis of uniform oligoethylenes of up to 576 carbon atoms based on the Julia–Kocienski reaction. Using these as building blocks, a series of high-density polyethylene-like materials with regularly distributed ester linkages were developed. The oligoethylene with 126 carbon atoms readily affords remarkable thermal (Tm ≈ 130 °C) and mechanical properties. Due to the uniformity of oligoethylene blocks, closed-loop chemical recyclability of high-density polyethylene-like materials is possible for at least five cycles, excluding compositional heterogeneity and batch-to-batch fluctuation. Our strategy for constructing uniform oligoethylenes with exceptionally high chain lengths is interesting for new-generation recyclable materials.
类聚乙烯材料由长链聚乙烯块和化学上可切割的键组成,为化学惰性聚乙烯提供了一种有希望的替代品,同时保持了相当的性能。为了保持聚乙烯结晶度,更大和均匀的链长的聚乙烯块是优选的;然而,保证纯度的均匀超长低聚乙烯的高效合成仍然具有挑战性。本文报道了基于Julia-Kocienski反应精确合成了576个碳原子的均匀聚乙烯。以此为基础,开发了一系列具有规则分布的酯键的高密度类聚乙烯材料。具有126个碳原子的聚乙烯具有优异的热(Tm≈130°C)和机械性能。由于聚乙烯块的均匀性,高密度聚乙烯类材料的闭环化学可回收性至少在五个循环中是可能的,不包括成分的不均匀性和批次间的波动。对于新一代可回收材料来说,我们构建具有极高链长的均匀聚乙烯的策略非常有趣。
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引用次数: 0
Synthesis of goldene comprising single-atom layer gold 含单原子层金的金的合成
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-02 DOI: 10.1038/s44160-025-00959-5
Sudhir Kumar Sharma, Ramesh Jagannathan
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引用次数: 0
Reply to: Synthesis of goldene comprising single-atom layer gold 回复:含单原子层金的金的合成
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-02 DOI: 10.1038/s44160-025-00960-y
Shun Kashiwaya, Yuchen Shi, Jun Lu, Davide G. Sangiovanni, Grzegorz Greczynski, Martin Magnuson, Mike Andersson, Johanna Rosen, Lars Hultman
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引用次数: 0
Divergent synthesis of N heterocycles from carbocycles enabled by electrochemical nitrogen atom insertion 电化学氮原子插入使碳环发散合成N杂环成为可能
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-18 DOI: 10.1038/s44160-025-00945-x
Guo-Quan Sun, Xiyan Wang, Rui Hu, Weidong Rao, Yu Zhao, Ming Joo Koh
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引用次数: 0
Alkyl sulfonyl fluorides as ambiphiles in the stereoselective palladium(II)-catalysed cyclopropanation of unactivated alkenes 烷基磺酰氟在立体选择性钯(II)催化非活化烯烃环丙烷化反应中的两性亲和作用
IF 2 0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-16 DOI: 10.1038/s44160-025-00925-1
Yilin Cao, Warabhorn Rodphon, Turki M. Alturaifi, Al Vicente Riano D. Lisboa, Zhouyang Ren, Job J. C. Struijs, Hui-Qi Ni, Taras Savchuk, Richard P. Loach, Shouliang Yang, Indrawan J. McAlpine, Donna G. Blackmond, Pavel K. Mykhailiuk, Peng Liu, K. Barry Sharpless, Keary M. Engle
Here we present the ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis of diverse cyclopropanes from olefins, under palladium(II) catalysis. The sulfonyl fluoride functionality serves as both an acidifying group and an internal oxidant within the ambiphile, enabling successive carbopalladation and oxidative addition steps in the catalytic cycle, respectively. The transformation grants access to cis-substituted cyclopropanes and exhibits broad compatibility with various alkyl sulfonyl fluorides, including those bearing –CN, –CO2R, isoxazolyl, pyrazolyl and aryl groups. With internal alkene substrates, 1,2,3-trisubstituted cyclopropanes that are otherwise challenging to synthesize are formed in good-to-moderate yields and predictable diastereoselectivity. Detailed mechanistic insights from reaction progress kinetic analysis and density functional theory calculations reveal that the SN2-type C–SO2F oxidative addition is the turnover-limiting and diastereoselectivity-determining step. The ambiphilic reactivity of alkyl sulfonyl fluorides in stereoselective cyclopropanation under Pd(II) catalysis is reported. The method provides convenient access to cis-disubstituted cyclopropanes that are otherwise challenging to access. A representative carboxylic acid cyclopropane building block is scaled up to 100 mmol, demonstrating the practicality of this transformation.
本文报道了在钯(II)催化下,烷基磺酰氟化合物在烯烃立体选择性合成多种环丙烷过程中的亲和性。磺酰氟的功能在两亲性化合物中充当酸化基团和内部氧化剂,分别在催化循环中实现连续的碳化和氧化加成步骤。这种转化可以得到顺式取代的环丙烷,并与各种烷基磺酰氟化合物表现出广泛的相容性,包括那些含有-CN、- co2r、异恶唑、吡唑和芳基的化合物。在烯烃内底物的作用下,1,2,3-三取代环丙烷以良好到中等的产率和可预测的非对映选择性形成。通过对反应过程的动力学分析和密度泛函理论计算,揭示了sn2型c - so2f氧化加成是限制转化率和非对选性的步骤。
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引用次数: 0
Scalable ultrathin sodium metal anodes 可伸缩的超薄金属钠阳极
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-10 DOI: 10.1038/s44160-025-00934-0
Mengyao Tang, Shuai Dong, Ke Yue, Jinhui Zhao, Weiping Li, Xuefeng Wang, Peng Chen, Ruizhi Liu, Rui Wen, Shuangyu Song, Yujing Liu, Jianwei Nai, Jiawei Wang, Qiaonan Zhu, Liwei Cheng, Hao Lan, Liqiang Wu, Bin Zhou, Daojun Yang, Xinyong Tao, Lin Guo, Hua Wang
Sodium-ion batteries have been attracting extensive attention in both academic and industrial fields. However, the lack of large-area and ultrathin sodium (Na) metal foil hinders basic research on and commercialization of energy-dense Na-ion batteries. Here we successfully fabricated a metre-length, ultrathin (≤50 μm), mechanically strengthened Na metal foil by a roll-to-roll calendaring process with interfacial lubrication and functional modification. By developing self-lubricating polydimethylsiloxane as the multifunctional agent, the poor processibility of metallic Na is addressed by forming a mechanically strong interface as well as a surface lubricant film during rolling. Furthermore, polydimethylsiloxane-derived (Si–O)n-Na interphases can guide Na+-ion interfacial diffusion and enable a robust solid electrolyte interphase. Consequently, the large-area ultrathin Na foil exhibits a stable electrode potential and stripping capacity, as well as prolonged lifespan compared with bare Na anodes. This approach enables the realization of amp-hour-level Na metal pouch cells under a low negative-to-positive capacity ratio of 1.9, showing an energy density of 180.2 Wh kg−1. This scalable ultrathin Na foil establishes a materials foundation for fundamental studies on Na-ion batteries and the potential manufacture of high-energy-density Na metal batteries.
钠离子电池已经引起了学术界和工业界的广泛关注。然而,大面积超薄钠(Na)金属箔的缺乏阻碍了高能量钠离子电池的基础研究和商业化。本研究成功制备了一种具有界面润滑和功能修饰的超薄(≤50 μm)机械强化Na金属箔。通过开发自润滑聚二甲基硅氧烷作为多功能剂,解决了金属Na在轧制过程中形成机械强界面和表面润滑膜的可加工性差的问题。此外,聚二甲基硅氧烷衍生的(Si-O)n-Na界面可以引导Na+离子界面扩散,并形成坚固的固体电解质界面。因此,与裸钠阳极相比,大面积超薄钠箔具有稳定的电极电位和剥离能力,并且寿命更长。这种方法可以实现安培小时级的Na金属袋状电池,其负正容量比为1.9,能量密度为180.2 Wh kg−1。这种可扩展的超薄钠箔为钠离子电池的基础研究和高能量密度钠金属电池的潜在制造奠定了材料基础。
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引用次数: 0
Heck-type reactions with bismuth photocatalysts 与铋光催化剂的heck型反应
IF 2 0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-09 DOI: 10.1038/s44160-025-00962-w
Eric J. Piechota
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引用次数: 0
Mechanochemical synthesis of organosodium compounds through direct sodiation of organic halides 有机卤化物直接钠化合成有机钠化合物的机械化学方法
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-08 DOI: 10.1038/s44160-025-00949-7
Keisuke Kondo, Matthew Lowe, Nathan Davison, Paul G. Waddell, Roly J. Armstrong, Erli Lu, Koji Kubota, Hajime Ito
Organometallic reagents are essential in organic synthesis, with organolithium compounds being most widely used. However, as lithium becomes less abundant and increasingly expensive, organosodium compounds have emerged as promising alternatives, but their use in organic synthesis is limited by their poor solubility in organic solvents, the need for pre-activated sodium sources and the necessity for highly anhydrous conditions. Here we report a mechanochemical protocol for the direct generation of organosodium compounds from cheap and shelf-stable sodium lumps and readily available organic halides under bulk, solvent-free conditions. These reactions generate an array of organosodium compounds in minutes, without special precautions against moisture or temperature control. These nucleophiles can be used directly for one-pot nucleophilic addition reactions with electrophiles and nickel-catalysed cross-coupling reactions. Furthermore, this mechanochemical approach enables the sodiation of inert C–F bonds in organic fluorides. This method is anticipated to drive progress in sodium-based synthetic chemistry.
有机金属试剂在有机合成中是必不可少的,其中有机锂化合物的应用最为广泛。然而,随着锂的储量越来越少,价格越来越贵,有机钠化合物已经成为有前途的替代品,但它们在有机合成中的应用受到限制,因为它们在有机溶剂中的溶解度差,需要预活化的钠源,并且必须在高度无水的条件下使用。在这里,我们报告了一种在散装,无溶剂条件下,从廉价且货架稳定的钠块和易得的有机卤化物直接生成有机钠化合物的机械化学方案。这些反应在几分钟内产生一系列有机钠化合物,不需要特别的防潮或温度控制措施。这些亲核试剂可直接用于与亲电试剂的一锅亲核加成反应和镍催化的交叉偶联反应。此外,这种机械化学方法使有机氟化物中惰性C-F键的碱化成为可能。这种方法有望推动钠基合成化学的发展。
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引用次数: 0
Laser-assisted materials engineering at the atomic and nanoscales 原子和纳米尺度的激光辅助材料工程
IF 2 0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-05 DOI: 10.1038/s44160-025-00936-y
Weihua Guo, Zihao Li, Libei Huang, Ma Qian, James M. Tour, Ruquan Ye
Laser technology has revolutionized industrial manufacturing by offering localized high energy, precise spatial resolution and seamless automation. Compared with traditional thermal processes, laser-assisted manufacturing integrates materials synthesis and structural design, thereby reducing waste and enhancing productivity. The rapid kinetics and transient behaviour of laser processes enable control over phase transitions, heterostructure design, defect engineering, nucleation, compositional variations, recrystallization and amorphization, producing materials with interesting properties. Here we examine atomic- and nanoscale control in laser-assisted materials manufacturing. We discuss the laser processing synthesis and resultant properties of materials including metals, perovskites, graphene and other inorganic materials. The efficacy of atomic- and nanoscale modulation by laser processing is demonstrated by improved performance in diverse domains, including catalysis, mechanical reinforcement, electronics or optoelectronics, and drug screening. By emphasizing atomic-scale perspectives, this Review offers understanding of laser-assisted materials manufacturing while inspiring materials development. Laser technology offers high energy, precise spatial resolution and seamless automation for materials synthesis and device fabrication. This Review highlights laser-assisted materials engineering at the atomic and nanoscales and examines the laser-assisted discovery of materials with interesting properties and applications.
激光技术通过提供本地化的高能量、精确的空间分辨率和无缝自动化,彻底改变了工业制造。与传统的热工艺相比,激光辅助制造集成了材料合成和结构设计,从而减少了浪费,提高了生产率。激光过程的快速动力学和瞬态行为可以控制相变、异质结构设计、缺陷工程、成核、成分变化、再结晶和非晶化,从而生产出具有有趣性能的材料。在这里,我们研究了激光辅助材料制造中的原子和纳米级控制。讨论了金属、钙钛矿、石墨烯等无机材料的激光加工合成及其性能。通过激光处理的原子和纳米级调制的有效性通过在催化,机械增强,电子或光电子以及药物筛选等多个领域的改进性能得到证明。通过强调原子尺度的观点,本综述提供了对激光辅助材料制造的理解,同时启发了材料的发展。激光技术为材料合成和器件制造提供了高能量、精确的空间分辨率和无缝自动化。本文重点介绍了原子和纳米尺度的激光辅助材料工程,并探讨了激光辅助发现具有有趣性质和应用的材料。
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引用次数: 0
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Nature synthesis
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