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Molecular low-oxidation-state chemistry with tetra-anionic group 14 elements 四阴离子基团14元素的分子低氧化态化学
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-03 DOI: 10.1038/s44160-026-01006-7
J. Maurer, J. Langer, J. Mai, M. A. Schmidt, C. Färber, L. Klerner, T. Vilpas, M. H. Linden, H. B. Linden, A. Koldemir, J. Wiethölter, R. Pöttgen, S. Harder
The group 14 tetrel elements carbon, silicon, germanium, tin and lead need to lose or gain four electrons to reach a stable full-valence shell. However, despite fulfilling the octet rule, tetra-anionic tetrels are highly reactive anions. The considerable 4− charge on single atoms dictates their chemistry, making such anions highly reducing, nucleophilic or strongly basic. Here we report facile full reduction of silicon, germanium, tin and lead precursors to tetra-anions using a molecular Mg0 complex at room temperature. These anions, which are stabilized by a crown consisting of metal cations and bridging ligands, are in the −IV oxidation state. They are found to be strong Brønsted bases and can react as quadruple nucleophiles or eight-electron reducing agents. This work extends the low-valent chemistry of tetrel complexes to its ultimate negative oxidation state.
14族四元元素碳、硅、锗、锡和铅需要失去或获得4个电子才能达到稳定的满价层。然而,尽管满足八隅体规则,四阴离子四隅体是高活性阴离子。单个原子上可观的4 -电荷决定了它们的化学性质,使这些阴离子具有高度还原性、亲核性或强碱性。在这里,我们报告了在室温下使用分子Mg0配合物容易地将硅,锗,锡和铅前体完全还原为四阴离子。这些阴离子由金属阳离子和桥接配体组成的冠状结构稳定,处于- IV氧化态。它们是强Brønsted碱,可以作为四重亲核试剂或八电子还原剂反应。这项工作将四萜配合物的低价化学扩展到其最终的负氧化态。
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引用次数: 0
Preparation of meta-cyclophanes via stereospecific ring-expansion rearrangement 立体定向扩环重排法制备间环烷
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-02 DOI: 10.1038/s44160-026-01016-5
Min Tan, Yongsheng Shen, Haohua Chen, Wenfu Yan, Dachuan Qiu, Yang Li
meta-Cyclophanes represent a ubiquitous and versatile structural motif in macrocycles. While conventional synthetic strategies predominantly rely on end-to-end cyclization, these methods are often hampered by unfavourable enthalpic and entropic constraints, and are limited to unstrained meta-cyclophanes. Here we present an aryne-mediated ring-expansion strategy based on sequential aryne insertion into the S=O bond of cyclic sulfoxides followed by an anionic [4,5]-sigmatropic rearrangement. A pivotal aspect of this strategy is the ability of the generated phenolate oxygen to redirect the rearrangement pathway from a [5,5]- to an anionic [4,5]-sigmatropic rearrangement. This methodology enables efficient access to strained meta-cyclophanes with diverse substitution patterns. Moreover, it not only supports the use of meta-cyclophane-based aryne precursors but also enables the orthogonal assembly of a secondary cyclophane ring on the antipodal face of the central benzene scaffold. Furthermore, a chirality transfer process is observed, underscoring the stereospecific nature of both the S=O bond insertion and the [4,5]-sigmatropic rearrangement steps.
元环是宏观环中普遍存在的多用途结构母题。虽然传统的合成策略主要依赖于端到端环化,但这些方法往往受到不利的焓和熵约束的阻碍,并且仅限于非张力的间环。在这里,我们提出了一种芳烷介导的扩环策略,该策略基于在环亚砜的S=O键中依次插入芳烷,然后进行阴离子[4,5]-异位重排。该策略的一个关键方面是生成的酚酸氧能够将重排途径从[5,5]-重定向到阴离子[4,5]-异位重排。这种方法可以有效地获得具有不同取代模式的张力间环烷。此外,它不仅支持使用基于间环烷的芳烃前体,而且使仲环在中心苯支架的对映面上的正交组装成为可能。此外,还观察到手性转移过程,强调了S=O键插入和[4,5]-符号重排步骤的立体特异性。
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引用次数: 0
Electrosynthesis of urea on cadmium-modified iron oxide 镉修饰氧化铁上电合成尿素
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-02 DOI: 10.1038/s44160-026-00995-9
Bihao Hu, Yan Liu, Yifan Zhou, Siming Yang, Zhihao Wang, Yi Shen Tew, Harshini Shankar, Xiaonan Wang, Pengfei Ou, Lei Wang
Electrosynthesis of urea at practical relevant current densities remains challenging due to competing side reactions, particularly at the elevated overpotentials required to sustain high currents. Here we propose a catalyst design strategy for selective urea production at practical current densities, emphasizing materials with low activity for competing CO2 reduction and hydrogen evolution, and high activity for nitrate activation under high overpotentials. We develop a cadmium-modified Fe2O3 (Cd–Fe2O3) catalyst composite, achieving a high urea partial current density of approximately 140 mA cm−2 at a modest cathodic potential of −0.5 V versus reversible hydrogen electrode, with an appreciable Faradaic efficiency of 52%. Through detailed kinetics analysis, in situ spectroscopic investigations and density functional theory calculations, we reveal that Cd incorporation into Fe2O3 substantially weakens *CO adsorption by altering the electronic structure and preserving oxidized Fe species. This modification suppresses undesired Volmer-type hydrogen adsorption while promoting *CO2NH2 intermediate protonation, enhancing urea formation. As a result, competing hydrogen evolution is effectively suppressed, and high urea selectivity is maintained at elevated current densities on Cd–Fe2O3.
在实际相关的电流密度下,由于相互竞争的副反应,特别是在维持高电流所需的高过电位下,尿素的电合成仍然具有挑战性。在此,我们提出了在实际电流密度下选择性尿素生产的催化剂设计策略,强调具有低活性的竞争CO2还原和析氢,以及高过电位下高活性的硝酸盐活化的材料。我们开发了一种镉修饰Fe2O3 (Cd-Fe2O3)催化剂复合材料,在- 0.5 V的适度阴极电位下,相对于可逆氢电极,实现了约140 mA cm - 2的高尿素分电流密度,具有可观的52%的法拉第效率。通过详细的动力学分析、原位光谱研究和密度泛函理论计算,我们发现Cd掺入Fe2O3中,通过改变电子结构和保留氧化的Fe物种,大大削弱了*CO的吸附。这种修饰抑制了不想要的volmer型氢吸附,同时促进了*CO2NH2中间质子化,增强了尿素的形成。结果,竞争析氢被有效抑制,并且在Cd-Fe2O3上的高电流密度下保持了高尿素选择性。
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引用次数: 0
Photoinduced nitrogen spillover enables ammonia synthesis on iron–aluminium dual-site catalysts 光诱导氮溢出使铁铝双址催化剂上的氨合成成为可能
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-02 DOI: 10.1038/s44160-026-01013-8
Wen-Qian Li, Yijian Chen, Xiaojun Lu, Hui Zhang, Zichuang Li, Kailong Qian, Bo Dai, Ruoqian Jiang, Sijia Zheng, Jiaqi Wang, Xianzheng Zhao, Yangfan Lu, Xiaoning Liu, Zhi Liu, Yanpeng Qi, Bin Zhang, Xin-Hao Li, Jie-Sheng Chen, Tian-Nan Ye
Despite the development of the Haber–Bosch process, ammonia synthesis under mild conditions remains challenging due to the high bond energy (945 kJ mol⁻1) of the N≡N triple bond. Both thermal- and photocatalytic processes often suffer from the intrinsic scaling relationship between N2 activation and NH3 desorption efficiencies. Here we report that the photocatalytic process over an AlFe nanoalloy catalyst provides a promising solution through a photoinduced nitrogen spillover reaction mechanism. Fe acts as the primary active site for N2 adsorption and dissociation. The transferred photoexcited electrons from Al to Fe enhance N2 activation. Al serves as a secondary active site, facilitating N spillover from Fe to Al sites under photoexcitation, promoting NH3 desorption. This dual-site strategy enables an ammonia synthesis rate of 8.6 mmol gcat−1 h−1 at 4.28 W cm−2 without additional thermal input under ambient pressure. The performance surpasses that of conventional industrial Fe catalysts under thermocatalytic conditions. This study proposes a photoassisted active site modulation strategy for efficient ammonia synthesis catalyst to circumvent scaling relationships.
尽管Haber-Bosch法得到了发展,但由于N≡N三键的高键能(945 kJ mol⁻1),在温和条件下合成氨仍然具有挑战性。热催化和光催化过程通常都受到N2活化和NH3脱附效率之间固有的标度关系的影响。在这里,我们报道了AlFe纳米合金催化剂上的光催化过程通过光诱导氮溢出反应机制提供了一个有前途的解决方案。Fe是N2吸附和解离的主要活性位点。从Al转移到Fe的光激发电子增强了N2的活化。Al作为二级活性位点,在光激发下促进N从Fe位点向Al位点溢出,促进NH3的脱附。这种双位点策略使氨合成速率为8.6 mmol gcat−1 h−1,温度为4.28 W cm−2,在环境压力下无需额外的热输入。在热催化条件下,性能优于传统工业铁催化剂。本研究提出了一种光辅助活性位点调制策略,用于有效的氨合成催化剂,以避免结垢关系。
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引用次数: 0
A water-based solid-phase peptide synthesis 一种水基固相肽合成方法
IF 2 0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-27 DOI: 10.1038/s44160-026-01029-0
Bei Zhang
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引用次数: 0
Engineering non-haem enzymes for nickel-catalysed C(sp2)‒S coupling via ligand-to-metal charge transfer photocatalysis 通过配体-金属电荷转移光催化实现镍催化C(sp2) -S偶联的工程非血红素酶
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-27 DOI: 10.1038/s44160-026-01003-w
Xiuze Wang, Xianhai Tian, Xiahe Chen, Guoxiong Xu, Jared C. Paris, Yuqi Song, Yuxuan Su, James G. Zhang, Xin Hong, Marc Garcia-Borràs, Arthur E. Bragg, Yisong Guo, Yunfang Yang, Xiongyi Huang
Integrating metal-catalysed transformations into enzymes is a key objective in biocatalysis. This study uses a photoinduced ligand-to-metal charge transfer strategy to enable abiotic cross-coupling reactions in metalloenzymes. By tailoring the primary coordination sphere to establish a 2-histidine metal-binding site and replacing the iron centre with nickel, the ethylene-forming enzyme from Pseudomonas savastanoi (PsEFE) was activated for nickel-catalysed C(sp2)‒S cross-coupling between aryl bromides and thiols. Directed evolution of PsEFE produced variants capable of generating a range of thioether products in up to 98% yield and 530 total turnover numbers. Mechanistic investigations suggest that this photoenzymatic reaction involves a Ni(II)/Ni(I)/Ni(III) catalytic cycle with generation of a reactive Ni(I) species and thiyl radical via photoinduced ligand-to-metal charge transfer. We anticipate that these findings will inspire further exploration of integrating abiotic cross-coupling transformations into enzymatic catalysis.
将金属催化转化转化为酶是生物催化的一个关键目标。本研究利用光诱导配体到金属的电荷转移策略来实现金属酶的非生物交叉偶联反应。通过调整初级配位球以建立2-组氨酸金属结合位点,并用镍取代铁中心,激活来自savastanoi假单胞菌(Pseudomonas savastanoi)的乙烯形成酶(PsEFE),使其在镍催化下进行芳基溴和硫醇之间的C(sp2) -S交叉偶联。PsEFE的定向进化产生的变体能够产生一系列的硫醚产品,收率高达98%,总周转率为530。机理研究表明,该光酶反应涉及Ni(II)/Ni(I)/Ni(III)催化循环,并通过光诱导配体到金属的电荷转移产生活性Ni(I)和巯基自由基。我们预计这些发现将激发进一步探索整合非生物交叉偶联转化到酶催化。
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引用次数: 0
Crystal-solvate pre-seeded synthesis for scalable perovskite solar cell fabrication 可扩展钙钛矿太阳能电池制备的晶体溶剂化物预播种合成
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-27 DOI: 10.1038/s44160-026-00993-x
Xiuhong Sun, Mingwei Hao, Kaiyu Wang, Kuan Wang, Yalan Zhang, Bingqian Zhang, Xuexuan Huang, Chenghao Bi, Shuping Pang, Yuanyuan Zhou
Buried morphological and electronic defects of solution-synthesized perovskite films are detrimental to the photovoltaic stability and performance of state-of-the-art inverted perovskite solar cells based on self-assembled monolayers (SAMs). Previous studies have attempted to alleviate this synthesis issue by molecular tailoring of SAMs. Here we use pre-seeding of low-dimensional halide crystal solvates (CSVs) to trigger the formation of perovskite film bottoms with suppressed morphological and electronic defects. CSVs enable nanostructure-guided wetting of the perovskite precursor solution on SAMs and unlock lattice-confined solvent annealing of the perovskite film bottom, mitigating interfacial voids and nanogrooves. This method also leads to CSV-derived halide compound passivation at the film bottom, reducing electronic defects and enabling hole-extraction-favouring interfacial energetics. The sequential multi-functionality enabled by CSV pre-seeding surpasses the nucleation control in conventional seeding strategies. Resultant inverted perovskite solar cells deliver a power conversion efficiency of 26.13% with a high fill factor of 86.75%. These devices demonstrate improved light and thermal stabilities under ISOS-L-1 and ISOS-T-1 test protocols. The scalability of CSV pre-seeding is demonstrated with 23.15% power conversion efficiency achieved for a 49.91 cm2 perovskite solar mini-module.
溶液合成钙钛矿薄膜中埋藏的形态缺陷和电子缺陷严重影响了自组装单层(SAMs)倒钙钛矿太阳能电池的光伏稳定性和性能。以前的研究试图通过分子裁剪来缓解这种合成问题。在这里,我们使用低维卤化物晶体溶剂化物(CSVs)的预播种来触发钙钛矿薄膜底部的形成,并抑制形貌和电子缺陷。csv使钙钛矿前驱体溶液在sam上的纳米结构导向润湿,解开钙钛矿薄膜底部的晶格限制溶剂退火,减轻界面空洞和纳米沟槽。该方法还导致csv衍生的卤化物化合物在薄膜底部钝化,减少电子缺陷并实现有利于空穴提取的界面热力学。CSV预播种的顺序多功能性超越了传统播种策略中的成核控制。所得倒置钙钛矿太阳能电池的功率转换效率为26.13%,填充系数高达86.75%。这些器件在iso - l -1和iso - t -1测试协议下表现出更好的光稳定性和热稳定性。在49.91 cm2的钙钛矿太阳能微型组件上实现了23.15%的功率转换效率,证明了CSV预播种的可扩展性。
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引用次数: 0
Click-locking strategy enables automated synthesis of single-atom catalysts with industrial compatibility 点击锁定策略使自动化合成具有工业兼容性的单原子催化剂
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-27 DOI: 10.1038/s44160-026-01004-9
Weibin Chen, Long Feng, Bingbing Ma, Lina Zhang, Zhou Du, Fanqi Meng, Shengyao Wang, Shibo Xi, Xiao Hai, Ruiqin Zhong, Jin Zhang, Jiong Lu, Ju Li, Ruqiang Zou
Developing scalable methods to synthesize single-atom catalysts (SACs) while maintaining high stability and activity remains a substantial challenge. Here, inspired by click chemistry, we propose a click-locking strategy that utilizes clicking auxiliaries to enable the synthesis of SACs. These clicking auxiliaries function as molecular ‘click-locking seat belts’, ensuring precise atomic anchoring, optimizing electronic structures and enhancing stability, while minimizing raw material loss. By integrating a robotic platform, we achieve high-throughput synthesis, generating extensive libraries of clicking-SACs and enabling rapid performance evaluation. This approach greatly accelerates the discovery of high-performance catalysts for electrocatalytic, photocatalytic and thermocatalytic processes. Furthermore, we demonstrate the kilogram-scale production of clicking-SACs, achieving exceptional catalytic activity and long-term stability. Extensive upscaling and stability tests validate the broad applicability and reliability of clicking-SACs, underscoring their potential as a transformative strategy in industrial catalysis.
开发可扩展的方法合成单原子催化剂(SACs),同时保持高稳定性和活性仍然是一个重大挑战。在这里,受点击化学的启发,我们提出了一种点击锁定策略,利用点击助剂来合成SACs。这些点击助剂的功能就像分子的“点击锁定安全带”,确保精确的原子锚定,优化电子结构并增强稳定性,同时最大限度地减少原材料损失。通过集成机器人平台,我们实现了高通量合成,生成了广泛的点击sac库,并实现了快速的性能评估。这种方法极大地加速了电催化、光催化和热催化过程中高性能催化剂的发现。此外,我们展示了公斤级的点击sacs生产,实现了卓越的催化活性和长期稳定性。广泛的升级和稳定性测试验证了点击sac的广泛适用性和可靠性,强调了它们作为工业催化变革战略的潜力。
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引用次数: 0
Arylhydrazine reductants for cross-coupling 交联用芳酰肼还原剂
IF 2 0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-25 DOI: 10.1038/s44160-026-01028-1
Peter W. Seavill
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引用次数: 0
Divergent housane synthesis via intramolecular [2 + 2] cycloaddition of 1,4-dienes 1,4-二烯分子内[2 + 2]环加成合成发散型房甾烷
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-19 DOI: 10.1038/s44160-026-00997-7
Fuhao Zhang, Julius Domack, Niklas Hölter, Constantin G. Daniliuc, Frank Glorius
{"title":"Divergent housane synthesis via intramolecular [2 + 2] cycloaddition of 1,4-dienes","authors":"Fuhao Zhang, Julius Domack, Niklas Hölter, Constantin G. Daniliuc, Frank Glorius","doi":"10.1038/s44160-026-00997-7","DOIUrl":"https://doi.org/10.1038/s44160-026-00997-7","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"322 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Nature synthesis
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