Ruiliang Gao, Shanjun Mao, Bing Lu, Wencong Liu, Yong Wang
The upcycling of waste polyolefins into light aromatics has great potential to generate hundreds of millions of tons of valuable aromatic carbon feedstock. However, the conventional high-temperature radical cracking method for aromatizing polyolefins on zeolites faces challenges in aromaticity control and rapid deactivation due to coke. Here, we present a unique strategy that integrates traditional cracking-aromatization process of PE with CO insertion, a key step of Fischer–Tropsch synthesis, achieving a rise of yield of light aromatics by 4 times, with an absolute value up to 67% by weight at only 280 °C. The insertion of CO into the Ru-alkyl intermediates formed during polyolefin cracking facilitates the generation of active oxygenate species, guarantees an ideal C-C chain length range, and smoothing the way for subsequent efficient aromatization on Hol-ZSM-5@S1 with a short b-axis. According to the technical economic analysis, this low-carbon-footprint and economic approach can reduce approximately 1/3 of carbon emissions compared to traditional naphtha cracking technologies, and holds promise for reshaping the global aromatic hydrocarbon cycle of petrochemical industry through polyolefin degradation.
{"title":"Efficient Upcycling of Polyolefin Waste to Light Aromatics via Coupling C-C Scission and Carbonylation","authors":"Ruiliang Gao, Shanjun Mao, Bing Lu, Wencong Liu, Yong Wang","doi":"10.1002/anie.202424334","DOIUrl":"https://doi.org/10.1002/anie.202424334","url":null,"abstract":"The upcycling of waste polyolefins into light aromatics has great potential to generate hundreds of millions of tons of valuable aromatic carbon feedstock. However, the conventional high-temperature radical cracking method for aromatizing polyolefins on zeolites faces challenges in aromaticity control and rapid deactivation due to coke. Here, we present a unique strategy that integrates traditional cracking-aromatization process of PE with CO insertion, a key step of Fischer–Tropsch synthesis, achieving a rise of yield of light aromatics by 4 times, with an absolute value up to 67% by weight at only 280 °C. The insertion of CO into the Ru-alkyl intermediates formed during polyolefin cracking facilitates the generation of active oxygenate species, guarantees an ideal C-C chain length range, and smoothing the way for subsequent efficient aromatization on Hol-ZSM-5@S1 with a short b-axis. According to the technical economic analysis, this low-carbon-footprint and economic approach can reduce approximately 1/3 of carbon emissions compared to traditional naphtha cracking technologies, and holds promise for reshaping the global aromatic hydrocarbon cycle of petrochemical industry through polyolefin degradation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
David Dellemme, Sinan Kardas, Corentin Tonneaux, Julien Lernould, Mathieu Fossépré, Mathieu Surin
Inspired by the exquisite properties emerging from the sequence order in nucleic acids and proteins, researchers are increasingly considering synthetic sequence-defined macromolecules (SDMs) to reach precise functions, e.g. for catalysis, data storage, energy, and health. While researchers develop iterative techniques permitting the synthesis of perfectly defined sequences, there is still an important gap to achieve the desired properties leading to their utilization as materials. This arises from the fact that the effect of the sequence order on the 3D structure is unknown for most synthetic SDMs. While the Protein Data Bank gathers hundreds of thousands of elucidated 3D structures, and many more computed (using e.g. AlphaFold), extended information on sequence-structure relationships do not exist yet for synthetic SDMs. To tackle this problem for relatively flexible macromolecules, one can nowadays utilize the existing tools of molecular modeling. In this Review, we report advanced practices to reveal the 3D structures and the interactions, through the combination of molecular dynamics simulations and network analysis applied to different SDMs. By combining the computational results to the experimental ones, we show the potential of this approach for understanding sequence-structure-property relationships in discrete macromolecular systems, towards guiding their rational design for specific functions.
{"title":"From sequence definition to structure-property relationships in discrete synthetic macromolecules: insights from molecular modeling","authors":"David Dellemme, Sinan Kardas, Corentin Tonneaux, Julien Lernould, Mathieu Fossépré, Mathieu Surin","doi":"10.1002/anie.202420179","DOIUrl":"https://doi.org/10.1002/anie.202420179","url":null,"abstract":"Inspired by the exquisite properties emerging from the sequence order in nucleic acids and proteins, researchers are increasingly considering synthetic sequence-defined macromolecules (SDMs) to reach precise functions, e.g. for catalysis, data storage, energy, and health. While researchers develop iterative techniques permitting the synthesis of perfectly defined sequences, there is still an important gap to achieve the desired properties leading to their utilization as materials. This arises from the fact that the effect of the sequence order on the 3D structure is unknown for most synthetic SDMs. While the Protein Data Bank gathers hundreds of thousands of elucidated 3D structures, and many more computed (using e.g. AlphaFold), extended information on sequence-structure relationships do not exist yet for synthetic SDMs. To tackle this problem for relatively flexible macromolecules, one can nowadays utilize the existing tools of molecular modeling. In this Review, we report advanced practices to reveal the 3D structures and the interactions, through the combination of molecular dynamics simulations and network analysis applied to different SDMs. By combining the computational results to the experimental ones, we show the potential of this approach for understanding sequence-structure-property relationships in discrete macromolecular systems, towards guiding their rational design for specific functions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiucheng Xu, Bjørt Óladóttir Joensen, Nishithan C. Kani, Andrea Sartori, Terry Wilson, John R. Varcoe, Luca Riillo, Anna Ramunni, Jakub Drnec, Ib Chorkendorff, Brian Seger
Membrane-electrode assembly (MEA)-based CO electrolysis (COE) has demonstrated the capability to produce C2+ products with high faradaic efficiency at ampere-level current densities. However, most studies on COE have achieved performance benchmarks under strongly alkaline conditions (e.g., ≥1 M KOH, pH ≥ 14), raising the question of whether such high pH levels are essential for optimal performance. In this study, we investigated the effects of different electrolytes (KHCO3, K2CO3, and KOH) on MEA-based CO electrolysis, focusing on the influence of pH and the impact of anodic oxidation on the selectivity of various liquid products. By adjusting electrolyte concentration and pH, we achieved significant partial current densities for ethanol (189 ± 5 mA cm-2) and propanol (89 ± 4 mA cm-2) using 0.5 M K2CO3. This high performance is attributed to the creation of a moderate local alkaline environment and the relatively high resistance to anodic oxidation. Additionally, durability measurements emphasized the critical importance of eliminating anodic oxidation to optimize MEA-based COE for ethanol and propanol production.
{"title":"Electrolyte Effects in Membrane-Electrode-Assembly CO Electrolysis","authors":"Qiucheng Xu, Bjørt Óladóttir Joensen, Nishithan C. Kani, Andrea Sartori, Terry Wilson, John R. Varcoe, Luca Riillo, Anna Ramunni, Jakub Drnec, Ib Chorkendorff, Brian Seger","doi":"10.1002/anie.202501505","DOIUrl":"https://doi.org/10.1002/anie.202501505","url":null,"abstract":"Membrane-electrode assembly (MEA)-based CO electrolysis (COE) has demonstrated the capability to produce C2+ products with high faradaic efficiency at ampere-level current densities. However, most studies on COE have achieved performance benchmarks under strongly alkaline conditions (e.g., ≥1 M KOH, pH ≥ 14), raising the question of whether such high pH levels are essential for optimal performance. In this study, we investigated the effects of different electrolytes (KHCO3, K2CO3, and KOH) on MEA-based CO electrolysis, focusing on the influence of pH and the impact of anodic oxidation on the selectivity of various liquid products. By adjusting electrolyte concentration and pH, we achieved significant partial current densities for ethanol (189 ± 5 mA cm-2) and propanol (89 ± 4 mA cm-2) using 0.5 M K2CO3. This high performance is attributed to the creation of a moderate local alkaline environment and the relatively high resistance to anodic oxidation. Additionally, durability measurements emphasized the critical importance of eliminating anodic oxidation to optimize MEA-based COE for ethanol and propanol production.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"91 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical reforming presents a sustainable route for the conversion of nitrate (NO3-) and polyethylene terephthalate (PET) into value-added chemicals, such as ammonia (NH3) and formic acid (HCOOH). However, its widespread application has been constrained by low selectivity due to the complexity of reduction processes and thus energy scaling limitations. In this study, the atomically dispersed Ru sites in Co3O4 synergistically interact with Co centers, facilitating the adsorption and activation of hydroxyl radicals (OH*) and ethylene glycol (EG), resulting in a remarkable HCOOH selectivity of 99 % and a yield rate of 11.2 mmol h-1 cm-2 surpassing that of pristine Co3O4 (55 % and 3.8 mmol h-1 cm-2). Furthermore, when applied as a bifunctional cathode catalyst, Ru-Co3O4 achieves a remarkable Faradaic efficiency (FE) of 98.5 % for NH3 production (3.54 mmol h-1 cm-2) at -0.3 V vs. RHE. Additionally, we developed a prototype device powered by a commercial silicon photovoltaic cell, enabling on-site solar-driven production of formate and NH3 through enzyme-catalyzed PET and NO3- conversion. This study offers a viable approach for waste valorization and green chemical production, paving the way for sustainable energy applications.
{"title":"Efficient Electrochemical-Enzymatic Conversion of PET to Formate Coupled with Nitrate Reduction over Ru-Doped Co3O4 Catalysts","authors":"Jiadi Jiang, Leting Zhang, Guanzheng Wu, Jianrui Zhang, Yidong Yang, Wenhui He, Jun Zhu, Jian Zhang, Qing Qin","doi":"10.1002/anie.202421240","DOIUrl":"https://doi.org/10.1002/anie.202421240","url":null,"abstract":"Electrochemical reforming presents a sustainable route for the conversion of nitrate (NO3-) and polyethylene terephthalate (PET) into value-added chemicals, such as ammonia (NH3) and formic acid (HCOOH). However, its widespread application has been constrained by low selectivity due to the complexity of reduction processes and thus energy scaling limitations. In this study, the atomically dispersed Ru sites in Co3O4 synergistically interact with Co centers, facilitating the adsorption and activation of hydroxyl radicals (OH*) and ethylene glycol (EG), resulting in a remarkable HCOOH selectivity of 99 % and a yield rate of 11.2 mmol h-1 cm-2 surpassing that of pristine Co3O4 (55 % and 3.8 mmol h-1 cm-2). Furthermore, when applied as a bifunctional cathode catalyst, Ru-Co3O4 achieves a remarkable Faradaic efficiency (FE) of 98.5 % for NH3 production (3.54 mmol h-1 cm-2) at -0.3 V vs. RHE. Additionally, we developed a prototype device powered by a commercial silicon photovoltaic cell, enabling on-site solar-driven production of formate and NH3 through enzyme-catalyzed PET and NO3- conversion. This study offers a viable approach for waste valorization and green chemical production, paving the way for sustainable energy applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"200 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Da Zhang, Yumin Chen, Xunwen Zheng, Pingxuan Liu, Ling Miao, Yaokang Lv, Ziyang Song, Lihua Gan, Mingxian Liu
Optimizing the crystalline orientation of Zn anode to achieve stable Zn (0002) plane growth is pursued for highly reversible zinc metal batteries (ZMBs). However, the lattice strain of Zn substrate hinders stable Zn2+ plating/stripping and sustainable epitaxial growth of Zn (0002) texture. Herein, we present a low strain strategy to mediate nucleated-Zn grains for stabilizing Zn2+ electrodeposition/stripping process and guiding sustainable Zn2+ growth along (0002) surfaces. Fluorinated anthracene triptycene polymer (FATP) photopolymerized on Zn exhibits nanocrystalline structure with highly ordered nanochannels (1.5 nm), enabling oriented nucleation and sustainable epitaxial stacking of Zn (0002) plane due to low nucleation energy (0.2 vs. 1.1 e−/Å3 of pure Zn) and low grain strain (−0.2 to 0.4 vs. −0.9 to 0.9 MPa). Besides, the ordered porous FATP nanofilm refines electroplating Zn grains (9.4 vs. 26.7 μm), alleviating strain accumulation (3.7 vs. 28.2 MPa) and lattice distortion. Consequently, FATP-Zn||Cu cell achieves a high average Coulombic efficiency of 99.6% over 6000 cycles, while FATP-Zn||FATP-Zn cell shows stable plating/stripping after 5000 h. Notably, FATP-Zn||MnO2 pouch cell (2.77 Ah) demonstrates stable operation over 1000 cycles. This work presents a new approach to designing Zn anodes with refined nucleated-Zn grains and sustainable Zn (0002) plane stacking for advanced ZMBs.
{"title":"Low Strain Mediated Zn (0002) Plane Epitaxial Plating for Highly Stable Zinc Metal Batteries","authors":"Da Zhang, Yumin Chen, Xunwen Zheng, Pingxuan Liu, Ling Miao, Yaokang Lv, Ziyang Song, Lihua Gan, Mingxian Liu","doi":"10.1002/anie.202500380","DOIUrl":"https://doi.org/10.1002/anie.202500380","url":null,"abstract":"Optimizing the crystalline orientation of Zn anode to achieve stable Zn (0002) plane growth is pursued for highly reversible zinc metal batteries (ZMBs). However, the lattice strain of Zn substrate hinders stable Zn2+ plating/stripping and sustainable epitaxial growth of Zn (0002) texture. Herein, we present a low strain strategy to mediate nucleated-Zn grains for stabilizing Zn2+ electrodeposition/stripping process and guiding sustainable Zn2+ growth along (0002) surfaces. Fluorinated anthracene triptycene polymer (FATP) photopolymerized on Zn exhibits nanocrystalline structure with highly ordered nanochannels (1.5 nm), enabling oriented nucleation and sustainable epitaxial stacking of Zn (0002) plane due to low nucleation energy (0.2 vs. 1.1 e−/Å3 of pure Zn) and low grain strain (−0.2 to 0.4 vs. −0.9 to 0.9 MPa). Besides, the ordered porous FATP nanofilm refines electroplating Zn grains (9.4 vs. 26.7 μm), alleviating strain accumulation (3.7 vs. 28.2 MPa) and lattice distortion. Consequently, FATP-Zn||Cu cell achieves a high average Coulombic efficiency of 99.6% over 6000 cycles, while FATP-Zn||FATP-Zn cell shows stable plating/stripping after 5000 h. Notably, FATP-Zn||MnO2 pouch cell (2.77 Ah) demonstrates stable operation over 1000 cycles. This work presents a new approach to designing Zn anodes with refined nucleated-Zn grains and sustainable Zn (0002) plane stacking for advanced ZMBs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641034","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Agamemnon Crumpton, Caitilín McManus, Simon Aldridge
Known boron carbonyl complexes either exploit very high Lewis acidity or a low oxidation state boron centre in order to capture CO. By contrast, we report a carbonyl complex featuring a simple tri-coordinate borane, characterized by a Lewis acidity which is only marginally higher than B(NMe2)3. {(Ph2P)xanth}3B features a solid-state structure in which two of the three B-bound xanth(PPh2) units are projected above the BC3plane, generating an up,up,down conformation. Quantum chemical methods, however, reveal that the alternative up,up,up alignment, characterized by a cage-like geometry and enhanced intramolecular non-covalent interactions, is favoured significantly in silico (by ca. 33.0 kcal mol-1). While this conformation is optimal for binding polar C3-symmetric H-bond donors such as NH3 (and related guests such as H2O and MeNH2) the binding of essentially non-polar substrates such as CO would be expected to be weak at best. However, exposure of {(Ph2P)xanth}3B to CO under mild conditions (1 bar, 25°C) reversibly yields {(Ph2P)xanth}3B·CO, a tractable cage-like borane carbonyl adduct featuring a central BCO moiety shrouded by xanth(PPh2) moieties. Dispersion forces are critical to substrate binding: the two binding modes in which the B-bound CO guest is located inside/outside the host cage differ in energy by 59.5 kcal mol-1.
已知的硼羰基复合物要么利用极高的路易斯酸度，要么利用低氧化态硼中心来捕获一氧化碳。{(Ph2P)xanth}3B的固态结构中，三个与硼结合的xanth(PPh2)单元中的两个单元凸出于BC3平面之上，从而产生了上、上、下的构象。然而，量子化学方法揭示了另一种向上、向上、向上的构象，这种构象的特点是具有笼状几何结构和增强的分子内非共价相互作用。虽然这种构象是结合极性 C3 对称氢键供体（如 NH3）（以及相关客体（如 H2O 和 MeNH2））的最佳构象，但与 CO 等基本非极性底物的结合充其量也只能是微弱的。然而，{(Ph2P)xanth}3B 在温和的条件下（1 bar，25°C）与 CO 接触，会可逆地产生{(Ph2P)xanth}3B-CO，这是一种笼状的硼烷羰基加合物，其特点是中心的 BCO 分子被 xanth(PPh2) 分子包裹。分散力对底物结合至关重要：B-结合的 CO 客体位于宿主笼内部/外部的两种结合模式的能量相差 59.5 kcal mol-1。
{"title":"Leveraging Non-Covalent Interactions for the Binding of CO by a Weakly Lewis Acidic Borane","authors":"Agamemnon Crumpton, Caitilín McManus, Simon Aldridge","doi":"10.1002/anie.202501774","DOIUrl":"https://doi.org/10.1002/anie.202501774","url":null,"abstract":"Known boron carbonyl complexes either exploit very high Lewis acidity or a low oxidation state boron centre in order to capture CO. By contrast, we report a carbonyl complex featuring a simple tri-coordinate borane, characterized by a Lewis acidity which is only marginally higher than B(NMe2)3. {(Ph2P)xanth}3B features a solid-state structure in which two of the three B-bound xanth(PPh2) units are projected above the BC3plane, generating an up,up,down conformation. Quantum chemical methods, however, reveal that the alternative up,up,up alignment, characterized by a cage-like geometry and enhanced intramolecular non-covalent interactions, is favoured significantly in silico (by ca. 33.0 kcal mol-1). While this conformation is optimal for binding polar C3-symmetric H-bond donors such as NH3 (and related guests such as H2O and MeNH2) the binding of essentially non-polar substrates such as CO would be expected to be weak at best. However, exposure of {(Ph2P)xanth}3B to CO under mild conditions (1 bar, 25°C) reversibly yields {(Ph2P)xanth}3B·CO, a tractable cage-like borane carbonyl adduct featuring a central BCO moiety shrouded by xanth(PPh2) moieties. Dispersion forces are critical to substrate binding: the two binding modes in which the B-bound CO guest is located inside/outside the host cage differ in energy by 59.5 kcal mol-1.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jia Song, Jianuo Liu, Xiaorong Zhu, Xiaoming Mou, Handuo Zheng, Huang Zhou, Wenyu Wang, Yong Guan, Jun Tang, Yue Lin, Lirong Zheng, Tao Yao, Juncai Dong, Shiqiang Wei, Weixin Huang, Lin Gu, Jun Luo, Yafei Li, Yafei Zhao, Yuen Wu
Tuning the catalytic pathways of atomically dispersed single-atom catalysts (SAC) has emerged as an effective strategy to optimize their overall catalytic activity. Herein, we present Ru1@m-tube, a hollow carbon nitride-supported Ru SAC, coated with eutectic galinstan (GaInSn), as a model catalyst, we demonstrate a performance inversion in vanillin conversion. Vanillin, as a biomass-derived compound with industrial relevance, presents challenges in catalytic hydrogenation, making it an ideal model reaction to test and compare the catalyst's selectivity and efficiency. The as-obtained Ru1@m-tube(GaInSn) achieved nearly 100% vanillin conversion within 5 hours and exhibited an impressive 93.8% selectivity for vanillyl alcohol . Electron spillover from gallium-based eutectic alloys to highly diluted ruthenium sites enhances the desorption of vanillyl alcohol, resulting in an exceptional performance shift between hydrogenation and hydrodeoxygenation. Our findings not only offer a novel approach for modulating SAC performance via liquid-metal interfaces but also expand the understanding of promoter screening for various challenging reactions.
{"title":"Gallium-Based Eutectic Alloys as Liquid Electron Donors to Ruthenium Single-Atom Catalysts for Selective Hydrogenation of Vanillin","authors":"Jia Song, Jianuo Liu, Xiaorong Zhu, Xiaoming Mou, Handuo Zheng, Huang Zhou, Wenyu Wang, Yong Guan, Jun Tang, Yue Lin, Lirong Zheng, Tao Yao, Juncai Dong, Shiqiang Wei, Weixin Huang, Lin Gu, Jun Luo, Yafei Li, Yafei Zhao, Yuen Wu","doi":"10.1002/anie.202505073","DOIUrl":"https://doi.org/10.1002/anie.202505073","url":null,"abstract":"Tuning the catalytic pathways of atomically dispersed single-atom catalysts (SAC) has emerged as an effective strategy to optimize their overall catalytic activity. Herein, we present Ru1@m-tube, a hollow carbon nitride-supported Ru SAC, coated with eutectic galinstan (GaInSn), as a model catalyst, we demonstrate a performance inversion in vanillin conversion. Vanillin, as a biomass-derived compound with industrial relevance, presents challenges in catalytic hydrogenation, making it an ideal model reaction to test and compare the catalyst's selectivity and efficiency. The as-obtained Ru1@m-tube(GaInSn) achieved nearly 100% vanillin conversion within 5 hours and exhibited an impressive 93.8% selectivity for vanillyl alcohol . Electron spillover from gallium-based eutectic alloys to highly diluted ruthenium sites enhances the desorption of vanillyl alcohol, resulting in an exceptional performance shift between hydrogenation and hydrodeoxygenation. Our findings not only offer a novel approach for modulating SAC performance via liquid-metal interfaces but also expand the understanding of promoter screening for various challenging reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aptamers, which are short, single-stranded DNA or RNA, are capable of binding to a wide array of targets with exceptional selectivity. Those with high affinity for theophylline have the potential to serve as biosensors, crucial for tracking theophylline levels in the treatment of respiratory conditions. Despite the extensive structural characterization of the RNA theophylline aptamer, the DNA counterpart’s ligand-recognition mechanism has remained unclear. Here, we elucidate the DNA theophylline aptamer’s ligand-binding mechanism through high-resolution crystal structures of its complexes with theophylline, 3-methylxanthine, and hypoxanthine. Guided by these structural insights, we computationally redesigned the theophylline-binding pocket via rational mutagenesis of key nucleotides, generating novel aptamers selective for adenine and prequeuosine (preQ1) ligands. These engineered aptamers were validated through biochemical and crystallographic analyses. By integrating structural biology with computational design, our work provides a relatively simple and effective method for developing new aptamers. While this strategy does not supplant SELEX, it serves as a beneficial complement to it.
{"title":"From Theophylline to Adenine or preQ1: Repurposing a DNA Aptamer Revealed by Crystal Structure Analysis","authors":"Lin Huang, Xiaowei Lin, Yuanyin Huang, Jinchao Huang, Hao Yuan, Yuhang Luo, Zhizhong Lu, Ying Ao, Jian Huang, Shuo-Bin Chen, Zhichao Miao","doi":"10.1002/anie.202504107","DOIUrl":"https://doi.org/10.1002/anie.202504107","url":null,"abstract":"Aptamers, which are short, single-stranded DNA or RNA, are capable of binding to a wide array of targets with exceptional selectivity. Those with high affinity for theophylline have the potential to serve as biosensors, crucial for tracking theophylline levels in the treatment of respiratory conditions. Despite the extensive structural characterization of the RNA theophylline aptamer, the DNA counterpart’s ligand-recognition mechanism has remained unclear. Here, we elucidate the DNA theophylline aptamer’s ligand-binding mechanism through high-resolution crystal structures of its complexes with theophylline, 3-methylxanthine, and hypoxanthine. Guided by these structural insights, we computationally redesigned the theophylline-binding pocket via rational mutagenesis of key nucleotides, generating novel aptamers selective for adenine and prequeuosine (preQ1) ligands. These engineered aptamers were validated through biochemical and crystallographic analyses. By integrating structural biology with computational design, our work provides a relatively simple and effective method for developing new aptamers. While this strategy does not supplant SELEX, it serves as a beneficial complement to it.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"14 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Scott G. Stewart, John Morgan, Nutt Michael, Josephine Offer, Jeremy A Duczynski, Ken Yamazaki, Miura Tomoya, Stephen Moggach, George A Koutsantonis, Reto Dorta
The synthesis and catalytic properties of Ni(II) complexes with the general formula Ni(NHC)[P(OR)3](Ar)Cl is described. These complexes are air-stable and extremely effective precatalysts in the Suzuki-Miyaura cross-coupling reaction. The reaction protocols described allow for the cross-coupling of aryl chlorides and arylboronic acids, employing low catalytic loading, to deliver a large variety of functionalized biaryl compounds. For the coupling of aryl chlorides with N-heterocyclic boronic acids, TBAF was used as an additive to afford nitrogen-containing biaryl products. Overall, these reaction protocols operate at room or mild temperatures and can be applied to a variety of electronically and sterically differentiated coupling partners. Fundamental insights into the mechanism of this reaction, including the proposed formation of the catalytically active Ni(NHC)[P(Oi-Pr)3] and resting state species, are also reported.
{"title":"Efficient Nickel Precatalysts for Suzuki-Miyaura Cross-Coupling of Aryl Chlorides and Arylboronic Acids under Mild Conditions","authors":"Scott G. Stewart, John Morgan, Nutt Michael, Josephine Offer, Jeremy A Duczynski, Ken Yamazaki, Miura Tomoya, Stephen Moggach, George A Koutsantonis, Reto Dorta","doi":"10.1002/anie.202504108","DOIUrl":"https://doi.org/10.1002/anie.202504108","url":null,"abstract":"The synthesis and catalytic properties of Ni(II) complexes with the general formula Ni(NHC)[P(OR)3](Ar)Cl is described. These complexes are air-stable and extremely effective precatalysts in the Suzuki-Miyaura cross-coupling reaction. The reaction protocols described allow for the cross-coupling of aryl chlorides and arylboronic acids, employing low catalytic loading, to deliver a large variety of functionalized biaryl compounds. For the coupling of aryl chlorides with N-heterocyclic boronic acids, TBAF was used as an additive to afford nitrogen-containing biaryl products. Overall, these reaction protocols operate at room or mild temperatures and can be applied to a variety of electronically and sterically differentiated coupling partners. Fundamental insights into the mechanism of this reaction, including the proposed formation of the catalytically active Ni(NHC)[P(Oi-Pr)3] and resting state species, are also reported.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Huining Wang, Lu Song, Ximeng Lv, Haozhen Wang, Fan Zhang, Shuya Hao, Ruilin Wei, Lijuan Zhang, Qing Han, Gengfeng Zheng
Photoreduction of CO2 using copper-based multi-atom catalysts (MACs) offers a potential approach to achieve value-added C2+ products. However, achieving MACs with high metal contents and suppressing the thermodynamically favored competing ethylene production pathway remain challenging, thus leading to unsatisfactory performance in ethanol production. Herein, we developed a ‘pre-locking and nanoconfined polymerization’ strategy for synthesis of an ultra-high-density Cu MAC with low-coordination triangular Cu3 motifs (Cu3 MAC) on polymeric carbon nitride mesoporous nanofibers. The Cu3 MAC with Cu contents of 36 wt% achieves a high reactivity of 117 μmol·g-1·h-1 for ethanol production from CO2 and H2O, with a remarkable selectivity of 98% under simulated sunlight irradiation, representing one of the highest performances in ambient conditions without sacrificial reagents. The superior catalytic efficiency is attributed to the triangular Cu3 configuration, in which both Cu(I) and Cu(II) coexist, predominantly as Cu(I). Such Cu3 motifs act as strong alkaline sites that effectively chemisorb and activate CO2, extend visible-light absorption range, while accumulating high-density electrons and favoring 12-electron-transfer products. An accelerated asymmetric C-C coupling with adsorption configuration of the bridge-adsorbed *CO at paired Cu sites and atop-adsorbed *CO at adjacent single Cu atom was observed, enabling preferential formation of *CHCHOH intermediates to produce ethanol.
{"title":"Low-Coordination Triangular Cu3 Motif Steers CO2 Photoreduction to Ethanol","authors":"Huining Wang, Lu Song, Ximeng Lv, Haozhen Wang, Fan Zhang, Shuya Hao, Ruilin Wei, Lijuan Zhang, Qing Han, Gengfeng Zheng","doi":"10.1002/anie.202500928","DOIUrl":"https://doi.org/10.1002/anie.202500928","url":null,"abstract":"Photoreduction of CO2 using copper-based multi-atom catalysts (MACs) offers a potential approach to achieve value-added C2+ products. However, achieving MACs with high metal contents and suppressing the thermodynamically favored competing ethylene production pathway remain challenging, thus leading to unsatisfactory performance in ethanol production. Herein, we developed a ‘pre-locking and nanoconfined polymerization’ strategy for synthesis of an ultra-high-density Cu MAC with low-coordination triangular Cu3 motifs (Cu3 MAC) on polymeric carbon nitride mesoporous nanofibers. The Cu3 MAC with Cu contents of 36 wt% achieves a high reactivity of 117 μmol·g-1·h-1 for ethanol production from CO2 and H2O, with a remarkable selectivity of 98% under simulated sunlight irradiation, representing one of the highest performances in ambient conditions without sacrificial reagents. The superior catalytic efficiency is attributed to the triangular Cu3 configuration, in which both Cu(I) and Cu(II) coexist, predominantly as Cu(I). Such Cu3 motifs act as strong alkaline sites that effectively chemisorb and activate CO2, extend visible-light absorption range, while accumulating high-density electrons and favoring 12-electron-transfer products. An accelerated asymmetric C-C coupling with adsorption configuration of the bridge-adsorbed *CO at paired Cu sites and atop-adsorbed *CO at adjacent single Cu atom was observed, enabling preferential formation of *CHCHOH intermediates to produce ethanol.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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