Angewandte Chemie International Edition最新文献_第8页

Insights Into the Role of π‐Electrons of Aromatic Aldehydes in Passivating Perovskite Defects 透视芳香族醛的π电子在钝化包晶缺陷中的作用

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-13 DOI: 10.1002/anie.202420369

Xiaoqing Jiang, Lina Zhu, Bingqian Zhang, Guangyue Yang, Likai Zheng, Kaiwen Dong, Yanfeng Yin, Minhuan Wang, Shiwei Liu, Shuping Pang, Xin Guo

{"title":"Insights Into the Role of π‐Electrons of Aromatic Aldehydes in Passivating Perovskite Defects","authors":"Xiaoqing Jiang, Lina Zhu, Bingqian Zhang, Guangyue Yang, Likai Zheng, Kaiwen Dong, Yanfeng Yin, Minhuan Wang, Shiwei Liu, Shuping Pang, Xin Guo","doi":"10.1002/anie.202420369","DOIUrl":"https://doi.org/10.1002/anie.202420369","url":null,"abstract":"Carbonyl‐containing aromatic ketones or aldehydes have been demonstrated to be effective defect passivators for perovskite films to improve performances of perovskite solar cells (PSCs). It has been claimed that both π‐electrons within aromatic units and carbonyl groups can, separately, interact with ionic defects, which, however, causes troubles in understanding the passivation mechanism of those aromatic ketone/aldehyde molecules. Herein, we clarify the effect of both moieties in one molecule on the defect passivation by investigating three aromatic aldehydes with varied conjugation planes, namely, biphenyl‐4‐carbaldehyde (BPCA), naphthalene‐2‐carbaldehyde (NACA) and pyrene‐1‐carbaldehyde (PyCA). Our findings reveal that the π‐electrons located in the conjugated system do not directly present strong passivation for defects, but enhance the electron cloud density of the carbonyl group augmenting its interaction with defect sites; thereby, with the extended conjugation plane of the three molecules, their defect passivation ability is gradually improved. PSCs incorporating PyCA with the most extended π‐electrons delocalization achieve maximum power conversion efficiencies of 25.67% (0.09 cm²) and 21.76% (14.0 cm²). Moreover, these devices exhibit outstanding long‐term stability, retaining 95% of their initial efficiency after operation for 1000 hours at the maximum power point.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815794","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}

引用次数: 0

Polarity-Reversed Functionalization of Aliphatic Aldehydes via Divergent Nickel Hydride Catalysis

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202419965

Changpeng Chen, Hanhong Xu, Shaolin Zhu

引用次数: 0

Autocatalytic Nucleation and Self-Assembly of Inorganic Nanoparticles into Complex Biosimilar Networks

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202413444

Nicholas Alexander Kotov, Connor N. McGlothin, Xiongye Xiao, Paul Bogdan, Kody Whisnant, Sumeyra Emre, Dickson Owuor, Jun Lu, Scott van Epps, Drew Vecchio

{"title":"Autocatalytic Nucleation and Self-Assembly of Inorganic Nanoparticles into Complex Biosimilar Networks","authors":"Nicholas Alexander Kotov, Connor N. McGlothin, Xiongye Xiao, Paul Bogdan, Kody Whisnant, Sumeyra Emre, Dickson Owuor, Jun Lu, Scott van Epps, Drew Vecchio","doi":"10.1002/anie.202413444","DOIUrl":"https://doi.org/10.1002/anie.202413444","url":null,"abstract":"Self-replication of molecules and microdroplets have been explored as models in prebiotic chemistry. An analogous process for inorganic nanomaterials would involve the autocatalytic nucleation of nanoparticles—an area that remains largely uncharted. Demonstrating such systems would be both fundamentally intriguing and practically relevant, especially if the resulting particles self-assemble. Here, we show that autocatalytic nucleation couples with self-assembly occurs with silver nanoparticles. In dispersions containing “hedgehog” particles, these reactions produce complex colloids with hierarchical spike organization. On solid surfaces, autocatalytic nucleation of nanoparticles yields conformal networks with hierarchical organization, including nanoparticle “colonies.” We analyzed the complexity of both types of solid-stabilized particle assemblies via graph theory (GT). The complexity index of idealized spiky colloids is comparable to that of complex algal skeletons. The GT analysis of the percolating nanoparticle networks revealed their similarities to the bacterial, but not fungal, biofilms. We conclude that coupling autocatalytic nucleation with self-assembly enables the generation of complex, biosimilar particles and films. This work establishes mathematical and structural parallels between biotic and abiotic matter, integrating self-organization, autocatalytic nucleation, and theoretical description of complex system. Utilization of quantitative descriptors of connectivity patterns opens possibility to GT-based biomimetic engineering of conductive coatings and other complex nanostructures.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"50 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809960","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}

引用次数: 0

Metal-Free Electrocatalytic Alkaline Water Splitting by Porous Macrocyclic Proton Sponges

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202419377

Ananda Basak, Arun Karmakar, Sayantani Dutta, Diptendu Roy, Satyadip Paul, Yusuke Nishiyama, Biswarup Pathak, Subrata Kundu, Rahul Banerjee

{"title":"Metal-Free Electrocatalytic Alkaline Water Splitting by Porous Macrocyclic Proton Sponges","authors":"Ananda Basak, Arun Karmakar, Sayantani Dutta, Diptendu Roy, Satyadip Paul, Yusuke Nishiyama, Biswarup Pathak, Subrata Kundu, Rahul Banerjee","doi":"10.1002/anie.202419377","DOIUrl":"https://doi.org/10.1002/anie.202419377","url":null,"abstract":"Macrocycles are unique as they encapsulate and transfer guest molecules or ions and facilitate catalytic processes. Although metalated macrocycles are pivotal in electrocatalytic processes, using metal-free analogs has been rare. Following the strategy of Kanbara et al., we synthesized an azacalixarene macrocycle— N, N’, N’’-tris(p-aminophenyl)azacalix[3](2,6)pyridine (CalixNH2). The macrocycle encapsulates a proton in its cavity, maintaining the protonation even in highly alkaline media. Notably, it retains almost 50% protonated form in 1 M KOH (~pH 14)—acting as a proton sponge. As hydrogen evolution is complex in alkaline media owing to sluggish water dissociation, we implemented the proton sponge (CalixNH2) in an alkaline hydrogen evolution reaction. Conjugated Porous polymers, TpCalix and DhaCalix, have been synthesized from the triamine—CalixNH2. The most efficient catalyst, TpCalix, has shown excellent performance in alkaline HER and OER in 1 M KOH (~pH 14), with low overpotentials of only 112(±2) and 290(±2) mV at 10 mA cm-2, respectively, and durable up to 24 hours. A full-cell reaction using TpCalix in both the cathode and anode exhibited a low full-cell voltage of 1.73 V and was stable for 12 hours. DFT calculations verified the tripyridinic core, which acts as the principal site for proton abstraction and binding.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"14 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142810055","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}

引用次数: 0

Spiro‐Fused vs 575‐Ringed Boron‐Doped Polycyclic π‐Systems: Selective Synthesis, Reactivity and Properties

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202422031

Yujia Liu, Xinyu Tian, Zeyi Li, Tianyu Zhang, Liuzhong Yuan, Yue Wang, Chuandong Dou

{"title":"Spiro‐Fused vs 575‐Ringed Boron‐Doped Polycyclic π‐Systems: Selective Synthesis, Reactivity and Properties","authors":"Yujia Liu, Xinyu Tian, Zeyi Li, Tianyu Zhang, Liuzhong Yuan, Yue Wang, Chuandong Dou","doi":"10.1002/anie.202422031","DOIUrl":"https://doi.org/10.1002/anie.202422031","url":null,"abstract":"Incorporation of heteroatoms and/or non‐hexagonal rings into polycyclic aromatic hydrocarbons (PAHs) can alter their intrinsic structures and physical properties. However, it is challenging to construct PAHs featuring boron/carbon composition and non‐hexagonal combination. Herein, we disclose the selective synthesis of spiro‐type and pentagon/heptagon‐containing boron‐doped polycyclic π‐systems by the Scholl reaction. Two spiro‐fused organoboranes 1 and 2 and one 575‐ringed boron‐doped nanographene 3 were synthesized. The key point is that the boron‐edged π‐system enabled unexpected spiro‐formation via dearomatization, whereas the boron‐centered π‐system enabled desired 575‐ringed π‐extension via cyclodehydrogenation. The thus‐obtained molecules exhibit the intriguing but fully distinct reactivity, electronic structures and properties, for instance, while 2 may react with Brønsted acid to display reversible chemochromism and further convert into 1, 3 possesses very broad absorption, short excited‐state lifetime and no fluorescence nature. As disclosed, the boron atom together with the spirocycle region or 575‐ringed structural motif significantly contribute to their characteristic properties. Thus, this study sheds light on control over the Scholl reaction using organoborane π‐systems and will promote the exploration of more sophisticated polycyclic π‐systems as organic reactive and optical scaffolds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"98 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809182","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}

引用次数: 0

A Kinetically Stabilized Dianthraceno[2,3-a:3',2'-h]-s-indacene: Stable Kekulé Diradical Polycyclic Hydrocarbon with Triplet Ground State

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202422994

Qing Jiang, Lei Wang, Haipeng Wei, Yuchen Peng, Guangyan Xu, Zhaoyang Li, Pengfei Liu, Zhenni Hu, Weiwei Niu, Yifan Chen, Hui Tang, Wangdong Zeng, Guangwu Li

{"title":"A Kinetically Stabilized Dianthraceno[2,3-a:3',2'-h]-s-indacene: Stable Kekulé Diradical Polycyclic Hydrocarbon with Triplet Ground State","authors":"Qing Jiang, Lei Wang, Haipeng Wei, Yuchen Peng, Guangyan Xu, Zhaoyang Li, Pengfei Liu, Zhenni Hu, Weiwei Niu, Yifan Chen, Hui Tang, Wangdong Zeng, Guangwu Li","doi":"10.1002/anie.202422994","DOIUrl":"https://doi.org/10.1002/anie.202422994","url":null,"abstract":"High-spin polycyclic hydrocarbons (PHs) hold significant potential in organic spintronics and organic magnets. However, their synthesis is very challenging due to their extremely high reactivity. Herein, we report the successful synthesis and isolation of a kinetically blocked derivative (1) of dianthraceno[2,3-a:3',2'-h]-s-indacene, which represents a rare persistent triplet diradical of a Kekulé PH. Its triplet ground state was unambiguously confirmed by electron paramagnetic resonance and superconducting quantum interference device measurements. Its structure was also unequivocally confirmed through X-ray crystallographic analysis, and its electronic properties were systematically investigated by both experiments and theoretical calculations. The key design principle is to extend the π-conjugation for achieving the decrease of the bonding interaction and the increase of the exchange interaction between unpaired electrons, which are essential for accessing the stable triplet ground state. Due to kinetic blocking, 1 shows a reasonable stability with a half-life time of 64 h under ambient conditions. It has a narrow HOMO–LUMO energy gap and displays amphoteric redox behavior. Notably, its dication and dianion exhibit a closed-shell ground state and near-infrared absorption, and the structures were identified by X-ray crystallographic analysis. This study will shed new light on the design and synthesis of novel stable PHs with high-spin multiplicity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809957","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}

引用次数: 0

Photochromic Dysprosium Single-Molecule Magnet Featuring Reversible Redox Transformation of Polyoxomolybdate Moiet

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202422557

Hui Kong, Jing-Yu Wang, Jia-Chuan Liu, Lu Zhang, Pei-Yu Liao, Yu-Quan Qi, Zheng Liu, Si-Guo Wu, Ming-Liang Tong

引用次数: 0

Molecular Conjugated-Polymer Electrode Enables Rapid Proton Conduction for Electrosynthesis of Ammonia from Nitrate

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202422072

Xinhao Su, Feiyang Hong, Yanjie Fang, Yingke Wen, Bing Shan

{"title":"Molecular Conjugated-Polymer Electrode Enables Rapid Proton Conduction for Electrosynthesis of Ammonia from Nitrate","authors":"Xinhao Su, Feiyang Hong, Yanjie Fang, Yingke Wen, Bing Shan","doi":"10.1002/anie.202422072","DOIUrl":"https://doi.org/10.1002/anie.202422072","url":null,"abstract":"Electrosynthesis of ammonia (NH3) from nitrate (NO3-) using renewable energy holds promise as a supplementary alternative to the Haber-Bosch process for NH3 production. Most research focuses on tuning the catalytic activity of metal catalysts by modification of the catalyst structures. However, the electrode supports which could influence the catalytic activity have not been well-explored. The state-of-the-art electrocatalysts for NO3- reduction to NH3 still exhibit limited energy efficiency at ampere-level current density. Herein, we report a polyaniline-based molecular electrode with Cu catalyst for selective and energy-efficient NO3- reduction to NH3. In the electrode, the polyaniline promotes protonation of the key intermediate formed during NO3- reduction at Cu, which circumvents the limitation of the Cu catalyst in the efficiency-limiting proton transfer step. The molecular electrode produces NH3 at a partial current density of 2.7 A cm-2 with an energy efficiency of 62%, demonstrating much better electrochemical performance than common Cu-based electrocatalysts and indicating the great potential in molecular engineering of electrode supports for selective NO3- reduction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816443","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}

引用次数: 0

Sub-nanometer Pt Nanowires with Disordered Shells for Highly Active Elelctrocatalytic Oxidation of Formic Acid

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202422199

Gui Liu, Ruichun Luo, Junhao Ma, Tianqi Guo, Jianxin Kang, Wenxiong Shi, Wu Zhou, Lin Guo

{"title":"Sub-nanometer Pt Nanowires with Disordered Shells for Highly Active Elelctrocatalytic Oxidation of Formic Acid","authors":"Gui Liu, Ruichun Luo, Junhao Ma, Tianqi Guo, Jianxin Kang, Wenxiong Shi, Wu Zhou, Lin Guo","doi":"10.1002/anie.202422199","DOIUrl":"https://doi.org/10.1002/anie.202422199","url":null,"abstract":"Controlled synthesis of one-dimensional materials at atomic-scale dimensions represents a milestone in nanotechnology, offering the potential to maximize atom utilization while enhancing catalytic performance. However, achieving structural stability and durability at such fine scales requires precise control over material structure and local chemical environment. Here, we introduce dimethylamine (DMA) as a small-molecule modifier, in contrast to conventional long-chain surfactants, to interact with surface Pt atoms. This approach facilitates the removal of surface Pt atoms bonded to nitrogen atoms in DMA during solubilization in water, effectively stripping the size of Pt nanowires down to sub-nanometer. The resulting Pt subnanometer nanowires (subNWs) feature a monoatomic-layer surface composed of disordered, bonding-unsaturated Pt atoms, and an interior crystalline core as narrow as 0.58 nm in diameter. These unique structural characteristics confer the Pt subNWs with an electrochemically active surface-area of 189 m2·g−1 during formic acid oxidation. Furthermore, the amorphous-like surface structure lowers the free energy of *OCOH intermediates and inhibits the formation of toxic byproducts CO, demonstrating exceptional electrocatalytic activity of 18.1 A·mg−1, surpassing all reported Pt-based electrocatalysts. Our work introduces a novel strategy for the controlled construction of nanowire-structures at sub-nanometer scale, effectively bridging the gap between ultrafine structural design and performance stability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816444","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}

引用次数: 0

3,6‐Bis(methylthio)‐9H‐carbazole Based Self‐Assembled Monolayer for Highly Efficient and Stable Inverted Perovskite Solar Cells

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-12 DOI: 10.1002/anie.202423206

BongSoo Kim, Shahid Ameen, Dongmin Lee, Abdullah Bin Faheem, Jung Geon Son, Youngwan Lee, Hyunjoon Yoo, Sujung Park, Yun Seop Shin, Jaehwi Lee, Jongdeuk Seo, Hyungsu Jang, Jina Roe, Ji Won Song, Shinuk Cho, Yongsup Park, Kyung-Koo Lee, Jin Young Kim, Dong Suk Kim

{"title":"3,6‐Bis(methylthio)‐9H‐carbazole Based Self‐Assembled Monolayer for Highly Efficient and Stable Inverted Perovskite Solar Cells","authors":"BongSoo Kim, Shahid Ameen, Dongmin Lee, Abdullah Bin Faheem, Jung Geon Son, Youngwan Lee, Hyunjoon Yoo, Sujung Park, Yun Seop Shin, Jaehwi Lee, Jongdeuk Seo, Hyungsu Jang, Jina Roe, Ji Won Song, Shinuk Cho, Yongsup Park, Kyung-Koo Lee, Jin Young Kim, Dong Suk Kim","doi":"10.1002/anie.202423206","DOIUrl":"https://doi.org/10.1002/anie.202423206","url":null,"abstract":"The photovoltaic performance of inverted perovskite solar cells (PSCs) relies on effectively managing the interface between the hole extraction layer and the light‐absorbing perovskite layer. In this study, we have synthesised (4‐(3,6‐bis(methylthio)‐9H‐carbazol‐9‐yl)butyl)phosphonic acid (MeS‐4PACz), which forms a self‐assembled monolayer on the fluorine‐doped tin oxide (FTO) electrode. The molecule's methylthio substituents generate a favourable interfacial dipole moment and interact with the perovskite layer. This interaction results in well‐aligned energy levels among the FTO/SAM/perovskite layers, promoting efficient hole extraction and significantly reducing carrier recombination losses. Additionally, the methylthio groups passivate iodide vacancies and interact with Pb2+ ions of the perovskite, reducing defect‐induced trap states and enhancing the crystalline growth of the perovskite layer. Consequently, inverted PSCs incorporating MeS‐4PACz achieve a remarkable power conversion efficiency of 25.13%, along with outstanding photostability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"231 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809185","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}

引用次数: 0