Site-selective C-H bond functionalization of arenes at the para position remains extremely challenging primarily due to its relative inaccessibility from the catalytic site. As a consequence, it is significantly restricted to limited molecular scaffolds. Herein, we report a method for the para-C-H borylation of aromatic aldimines and benzylamines using commercially available ligands under iridium catalysis. The established method displays excellent para selectivity for variously substituted aromatic aldimines, benzylamines and bioactive molecules. Based on several control experiments, it is proposed that a Lewis acid-base interaction between the nitrogen and boron functionality guides the para selectivity via a steric shield for the aromatic aldimines, where Bpin acts as a transient directing group. However, the steric shield of the in situ generated N-Bpin moiety controlled the overall selectivity for the para borylation of benzylamines.
{"title":"Sterically Controlled Lewis Acid-Base Interaction Toward para-Selective Borylation of Aromatic Aldimines and Benzylamines.","authors":"Saikat Guria, Mirja Md Mahamudul Hassan, Sayan Dey, Krishna Nand Singh, Buddhadeb Chattopadhyay","doi":"10.1002/anie.202409010","DOIUrl":"10.1002/anie.202409010","url":null,"abstract":"<p><p>Site-selective C-H bond functionalization of arenes at the para position remains extremely challenging primarily due to its relative inaccessibility from the catalytic site. As a consequence, it is significantly restricted to limited molecular scaffolds. Herein, we report a method for the para-C-H borylation of aromatic aldimines and benzylamines using commercially available ligands under iridium catalysis. The established method displays excellent para selectivity for variously substituted aromatic aldimines, benzylamines and bioactive molecules. Based on several control experiments, it is proposed that a Lewis acid-base interaction between the nitrogen and boron functionality guides the para selectivity via a steric shield for the aromatic aldimines, where Bpin acts as a transient directing group. However, the steric shield of the in situ generated N-Bpin moiety controlled the overall selectivity for the para borylation of benzylamines.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618720","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}
Three dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero-superlattice Zn/ZnLi (HS-Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite-free zinc deposition, which significantly improves the cycling stability of the HS-Zn/ZnLi alloy (over 2800 h without a short-circuit at 2 mA cm-2). More importantly, this strategy can be extended to HS-Zn/ZnNa and HS-Zn/ZnK anodes that are similar to the HS-Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite-free metal anodes with stable cycling performance.
{"title":"Lithiation Induced Hetero-Superlattice Zn/ZnLi as Stable Anode for Aqueous Zinc-Ion Batteries.","authors":"Chao Hu, Zefang Yang, Qi Zhang, Mingze Zhang, Tingqing Wu, Chunlin Xie, Hao Wang, Yougen Tang, Haiyan Wang","doi":"10.1002/anie.202409096","DOIUrl":"10.1002/anie.202409096","url":null,"abstract":"<p><p>Three dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero-superlattice Zn/ZnLi (HS-Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite-free zinc deposition, which significantly improves the cycling stability of the HS-Zn/ZnLi alloy (over 2800 h without a short-circuit at 2 mA cm<sup>-2</sup>). More importantly, this strategy can be extended to HS-Zn/ZnNa and HS-Zn/ZnK anodes that are similar to the HS-Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite-free metal anodes with stable cycling performance.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562093","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}
Pub Date : 2024-10-07Epub Date: 2024-09-05DOI: 10.1002/anie.202410291
Johannes Schwarzmann, Toni Eskelinen, Sascha Reith, Jacqueline Ramler, Antti J Karttunen, Jordi Poater, Crispin Lichtenberg
Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element-element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2.
建立前所未有的键合相互作用类型是合成化学的基本挑战之一,它为新的(电子)结构、理化性质和反应性铺平了道路。在这种情况下,无支撑元素之间的相互作用尤其值得注意,因为它们提供了关于新发现结构基团的原始科学信息。在此,我们报告了杂多金属 Bi / Pt 化合物 [Pt(PCy3)2(BiMe2)(SbF6)](1)的合成、分离和全面表征。1 具有出人意料的稳健性,其电子能谱可以用完全相对论的方法进行解释,并显示出对 H2 的前所未有的反应活性。
{"title":"Bismuth as a Z-Type Ligand: an Unsupported Pt-Bi Donor-Acceptor Interaction and its Umpolung by Reaction with H<sub>2</sub>.","authors":"Johannes Schwarzmann, Toni Eskelinen, Sascha Reith, Jacqueline Ramler, Antti J Karttunen, Jordi Poater, Crispin Lichtenberg","doi":"10.1002/anie.202410291","DOIUrl":"10.1002/anie.202410291","url":null,"abstract":"<p><p>Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element-element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy<sub>3</sub>)<sub>2</sub>(BiMe<sub>2</sub>)(SbF<sub>6</sub>)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H<sub>2</sub>.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578347","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}
Pub Date : 2024-10-07Epub Date: 2024-09-09DOI: 10.1002/anie.202403618
{"title":"Withdrawal: Steering Sulfur Reduction Pathways via Cisplatin Enables High Performance in Lithium-Sulfur Batteries.","authors":"","doi":"10.1002/anie.202403618","DOIUrl":"10.1002/anie.202403618","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141178355","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}
Deep eutectic electrolytes (DEEs) have attracted significant interest due to the unique physiochemical properties, yet challenges persist in achieving satisfactory Li anode compatibility through a binary DEE formula. In this study, we introduce a nonflammable binary DEE electrolyte comprising of lithium bis(trifluoro-methane-sulfonyl)imide (LiTFSI) and solid butadiene sulfone (BdS), which demonstrates enhanced Li metal compatibility while exhibiting high Li+ ion migration number (0.52), ionic conductivity (1.48 mS ⋅ cm-1), wide electrochemical window (~4.5 V vs. Li/Li+) at room temperature. Experimental and theoretical results indicate that the Li compatibility derives from the formation of a LiF-rich SEI, attributed to the undesirable adsorption and deformation of BdS on Li surface that facilitates the preferential reactions between LiTFSI and Li metal. This stable SEI effectively suppresses dendrites growth and gas evolution reactions, ensuring a long lifespan and high coulombic efficiency in both the Li||Li symmetric cells, Li||LiCoO2 and Li||LiNi0.8Co0.1Mn0.1O2 full cells. Moreover, the BdS eutectic strategy exhibit universal applicability to other metal such as Na and Zn by pairing with the corresponding TFSI-based salts.
深共晶电解质(DEE)因其独特的物理化学特性而备受关注,但要通过二元 DEE 配方实现令人满意的锂阳极兼容性仍存在挑战。在本研究中,我们介绍了一种由双(三氟甲烷-磺酰基)亚胺锂(LiTFSI)和固体丁二烯砜(BdS)组成的不易燃二元 DEE 电解质,该电解质在室温下表现出较高的 Li+ 离子迁移数(0.52)、离子电导率(1.48 mS-cm-1)和较宽的电化学窗口(~4.5 V vs. Li/Li+),从而增强了锂金属的兼容性。实验和理论结果表明,锂的兼容性源于富含 LiF 的 SEI 的形成,这归因于 BdS 在锂表面的不良吸附和变形促进了 LiTFSI 与锂金属之间的优先反应。这种稳定的 SEI 有效抑制了枝晶的生长和气体演化反应,确保了 Li||Li 对称电池、Li||LiCoO2 和 Li||LiNi0.8Co0.1Mn0.1O2 全电池的长寿命和高库仑效率。此外,BdS 共晶策略通过与相应的基于 TFSI 的盐配对,显示出对 Na 和 Zn 等其他金属的普遍适用性。
{"title":"Butadiene Sulfone Based Binary Deep Eutectic Electrolyte for High Performance Lithium Metal Batteries.","authors":"Tiankun Zhou, Chengjun Lei, Jinye Li, Huijian Wang, Tingting Liu, Xin He, Xiao Liang","doi":"10.1002/anie.202408728","DOIUrl":"10.1002/anie.202408728","url":null,"abstract":"<p><p>Deep eutectic electrolytes (DEEs) have attracted significant interest due to the unique physiochemical properties, yet challenges persist in achieving satisfactory Li anode compatibility through a binary DEE formula. In this study, we introduce a nonflammable binary DEE electrolyte comprising of lithium bis(trifluoro-methane-sulfonyl)imide (LiTFSI) and solid butadiene sulfone (BdS), which demonstrates enhanced Li metal compatibility while exhibiting high Li<sup>+</sup> ion migration number (0.52), ionic conductivity (1.48 mS ⋅ cm<sup>-1</sup>), wide electrochemical window (~4.5 V vs. Li/Li<sup>+</sup>) at room temperature. Experimental and theoretical results indicate that the Li compatibility derives from the formation of a LiF-rich SEI, attributed to the undesirable adsorption and deformation of BdS on Li surface that facilitates the preferential reactions between LiTFSI and Li metal. This stable SEI effectively suppresses dendrites growth and gas evolution reactions, ensuring a long lifespan and high coulombic efficiency in both the Li||Li symmetric cells, Li||LiCoO<sub>2</sub> and Li||LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> full cells. Moreover, the BdS eutectic strategy exhibit universal applicability to other metal such as Na and Zn by pairing with the corresponding TFSI-based salts.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141615369","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}
Pub Date : 2024-10-07Epub Date: 2024-07-09DOI: 10.1002/anie.202406065
Bin Wang, Lu Wang, Muhammad Mamoor, Chang Wang, Yanjun Zhai, Fengbo Wang, Zhongxin Jing, Guangmeng Qu, Yueyue Kong, Liqiang Xu
The catalytic process of Li2S formation is considered a key pathway to enhance the kinetics of lithium-sulfur batteries. Due to the system's complexity, the catalytic behavior is uncertain, posing significant challenges for predicting activity. Herein, we report a novel cascaded dual-cavity nanoreactor (NiCo-B) by controlling reaction kinetics, providing an opportunity for achieving hierarchical catalytic behavior. Through experimental and theoretical analysis, the multilevel structure can effectively suppress polysulfides dissolution and accelerate sulfur conversion. Furthermore, we differentiate the adsorption (B-S) and catalytic effect (Co-S) in NiCo-B, avoiding catalyst deactivation caused by excessive adsorption. As a result, the as-prepared battery displays high reversible capacity, even with sulfur loading of 13.2 mg cm-2 (E/S=4 μl mg-1), the areal capacity can reach 18.7 mAh cm-2.
{"title":"Manipulating Atomic-Coupling in Dual-Cavity Boride Nanoreactor to Achieve Hierarchical Catalytic Engineering for Sulfur Cathode.","authors":"Bin Wang, Lu Wang, Muhammad Mamoor, Chang Wang, Yanjun Zhai, Fengbo Wang, Zhongxin Jing, Guangmeng Qu, Yueyue Kong, Liqiang Xu","doi":"10.1002/anie.202406065","DOIUrl":"10.1002/anie.202406065","url":null,"abstract":"<p><p>The catalytic process of Li<sub>2</sub>S formation is considered a key pathway to enhance the kinetics of lithium-sulfur batteries. Due to the system's complexity, the catalytic behavior is uncertain, posing significant challenges for predicting activity. Herein, we report a novel cascaded dual-cavity nanoreactor (NiCo-B) by controlling reaction kinetics, providing an opportunity for achieving hierarchical catalytic behavior. Through experimental and theoretical analysis, the multilevel structure can effectively suppress polysulfides dissolution and accelerate sulfur conversion. Furthermore, we differentiate the adsorption (B-S) and catalytic effect (Co-S) in NiCo-B, avoiding catalyst deactivation caused by excessive adsorption. As a result, the as-prepared battery displays high reversible capacity, even with sulfur loading of 13.2 mg cm<sup>-2</sup> (E/S=4 μl mg<sup>-1</sup>), the areal capacity can reach 18.7 mAh cm<sup>-2</sup>.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141157226","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}
Pub Date : 2024-10-07Epub Date: 2024-09-05DOI: 10.1002/anie.202402635
Liang Liu, Samantha I Johnson, Aaron M Appel, R Morris Bullock
Ammonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon-neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth-abundant transition metal complex, trans-[LFeII(MeCN)2][PF6]2, where L is a macrocyclic ligand bearing four N-heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N2 per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator (p-MeOC6H4)3N exhibited a catalytic half-wave potential (Ecat/2) of 0.18 V vs [Cp2Fe]+/0 in MeCN, and achieved 9.3 turnovers of N2 at an applied potential of 0.20 V vs [Cp2Fe]+/0 at -20 °C in controlled-potential electrolysis, with a Faradaic efficiency of 75 %. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFeIV(NH2)2]2+, and thereafter bimetallic coupling to form an N-N bond.
在寻求可持续清洁能源的过程中,氨是一种前景广阔的候选物质。由于氨具有作为能量载体的能力,氨的氧化为以碳中性方法解决全球日益增长的能源需求开辟了道路。我们报告了一种地球上丰富的过渡金属复合物--反式[LFeII(MeCN)2][PF6]2--对氨的催化化学氧化作用,其中 L 是一种大环配体,带有四个 N-杂环碳烯(NHC)供体。利用 MeCN 中的三芳基铵自由基阳离子,在铁催化剂负载量极低(0.043 mM,0.004 mol % 催化剂)的情况下,通过化学催化获得了每铁 182 次的 N2 转化。这种化学催化成功过渡到了氨氧化的介导电催化。铁催化剂和介质 (p-MeOC6H4)3N 的分子电催化在 MeCN 中的催化半波电位(Ecat/2)为 0.18 V vs [Cp2Fe]+/0,在 -20 °C 的受控电位电解中,应用 0.20 V vs [Cp2Fe]+/0的电位实现了 9.3 次 N2 转化,法拉第效率为 75%。根据计算结果,该催化剂依次经过氧化和去质子化步骤形成 [LFeIV(NH2)2]2+,然后经过双金属耦合形成 N-N 键。
{"title":"Oxidation of Ammonia Catalyzed by a Molecular Iron Complex: Translating Chemical Catalysis to Mediated Electrocatalysis.","authors":"Liang Liu, Samantha I Johnson, Aaron M Appel, R Morris Bullock","doi":"10.1002/anie.202402635","DOIUrl":"10.1002/anie.202402635","url":null,"abstract":"<p><p>Ammonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon-neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth-abundant transition metal complex, trans-[LFe<sup>II</sup>(MeCN)<sub>2</sub>][PF<sub>6</sub>]<sub>2</sub>, where L is a macrocyclic ligand bearing four N-heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N<sub>2</sub> per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator (p-MeOC<sub>6</sub>H<sub>4</sub>)<sub>3</sub>N exhibited a catalytic half-wave potential (E<sub>cat/2</sub>) of 0.18 V vs [Cp<sub>2</sub>Fe]<sup>+/0</sup> in MeCN, and achieved 9.3 turnovers of N<sub>2</sub> at an applied potential of 0.20 V vs [Cp<sub>2</sub>Fe]<sup>+/0</sup> at -20 °C in controlled-potential electrolysis, with a Faradaic efficiency of 75 %. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFe<sup>IV</sup>(NH<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>, and thereafter bimetallic coupling to form an N-N bond.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562097","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}
Pub Date : 2024-10-07Epub Date: 2024-09-05DOI: 10.1002/anie.202408673
Filip J Aubrecht, Kennalee Orme, Aiden Saul, Hongyi Cai, Tharindu A Ranathunge, Meredith N Silberstein, Benjamin R McDonald
Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra- and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co-solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion-specific interactions. In this study, we show for the first time that the ion-specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal- and ion-responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion-dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion-dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.
{"title":"Ion-Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes.","authors":"Filip J Aubrecht, Kennalee Orme, Aiden Saul, Hongyi Cai, Tharindu A Ranathunge, Meredith N Silberstein, Benjamin R McDonald","doi":"10.1002/anie.202408673","DOIUrl":"10.1002/anie.202408673","url":null,"abstract":"<p><p>Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra- and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co-solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion-specific interactions. In this study, we show for the first time that the ion-specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal- and ion-responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion-dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion-dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562091","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}
Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC systems suffer from limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO4 photoanodes with tailored deposition layers for customizing two PEC approaches toward C-N and C-P bond formation. Our process proceeds under mild reaction conditions, deploying easily available substrates and ultra-low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications.
{"title":"Customized Photoelectrochemical C-N and C-P Bond Formation Enabled by Tailored Deposition on Photoanodes.","authors":"Jinghao Wang, Caoyu Yang, Huiwen Gao, Lulu Zuo, Zhiyu Guo, Pengqi Yang, Siyang Li, Zhiyong Tang","doi":"10.1002/anie.202408901","DOIUrl":"10.1002/anie.202408901","url":null,"abstract":"<p><p>Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC systems suffer from limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO<sub>4</sub> photoanodes with tailored deposition layers for customizing two PEC approaches toward C-N and C-P bond formation. Our process proceeds under mild reaction conditions, deploying easily available substrates and ultra-low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141625437","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}
Pub Date : 2024-10-07Epub Date: 2024-09-05DOI: 10.1002/anie.202408849
Jiadong Chen, Tingjie Mao, Juan Wang, Jichang Wang, Shun Wang, Huile Jin
The electrochemical CO2 reduction reaction (CO2RR) to generate chemical fuels such as formate presents a promising route to a carbon-neutral future. However, its practical application is hindered by the competing CO production and hydrogen evolution reaction (HER), as well as the lack of pH-universal catalysts. Here, Te-modified Bi nanorods (Te-Bi NRs) were synthesized through in situ reconstruction of Bi2Te4O11 NRs under the CO2RR condition. Our study illustrates that the complex reconstruction process of Bi2Te4O11 NRs during CO2RR could be decoupled into three distinct steps, i.e., the destruction of Bi2Te4O11, the formation of Te/Bi phases, and the dissolution of Te. The thus-obtained Te-Bi NRs exhibit remarkably high performance in CO2RR towards formate production, showing high activity, selectivity, and stability across all pH conditions (acidic, neutral, and alkaline). In a flow cell reactor under neutral, alkaline, or acidic conditions, the catalysts achieved HCOOH Faradaic efficiencies of up to 94.3 %, 96.4 %, and 91.0 %, respectively, at a high current density of 300 mA cm-2. Density functional theory calculations, along with operando spectral measurements, reveal that Te manipulates the Bi sites to an electron-deficient state, enhancing the adsorption strength of the *OCHO intermediate, and significantly suppressing the competing HER and CO production. This study highlights the substantial influence of catalyst reconstruction under operational conditions and offers insights into designing highly active and stable electrocatalysts towards CO2RR.
电化学二氧化碳还原反应(CO2RR)的实际应用受到二氧化碳生成、氢进化反应(HER)等竞争性反应以及缺乏 pH 值通用催化剂的阻碍。在此,我们在 CO2RR 条件下通过原位重构 Bi2Te4O11 NRs 合成了 Te 修饰的 Bi 纳米棒(Te-Bi NRs)。我们的研究表明,Bi2Te4O11 NRs 在 CO2RR 过程中的复杂重构过程可以分解为三个不同的步骤,即 Bi2Te4O11 的破坏、Te/Bi 相的形成和 Te 的溶解。由此获得的 Te-Bi NR 在 CO2RR 生产甲酸盐方面表现出显著的高性能,在所有 pH 条件(酸性、中性和碱性)下都具有高活性、高选择性和高稳定性。在中性、碱性或酸性条件下的流动池反应器中,催化剂在 300 mA cm-2 的高电流密度下的 HCOOH 法拉第效率分别高达 94.3%、96.4% 和 91.0%。DFT 计算和操作光谱测量结果表明,Te 可使铋位点处于缺电子状态,从而增强*OCHO 中间体的吸附强度,并显著抑制 HER 和 CO 的竞争生成。这项研究强调了催化剂重构在操作条件下的重大影响,并为设计高活性、高稳定性的 CO2RR 电催化剂提供了启示。
{"title":"The Reconstruction of Bi<sub>2</sub>Te<sub>4</sub>O<sub>11</sub> Nanorods for Efficient and pH-universal Electrochemical CO<sub>2</sub> Reduction.","authors":"Jiadong Chen, Tingjie Mao, Juan Wang, Jichang Wang, Shun Wang, Huile Jin","doi":"10.1002/anie.202408849","DOIUrl":"10.1002/anie.202408849","url":null,"abstract":"<p><p>The electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to generate chemical fuels such as formate presents a promising route to a carbon-neutral future. However, its practical application is hindered by the competing CO production and hydrogen evolution reaction (HER), as well as the lack of pH-universal catalysts. Here, Te-modified Bi nanorods (Te-Bi NRs) were synthesized through in situ reconstruction of Bi<sub>2</sub>Te<sub>4</sub>O<sub>11</sub> NRs under the CO<sub>2</sub>RR condition. Our study illustrates that the complex reconstruction process of Bi<sub>2</sub>Te<sub>4</sub>O<sub>11</sub> NRs during CO<sub>2</sub>RR could be decoupled into three distinct steps, i.e., the destruction of Bi<sub>2</sub>Te<sub>4</sub>O<sub>11</sub>, the formation of Te/Bi phases, and the dissolution of Te. The thus-obtained Te-Bi NRs exhibit remarkably high performance in CO<sub>2</sub>RR towards formate production, showing high activity, selectivity, and stability across all pH conditions (acidic, neutral, and alkaline). In a flow cell reactor under neutral, alkaline, or acidic conditions, the catalysts achieved HCOOH Faradaic efficiencies of up to 94.3 %, 96.4 %, and 91.0 %, respectively, at a high current density of 300 mA cm<sup>-2</sup>. Density functional theory calculations, along with operando spectral measurements, reveal that Te manipulates the Bi sites to an electron-deficient state, enhancing the adsorption strength of the *OCHO intermediate, and significantly suppressing the competing HER and CO production. This study highlights the substantial influence of catalyst reconstruction under operational conditions and offers insights into designing highly active and stable electrocatalysts towards CO<sub>2</sub>RR.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589045","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}