Platinum–transition metal (PtM) alloys are among the most promising oxygen reduction reaction (ORR) catalysts, yet their practical deployment in proton-exchange membrane fuel cells (PEMFCs) is hindered by transition-metal dissolution, particle coarsening, and insufficient durability. Moreover, conventional alloying or intermetallic ordering strategies often aggravate these issues by inducing severe nanoparticle aggregation and instability. Here we report a controllable alloying–dealloying strategy to construct PtNi nanoparticles confined in an N-doped carbon framework (Pt1Ni1-x@Nix_NC). Ammonia-assisted dealloying produces a Pt-rich shell with an alloyed core, while the N-doped carbon anchors the released Ni atoms form Ni–N/C moieties, thereby suppressing agglomeration and strengthening metal–support interactions. This coordination–support coupling optimizes Pt 5d orbital occupation, weakens oxygen adsorption, and accelerates ORR kinetics. Consequently, Pt1Ni1-x@Nix_NC exhibits a half-wave potential of 0.932 V and an ultrahigh mass activity of 2.028 A mgPt−1, which is 8.75-fold higher than commercial Pt/C and among the best values reported to date for PtNi-based catalysts. Remarkably, it shows only a 6 mV half-wave potential loss after 30,000 cycles, demonstrating exceptional durability. In PEMFCs, the fuel cell delivers 975 mW cm−2 peak power density and retains 91.9% of initial performance, underscoring a generalizable approach for designing durable, high-performance low-PGM catalysts for next generation PEMFCs.
铂过渡金属（PtM）合金是最有前途的氧还原反应（ORR）催化剂之一，但其在质子交换膜燃料电池（pemfc）中的实际应用受到过渡金属溶解、颗粒粗化和耐久性不足的阻碍。此外，传统的合金化或金属间排序策略往往通过诱导严重的纳米颗粒聚集和不稳定性而加剧这些问题。在这里，我们报告了一种可控的合金化-脱合金策略，以构建限制在n掺杂碳框架中的PtNi纳米颗粒（Pt1Ni1-x@Nix_NC）。氨辅助脱合金产生了一个具有合金核的富pt壳，而n掺杂碳将释放的Ni原子锚定形成Ni - n /C基团，从而抑制团聚并加强金属-负载相互作用。这种配位-支撑耦合优化了Pt 5d轨道占用，减弱了氧吸附，加速了ORR动力学。因此，Pt1Ni1-x@Nix_NC具有0.932 V的半波电位和2.028 a mgPt−1的超高质量活性，比商用Pt/C高8.75倍，是迄今为止报道的ptni基催化剂的最佳值之一。值得注意的是，在30,000次循环后，它显示只有6 mV的半波潜在损失，显示出卓越的耐用性。在pemfc中，燃料电池可提供975 mW cm - 2的峰值功率密度，并保持91.9%的初始性能，这突显了为下一代pemfc设计耐用、高性能低pgm催化剂的通用方法。
{"title":"Harnessing Controlled Dealloying–Support Coupling for Ultrastable PtNi Catalysts in PEMFC Applications","authors":"Fei Guo, Manxi Gong, Longxiang Liu, Bochen Li, Ruwei Chen, Mengjun Gong, Wei Zong, Jianuo Chen, Qi Li, Jing Li, Yunpeng Zhong, Zeyi Zhang, Jianrui Feng, Rhodri Jervis, Guanjie He","doi":"10.1002/anie.4524344","DOIUrl":"https://doi.org/10.1002/anie.4524344","url":null,"abstract":"Platinum–transition metal (PtM) alloys are among the most promising oxygen reduction reaction (ORR) catalysts, yet their practical deployment in proton-exchange membrane fuel cells (PEMFCs) is hindered by transition-metal dissolution, particle coarsening, and insufficient durability. Moreover, conventional alloying or intermetallic ordering strategies often aggravate these issues by inducing severe nanoparticle aggregation and instability. Here we report a controllable alloying–dealloying strategy to construct PtNi nanoparticles confined in an N-doped carbon framework (Pt<sub>1</sub>Ni<sub>1-x</sub>@Ni<sub>x</sub>_NC). Ammonia-assisted dealloying produces a Pt-rich shell with an alloyed core, while the N-doped carbon anchors the released Ni atoms form Ni–N/C moieties, thereby suppressing agglomeration and strengthening metal–support interactions. This coordination–support coupling optimizes Pt 5d orbital occupation, weakens oxygen adsorption, and accelerates ORR kinetics. Consequently, Pt<sub>1</sub>Ni<sub>1-x</sub>@Ni<sub>x</sub>_NC exhibits a half-wave potential of 0.932 V and an ultrahigh mass activity of 2.028 A mgPt<sup>−1</sup>, which is 8.75-fold higher than commercial Pt/C and among the best values reported to date for PtNi-based catalysts. Remarkably, it shows only a 6 mV half-wave potential loss after 30,000 cycles, demonstrating exceptional durability. In PEMFCs, the fuel cell delivers 975 mW cm<sup>−2</sup> peak power density and retains 91.9% of initial performance, underscoring a generalizable approach for designing durable, high-performance low-PGM catalysts for next generation PEMFCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146412","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}
Yun Tang, Xiang-Ming Zeng, Xiaotian Wu, Minjian Wu, Lu Lin, Guo-Yu Yang, Liao-Yuan Yao
Photoluminescent metal nanoclusters hold promise for optoelectronics, photonics, and chemosensing, yet systematic modulation of their emission within a single system remains challenging. Here, we report two isostructural clusters, Au13@Au3-Cl and Au9Cu4@Au3-Cl, stabilized by a tridentate phosphine (NP3) metalloligand. Both adopt an unprecedented “Au9M4 (Au/Cu) icosahedron + Au3 crown” configuration and exhibit high solid-state PLQYs of 44.5% and 38.9%, respectively. In contrast, replacing NP3 with a monophosphine ligand (BPP) affords Au9Cu4-Cl lacking the Au3 crown, with a dramatically reduced PLQY of 0.6%, highlighting the crucial roles of NP3 and the Au3 crown in boosting luminescence. Distinct photophysical behaviors are observed: Au13@Au3-Cl shows phosphorescence, while Au9Cu4@Au3-Cl exhibits thermally activated delayed fluorescence (TADF), confirmed by femtosecond transient absorption spectroscopy. The role of Cu doping is further supported by the TADF activity of Au9Cu4-Cl. Coordinating anion substitution also modulates emission, with iodide promoting TADF in Au13@Au3-I. Moreover, the NP3 ligand confers reversible protonation-induced luminescence switching, enabling chemosensing potential. Collectively, these findings demonstrate a comprehensive investigation of TADF behavior and luminescence modulation in atomically precise metal nanoclusters, systematically engineered through heteroatom doping of the inner core, ligand design and anion exchange at the coordination surface, and outer-sphere complexation and protonation.
{"title":"Multifaceted Molecular Design Enables Comprehensive Luminescence Modulation in Metalloligand-Stabilized Gold Nanoclusters","authors":"Yun Tang, Xiang-Ming Zeng, Xiaotian Wu, Minjian Wu, Lu Lin, Guo-Yu Yang, Liao-Yuan Yao","doi":"10.1002/anie.202518269","DOIUrl":"https://doi.org/10.1002/anie.202518269","url":null,"abstract":"Photoluminescent metal nanoclusters hold promise for optoelectronics, photonics, and chemosensing, yet systematic modulation of their emission within a single system remains challenging. Here, we report two isostructural clusters, <b>Au<sub>13</sub>@Au<sub>3</sub>-Cl</b> and <b>Au<sub>9</sub>Cu<sub>4</sub>@Au<sub>3</sub>-Cl</b>, stabilized by a tridentate phosphine (NP<sub>3</sub>) metalloligand. Both adopt an unprecedented “Au<sub>9</sub>M<sub>4</sub> (Au/Cu) icosahedron + Au<sub>3</sub> crown” configuration and exhibit high solid-state PLQYs of 44.5% and 38.9%, respectively. In contrast, replacing NP<sub>3</sub> with a monophosphine ligand (BPP) affords <b>Au<sub>9</sub>Cu<sub>4</sub>-Cl</b> lacking the Au<sub>3</sub> crown, with a dramatically reduced PLQY of 0.6%, highlighting the crucial roles of NP<sub>3</sub> and the Au<sub>3</sub> crown in boosting luminescence. Distinct photophysical behaviors are observed: <b>Au<sub>13</sub>@Au<sub>3</sub>-Cl</b> shows phosphorescence, while <b>Au<sub>9</sub>Cu<sub>4</sub>@Au<sub>3</sub>-Cl</b> exhibits thermally activated delayed fluorescence (TADF), confirmed by femtosecond transient absorption spectroscopy. The role of Cu doping is further supported by the TADF activity of <b>Au<sub>9</sub>Cu<sub>4</sub>-Cl</b>. Coordinating anion substitution also modulates emission, with iodide promoting TADF in <b>Au<sub>13</sub>@Au<sub>3</sub>-I</b>. Moreover, the NP<sub>3</sub> ligand confers reversible protonation-induced luminescence switching, enabling chemosensing potential. Collectively, these findings demonstrate a comprehensive investigation of TADF behavior and luminescence modulation in atomically precise metal nanoclusters, systematically engineered through heteroatom doping of the inner core, ligand design and anion exchange at the coordination surface, and outer-sphere complexation and protonation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"93 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146415","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}
Oxygen, nitrogen, and halogen-containing functional groups are ubiquitous in complex small molecules. The installation of multiple carbon-heteroatom bonds by the simultaneous functionalization of contiguous C–H/C–C bonds in a selective fashion is highly desirable in polymers degradation, skeletal editing, and petroleum cracking. However, achieving simultaneous, multi-site functionalization of relatively inert C–C/C–H bonds with precise control over site-, regio-, and oxidation-state selectivity remains challenging, particularly due to competing overoxidation and decomposition. Here we report the electrooxidative selective C-C fragmentation of aromatic radical cations for cascade benzylic di- and trifunctionalization in simple alkylarenes by iterative dehydrogenation and oxygenation. Central to our approach is the controlled formation of olefin intermediates in situ at a rate carefully balanced to prevent polymerization and overoxidation. This strategy provides efficient access to diverse, high-value di- or trifunctionalized products, including di- and triacetates, 2-oxazolines, 1,2-dibromoethanes, 1,3-dibromo-2-ols, and 2-(bromomethyl)oxiranes via controlled 4-electron, 6-electron, or 10-electron oxidation events. Notably, the selective synthesis of di- versus trifunctionalization products is readily controlled through judicious choice of acids and nucleophiles.
{"title":"Electrooxidative C-C Fragmentation of Aromatic Radical Cations for Cascade Benzylic Multifunctionalization","authors":"Kai-Xuan Yang, Shu-Fan He, Yu-Rou Huang, Tianyi Xu, Yexin Wang, Ke-Xin Liu, Ling Zhang, Wenying Ai, Daixi Li, Tao Shen","doi":"10.1002/anie.202522498","DOIUrl":"https://doi.org/10.1002/anie.202522498","url":null,"abstract":"Oxygen, nitrogen, and halogen-containing functional groups are ubiquitous in complex small molecules. The installation of multiple carbon-heteroatom bonds by the simultaneous functionalization of contiguous C–H/C–C bonds in a selective fashion is highly desirable in polymers degradation, skeletal editing, and petroleum cracking. However, achieving simultaneous, multi-site functionalization of relatively inert C–C/C–H bonds with precise control over site-, regio-, and oxidation-state selectivity remains challenging, particularly due to competing overoxidation and decomposition. Here we report the electrooxidative selective C-C fragmentation of aromatic radical cations for cascade benzylic di- and trifunctionalization in simple alkylarenes by iterative dehydrogenation and oxygenation. Central to our approach is the controlled formation of olefin intermediates in situ at a rate carefully balanced to prevent polymerization and overoxidation. This strategy provides efficient access to diverse, high-value di- or trifunctionalized products, including di- and triacetates, 2-oxazolines, 1,2-dibromoethanes, 1,3-dibromo-2-ols, and 2-(bromomethyl)oxiranes via controlled 4-electron, 6-electron, or 10-electron oxidation events. Notably, the selective synthesis of di- versus trifunctionalization products is readily controlled through judicious choice of acids and nucleophiles.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146410","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}
Xianhong Chen, Yang Wang, Jiaxiong Zhu, Chunyi Zhi, Wai-Yeung Wong
Green electrochemical energy storage is essential for carbon neutrality, and alkaline zinc batteries offer a compelling solution due to their inherent safety, low cost, and high energy density. However, their performance is limited by parasitic reactions, including corrosion, gas evolution, and slow Zn/ZnO conversion kinetics stemming from inefficient dissociation of the tetrahydroxozincate [Zn(OH)42−] intermediate. We address this by designing a series of cobalt porphyrins (Co-4N, Co-3N-O, Co-3N-S) that modulate the metal center's charge density for accelerating Zn(OH)42− decomposition, and control Zn2+ transport through the carboxyl-functionalized peripheries. The Co-3N-O-modified electrolyte achieves exceptional stability, maintaining stable cycle for over 80,000 s at 5 mA cm−2, which is more than four times longer than the <20,000 s achieved by the conventional KOH + ZnO electrolyte. In Zn||Ni batteries, this molecularly engineered electrolyte enables 110 stable cycles at 1 mA cm−2, significantly outperforming the unmodified system, which sustained only 20 cycles. These findings elucidate a structure-kinetics relationship for zincate regulation and demonstrate how customized molecular asymmetry can overcome persistent challenges in aqueous battery chemistry, offering a pathway to high-performance, durable energy storage systems.
绿色电化学能量存储对于碳中和至关重要，碱性锌电池因其固有的安全性、低成本和高能量密度而提供了令人信服的解决方案。然而，它们的性能受到寄生反应的限制，包括腐蚀、气体释放以及由于四羟基锌酸盐[Zn(OH)42−]中间体解离效率低而导致的Zn/ZnO转化动力学缓慢。我们通过设计一系列钴卟啉（Co-4N, Co-3N-O, Co-3N-S）来解决这个问题，这些卟啉可以调节金属中心的电荷密度，加速Zn(OH)42−的分解，并控制Zn2+通过羧基功能化外围的传输。co - 3n - o修饰的电解质具有优异的稳定性，在5 mA cm - 2下保持超过80,000 s的稳定周期，这是传统KOH + ZnO电解质实现的20,000 s的四倍多。在Zn||镍电池中，这种分子工程电解质可以在1ma cm - 2下实现110次稳定循环，显著优于未修改的系统，后者只能持续20次循环。这些发现阐明了锌酸盐调节的结构-动力学关系，并展示了定制分子不对称如何克服水电池化学中的持续挑战，为高性能、耐用的储能系统提供了一条途径。
{"title":"Asymmetric Electrolytes Govern Tetrahydroxozincate Dynamics for Stable Alkaline Zinc Batteries","authors":"Xianhong Chen, Yang Wang, Jiaxiong Zhu, Chunyi Zhi, Wai-Yeung Wong","doi":"10.1002/anie.202524438","DOIUrl":"https://doi.org/10.1002/anie.202524438","url":null,"abstract":"Green electrochemical energy storage is essential for carbon neutrality, and alkaline zinc batteries offer a compelling solution due to their inherent safety, low cost, and high energy density. However, their performance is limited by parasitic reactions, including corrosion, gas evolution, and slow Zn/ZnO conversion kinetics stemming from inefficient dissociation of the tetrahydroxozincate [Zn(OH)<sub>4</sub><sup>2−</sup>] intermediate. We address this by designing a series of cobalt porphyrins (Co-4N, Co-3N-O, Co-3N-S) that modulate the metal center's charge density for accelerating Zn(OH)<sub>4</sub><sup>2</sup><sup>−</sup> decomposition, and control Zn<sup>2</sup><sup>+</sup> transport through the carboxyl-functionalized peripheries. The Co-3N-O-modified electrolyte achieves exceptional stability, maintaining stable cycle for over 80,000 s at 5 mA cm<sup>−</sup><sup>2</sup>, which is more than four times longer than the <20,000 s achieved by the conventional KOH + ZnO electrolyte. In Zn||Ni batteries, this molecularly engineered electrolyte enables 110 stable cycles at 1 mA cm<sup>−2</sup>, significantly outperforming the unmodified system, which sustained only 20 cycles. These findings elucidate a structure-kinetics relationship for zincate regulation and demonstrate how customized molecular asymmetry can overcome persistent challenges in aqueous battery chemistry, offering a pathway to high-performance, durable energy storage systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139024","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}
Caroline V. I. Andersson, Sumali G. T. Mudiyanselage, Martin D. Peeks, Asja A. Kroeger, Jemma I. Virtue, Maximilian Mann, Justin M. Chalker, Michelle L. Coote, Martin R. Johnston, Witold M. Bloch
The removal of perfluoroalkyl substances (PFAS) from water is critical to protect human health and the environment. However, removing short-chain PFAS remains a significant challenge, and a molecular-level understanding of their binding is lacking. Here, we utilise a metal-organic cage (MOC 1) as a model “pore” to elucidate the host-guest chemistry of short- and long-chain PFAS in water. X-ray crystallography of six 1·(PFAS)n complexes reveals a broad range of PFAS are encapsulated as anionic aggregates, with the degree of guest-guest aggregation decreasing as the fluoroalkyl chain length increases. 1H and 19F NMR spectroscopy, together with isothermal titration calorimetry reveal the cage host displays unusually large, entropy-driven association constants in water (log K ≥ 5) which remain high for short-chain PFAS. Doping mesoporous silica 60A with only ∼1 wt% of the cage results in a host-in-host adsorbent that removes >98% of short- and long-chain PFAS at environmentally relevant concentrations under flow-through conditions. The adsorbent exhibits rapid PFAS uptake with high selectivity over common water-borne anions and full regenerability. These findings translate host-guest chemistry into an effective materials platform for PFAS remediation, including short-chain species that evade conventional removal methods.
{"title":"Efficient Removal of Short-Chain Perfluoroalkyl Substances by Cavity-Directed Aggregation in a Molecular Cage Host","authors":"Caroline V. I. Andersson, Sumali G. T. Mudiyanselage, Martin D. Peeks, Asja A. Kroeger, Jemma I. Virtue, Maximilian Mann, Justin M. Chalker, Michelle L. Coote, Martin R. Johnston, Witold M. Bloch","doi":"10.1002/anie.202526027","DOIUrl":"https://doi.org/10.1002/anie.202526027","url":null,"abstract":"The removal of perfluoroalkyl substances (PFAS) from water is critical to protect human health and the environment. However, removing short-chain PFAS remains a significant challenge, and a molecular-level understanding of their binding is lacking. Here, we utilise a metal-organic cage (MOC <b>1</b>) as a model “pore” to elucidate the host-guest chemistry of short- and long-chain PFAS in water. X-ray crystallography of six <b>1</b>·(PFAS)<sub>n</sub> complexes reveals a broad range of PFAS are encapsulated as anionic aggregates, with the degree of guest-guest aggregation decreasing as the fluoroalkyl chain length increases. <sup>1</sup>H and <sup>19</sup>F NMR spectroscopy, together with isothermal titration calorimetry reveal the cage host displays unusually large, entropy-driven association constants in water (log <i>K</i> ≥ 5) which remain high for short-chain PFAS. Doping mesoporous silica 60A with only ∼1 wt% of the cage results in a host-in-host adsorbent that removes >98% of short- and long-chain PFAS at environmentally relevant concentrations under flow-through conditions. The adsorbent exhibits rapid PFAS uptake with high selectivity over common water-borne anions and full regenerability. These findings translate host-guest chemistry into an effective materials platform for PFAS remediation, including short-chain species that evade conventional removal methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146382","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}
Dawid D. Kruger, María Cabrero-Antonino, Silvio Osella, Feiyan Xu, Jiaguo Yu, Ana Primo, Hermenegildo Garcia
The rational design of heterostructured photocatalysts that simultaneously enable efficient carrier separation, photothermal synergy, and controllable reaction pathways is crucial for advancing CO2 conversion. Here, a Ni/Ti3C2Clx MXene heterojunction is synthesized via Lewis acid molten-salt etching, featuring ultrathin Ni platelets strongly anchored to the MXene substrate through interfacial TiNi3 bonding. This architecture establishes an S-scheme charge transfer pathway, as evidenced by in situ irradiated X-ray photoelectron and X-ray absorption spectroscopy, which confirm efficient carrier transfer and separation, while femtosecond transient absorption spectroscopy reveals ultrafast interfacial dynamics. Under photothermal conditions, the cooperative interplay of metallic Ni, surface NiOx, and the conductive MXene substrate couples directional charge migration with thermally assisted molecular activation and barrier lowering, thereby enabling regulated CO2 hydrogenation product distribution between CH4 and CH3OH. Density functional theory demonstrates that surface-state evolution, rather than simple oxidation degree, modulates adsorption energetics and alters the relative barriers of CH4 and CH3OH pathways, such that moderately oxidized Ni–NiOx interfacial ensembles favour methanol forming intermediates, whereas extensive oxidation suppresses CH3OH formation. Collectively, these findings demonstrate a robust strategy for exploiting MXene-based heterojunction interfaces in photothermal catalysis and underscore the pivotal role of surface state regulated reaction pathways in steering product distribution during CO2 hydrogenation.
{"title":"Surface-State–Regulated Product Distribution in Photothermal CO2 Hydrogenation Over MXene-Based S-Scheme Catalyst","authors":"Dawid D. Kruger, María Cabrero-Antonino, Silvio Osella, Feiyan Xu, Jiaguo Yu, Ana Primo, Hermenegildo Garcia","doi":"10.1002/anie.8425918","DOIUrl":"https://doi.org/10.1002/anie.8425918","url":null,"abstract":"The rational design of heterostructured photocatalysts that simultaneously enable efficient carrier separation, photothermal synergy, and controllable reaction pathways is crucial for advancing CO<sub>2</sub> conversion. Here, a Ni/Ti<sub>3</sub>C<sub>2</sub>Cl<sub>x</sub> MXene heterojunction is synthesized via Lewis acid molten-salt etching, featuring ultrathin Ni platelets strongly anchored to the MXene substrate through interfacial TiNi<sub>3</sub> bonding. This architecture establishes an S-scheme charge transfer pathway, as evidenced by in situ irradiated X-ray photoelectron and X-ray absorption spectroscopy, which confirm efficient carrier transfer and separation, while femtosecond transient absorption spectroscopy reveals ultrafast interfacial dynamics. Under photothermal conditions, the cooperative interplay of metallic Ni, surface NiO<sub>x</sub>, and the conductive MXene substrate couples directional charge migration with thermally assisted molecular activation and barrier lowering, thereby enabling regulated CO<sub>2</sub> hydrogenation product distribution between CH<sub>4</sub> and CH<sub>3</sub>OH. Density functional theory demonstrates that surface-state evolution, rather than simple oxidation degree, modulates adsorption energetics and alters the relative barriers of CH<sub>4</sub> and CH<sub>3</sub>OH pathways, such that moderately oxidized Ni–NiO<sub>x</sub> interfacial ensembles favour methanol forming intermediates, whereas extensive oxidation suppresses CH<sub>3</sub>OH formation. Collectively, these findings demonstrate a robust strategy for exploiting MXene-based heterojunction interfaces in photothermal catalysis and underscore the pivotal role of surface state regulated reaction pathways in steering product distribution during CO<sub>2</sub> hydrogenation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"60 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146416","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 : 2026-02-09DOI: 10.1002/anie.2026-m0402125100
Yong-Zheng Zhang, Tao He, Xiang-Jing Kong, Yingjie Wang, Lin-Hua Xie, Jian-Rong Li
In the Research Article (e22510), Tao He, Jian-Rong Li, and co-workers report a building-unit symmetry tuning strategy that enables the first csq-type pyrazolate metal-organic framework (MOF). The resulting mesoporous framework integrates high structural robustness with redox activity, allowing rapid and fully reversible O2 sorption. Mechanistic study directly visualizes the reversible redox process, establishing a platform for elucidating gas-framework interactions and redox chemistry in stable MOFs.
{"title":"Outside Front Cover: A Redox-Active Mesoporous Cobalt–Pyrazolate Framework for Reversible O2 Sorption","authors":"Yong-Zheng Zhang, Tao He, Xiang-Jing Kong, Yingjie Wang, Lin-Hua Xie, Jian-Rong Li","doi":"10.1002/anie.2026-m0402125100","DOIUrl":"https://doi.org/10.1002/anie.2026-m0402125100","url":null,"abstract":"In the Research Article (e22510), Tao He, Jian-Rong Li, and co-workers report a building-unit symmetry tuning strategy that enables the first csq-type pyrazolate metal-organic framework (MOF). The resulting mesoporous framework integrates high structural robustness with redox activity, allowing rapid and fully reversible O<sub>2</sub> sorption. Mechanistic study directly visualizes the reversible redox process, establishing a platform for elucidating gas-framework interactions and redox chemistry in stable MOFs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146542","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}
Meltable organic–inorganic hybrid semiconductors are attractive for their potential for melt-based processing. Although meltable semiconducting metal halide perovskites have been extensively studied, meltable semiconducting coordination polymers (CPs) remain scarce, despite their excellent structural designability and the tunability of their optoelectronic properties. We report a new family of meltable semiconductive Pb(II) benzenethiolate CPs bearing long alkyl chains, formulated as [Pb(SPhOC6)2]n (KGF-34(C6); HSPhOC6 = 4-hexyloxybenzenethiol). For comparison, we also synthesized the classical analogue [Pb(SC6)2]n (KGF-59(C6); HSC6 = 1-hexanethiol). Single-crystal X-ray diffraction analyses revealed that both KGF-34(C6) and KGF-59(C6) adopt 2D architectures, albeit with distinct inorganic (–Pb–S–)n networks. A comprehensive characterization of the semiconducting properties, combined with first-principles calculations, revealed that KGF-34(C6) exhibits significantly higher photoconductivity, a narrower band gap, and a larger band dispersion than KGF-59(C6), attributable to differences in their inorganic (–Pb–S–)n network structures. Furthermore, both KGF-34(C6) and KGF-59(C6) exhibit multiple phase transitions, including melting and liquid crystalline formation, enabling the fabrication of optoelectronic devices via melt processing. Notably, this is the first report of meltable semiconducting CPs comprising benzenethiol-derived ligands. These findings offer a rational design strategy for developing melt-processable semiconductive materials based on metal–benzenethiolate CPs.
可熔融有机-无机杂化半导体因其在熔融基加工方面的潜力而具有吸引力。虽然可熔融半导体金属卤化物钙钛矿已经得到了广泛的研究，但可熔融半导体配位聚合物（CPs）仍然很少，尽管它们具有良好的结构可设计性和光电性能可调性。我们报道了一个新的可熔融半导体Pb（II）苯硫代酸CPs家族，它含有长烷基链，分子式为[Pb(SPhOC6)2]n (KGF-34(C6)；HSPhOC6 = 4-己氧基苯硫醇)。为了比较，我们还合成了经典类似物[Pb(SC6)2]n (KGF-59(C6)；HSC6 = 1-己硫醇)。单晶x射线衍射分析显示，KGF-34（C6）和KGF-59（C6）均采用二维结构，尽管具有不同的无机（- pb - s -）n网络。综合表征半导体性质，结合第一性原理计算，表明KGF-34（C6）具有比KGF-59（C6）更高的光电导率，更窄的带隙和更大的带色散，这是由于它们的无机（- pb - s -）n网络结构的差异。此外，KGF-34（C6）和KGF-59（C6）均表现出多种相变，包括熔融和液晶形成，从而能够通过熔融加工制造光电器件。值得注意的是，这是首次报道含有苯乙醇衍生配体的可熔融半导体CPs。这些发现为开发基于金属-苯磺酸CPs的可熔融加工半导体材料提供了合理的设计策略。
{"title":"Meltable Semiconductive Lead–Thiolate Coordination Polymers with Long Alkyl Chains","authors":"Ryohei Akiyoshi, Shunya Takamura, Chie Sawada, Naohiro Takahashi, Takashi Okubo, Akinori Saeki, Zi Lang Goo, Kunihisa Sugimoto, Yuki Mori, Shogo Kawaguchi, Yuiga Nakamura, Toshiaki Ina, Misaki Katayama, Hiroki Yamada, Seiya Shimono, Takuya Kurihara, Kazuyoshi Ogasawara, Daisuke Tanaka","doi":"10.1002/anie.202518379","DOIUrl":"https://doi.org/10.1002/anie.202518379","url":null,"abstract":"Meltable organic–inorganic hybrid semiconductors are attractive for their potential for melt-based processing. Although meltable semiconducting metal halide perovskites have been extensively studied, meltable semiconducting coordination polymers (CPs) remain scarce, despite their excellent structural designability and the tunability of their optoelectronic properties. We report a new family of meltable semiconductive Pb(II) benzenethiolate CPs bearing long alkyl chains, formulated as [Pb(SPhOC<sub>6</sub>)<sub>2</sub>]<i><sub>n</sub></i> (<b>KGF-34(C6)</b>; HSPhOC<sub>6</sub> = 4-hexyloxybenzenethiol). For comparison, we also synthesized the classical analogue [Pb(SC<sub>6</sub>)<sub>2</sub>]<i><sub>n</sub></i> (<b>KGF-59(C6)</b>; HSC<sub>6</sub> = 1-hexanethiol). Single-crystal X-ray diffraction analyses revealed that both <b>KGF-34(C6)</b> and <b>KGF-59(C6)</b> adopt 2D architectures, albeit with distinct inorganic (–Pb–S–)<i><sub>n</sub></i> networks. A comprehensive characterization of the semiconducting properties, combined with first-principles calculations, revealed that <b>KGF-34(C6)</b> exhibits significantly higher photoconductivity, a narrower band gap, and a larger band dispersion than <b>KGF-59(C6)</b>, attributable to differences in their inorganic (–Pb–S–)<i><sub>n</sub></i> network structures. Furthermore, both <b>KGF-34(C6)</b> and <b>KGF-59(C6)</b> exhibit multiple phase transitions, including melting and liquid crystalline formation, enabling the fabrication of optoelectronic devices via melt processing. Notably, this is the first report of meltable semiconducting CPs comprising benzenethiol-derived ligands. These findings offer a rational design strategy for developing melt-processable semiconductive materials based on metal–benzenethiolate CPs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"48 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139066","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}
Shengjie Huang, Yongrui Luo, Xunchu Cheng, Long Lu, Qilong Shen
We report herein the first copper-mediated three-component modular synthesis of N-fluoroalkyl amides from fluoroalkylcopper species ([CuI─CF3], [CuI─CF2CO2Et], and [CuI─C2F5]), a nitrene precursor (dioxazolone), and an electrophile, featuring broad substrate scope and the unprecedented construction of acyclic N-C2F5 and N-CF2CO2Et structures. The reaction proceeds via reaction of the dioxazolone with the fluoroalkylcopper complex to generate a nitrene/Cu intermediate, followed by nitrene migratory insertion into the [CuI─CRf] bond as the pivotal step that directly forges the N–fluoroalkyl bond. Such a key step was supported by isolation and single-crystal x-ray characterization of intermediates [(L1)CuIN(CF3)(COAr)] 5c and [CuI(N(CF3)(COAr))2]−5d. Leveraging the versatile reactivity of copper, these intermediates react with various electrophiles to access a wide range of N-fluoroalkyl-N-alkyl(aryl)amides, and the derivatization of several drug molecules further demonstrates the synthetic utility of this approach.
本文首次报道了由氟烷基铜（[CuI─CF3]、[CuI─CF2CO2Et]和[CuI─C2F5]）、亚硝基前体（二氧唑酮）和亲电试剂组成的铜介导的三组分模块化合成n -氟烷基酰胺，具有广泛的底物范围和前所未有的无环N-C2F5和N-CF2CO2Et结构。该反应通过二恶唑酮与氟烷基铜配合物反应生成亚硝基/Cu中间体，然后亚硝基迁移插入[CuI─CRf]键，这是直接形成n -氟烷基键的关键步骤。中间体[(L1)CuIN(CF3)(COAr)] 5c和[CuI(N(CF3)(COAr))2]−5d的分离和单晶x射线表征支持了这一关键步骤。利用铜的多功能反应活性，这些中间体与各种亲电试剂反应，获得广泛的n -氟烷基- n -烷基（芳基）酰胺，并且几种药物分子的衍生化进一步证明了这种方法的合成实用性。
{"title":"A Modular Approach to N-Fluoroalkyl Amides via Nitrene Insertion Into Fluoroalkylcopper(I)","authors":"Shengjie Huang, Yongrui Luo, Xunchu Cheng, Long Lu, Qilong Shen","doi":"10.1002/anie.1753273","DOIUrl":"https://doi.org/10.1002/anie.1753273","url":null,"abstract":"We report herein the first copper-mediated three-component modular synthesis of <i>N</i>-fluoroalkyl amides from fluoroalkylcopper species ([Cu<sup>I</sup>─CF<sub>3</sub>], [Cu<sup>I</sup>─CF<sub>2</sub>CO<sub>2</sub>Et], and [Cu<sup>I</sup>─C<sub>2</sub>F<sub>5</sub>]), a nitrene precursor (dioxazolone), and an electrophile, featuring broad substrate scope and the unprecedented construction of acyclic <i>N</i>-C<sub>2</sub>F<sub>5</sub> and <i>N</i>-CF<sub>2</sub>CO<sub>2</sub>Et structures. The reaction proceeds via reaction of the dioxazolone with the fluoroalkylcopper complex to generate a nitrene/Cu intermediate, followed by nitrene migratory insertion into the [Cu<sup>I</sup>─C<sub>Rf</sub>] bond as the pivotal step that directly forges the <i>N–</i>fluoroalkyl bond. Such a key step was supported by isolation and single-crystal x-ray characterization of intermediates [(<b>L1</b>)Cu<sup>I</sup>N(CF<sub>3</sub>)(COAr)] <b>5c</b> and [Cu<sup>I</sup>(N(CF<sub>3</sub>)(COAr))<sub>2</sub>]<sup>−</sup> <b>5d</b>. Leveraging the versatile reactivity of copper, these intermediates react with various electrophiles to access a wide range of <i>N</i>-fluoroalkyl-<i>N</i>-alkyl(aryl)amides, and the derivatization of several drug molecules further demonstrates the synthetic utility of this approach.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146407","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 : 2026-02-09DOI: 10.1002/anie.2026-m0402121700
Fan Cao, Zhimin Cao, Nuojin Yao, Ting Yang, Tianci He, Lin Cheng, Liping Cao
In the Research Article (e23981), Lin Cheng, Liping Cao, and co-workers designed and synthesized a crown-ether-functionalized tetraphenylethene-based cationic cage. This multi-cavity molecular cage establishes a multi-domain cooperative hydrophobic microenvironment that enhances hydrogen bonding among sequence-diverse dinucleotides in aqueous conditions. The study provides valuable insights into the sequence-dependent diversity of base hydrogen-bonding structures within artificial systems, potentially uncovering patterns that may also be present in nature.
{"title":"Outside Back Cover: Unraveling Biomimetic Hydrogen Bonds of Dinucleotides by a Crown-Ether-Functionalized Tetraphenylethene-Based Cage","authors":"Fan Cao, Zhimin Cao, Nuojin Yao, Ting Yang, Tianci He, Lin Cheng, Liping Cao","doi":"10.1002/anie.2026-m0402121700","DOIUrl":"https://doi.org/10.1002/anie.2026-m0402121700","url":null,"abstract":"In the Research Article (e23981), Lin Cheng, Liping Cao, and co-workers designed and synthesized a crown-ether-functionalized tetraphenylethene-based cationic cage. This multi-cavity molecular cage establishes a multi-domain cooperative hydrophobic microenvironment that enhances hydrogen bonding among sequence-diverse dinucleotides in aqueous conditions. The study provides valuable insights into the sequence-dependent diversity of base hydrogen-bonding structures within artificial systems, potentially uncovering patterns that may also be present in nature.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"315 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146543","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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