The underdevelopment of electron transport layer (ETL) materials remains a critical bottleneck limiting the overall photovoltaic performance of inverted perovskite solar cells (PSCs). Fullerene derivatives, such as PCBM, are widely employed ETL materials in PSCs due to their excellent electron affinity and energy level alignment with perovskite layer. However, PCBM suffers from high energy disorder, self-aggregation predilection, and insufficient defect passivation ability, leading to significant charge carrier recombination and accumulation at interfaces. Herein, a phosphate-substituted fullerene derivative, FuPE, is developed to enhance the performance of PCBM-based ETLs for PSCs. Incorporating FuPE efficiently compacts molecular stacking, enforces crystallinity and intermolecular interaction, suppresses self-aggregation and improves interfacial compatibility for the FuPE:PCBM blend. Such endows the FuPE:PCBM blend film with enhanced electron mobility (0.183 cm2 V-1 s-1), lower trap density, more uniform film morphology, and superior defect-passivation ability, compared to the PCBM pristine one. Consequently, PSCs employing FuPE:PCBM achieve reduced trap-assisted recombination, enhanced charge carrier extraction, and thus a remarkable power conversion efficiency exceeding 26% alongside improved operational stability. This work highlights an effective strategy for optimizing fullerene-based ETLs, advancing the development of highly efficient and durable PSCs.
{"title":"Compacting Molecular Stacking and Inhibiting Self-Aggregation in Fullerene Transporting Layer for Efficient and Stable Perovskite Solar Cells","authors":"Dan He, Jiahao Zhang, Xue-Yuan Gong, Xinying Ruan, Xin-Bo Ma, Chaoyi Yao, Xingxing Shen, Ming-Hua Li, Jianqi Zhang, Jin-Song Hu, Chunru Wang, Fuwen Zhao","doi":"10.1002/anie.202502950","DOIUrl":"https://doi.org/10.1002/anie.202502950","url":null,"abstract":"The underdevelopment of electron transport layer (ETL) materials remains a critical bottleneck limiting the overall photovoltaic performance of inverted perovskite solar cells (PSCs). Fullerene derivatives, such as PCBM, are widely employed ETL materials in PSCs due to their excellent electron affinity and energy level alignment with perovskite layer. However, PCBM suffers from high energy disorder, self-aggregation predilection, and insufficient defect passivation ability, leading to significant charge carrier recombination and accumulation at interfaces. Herein, a phosphate-substituted fullerene derivative, FuPE, is developed to enhance the performance of PCBM-based ETLs for PSCs. Incorporating FuPE efficiently compacts molecular stacking, enforces crystallinity and intermolecular interaction, suppresses self-aggregation and improves interfacial compatibility for the FuPE:PCBM blend. Such endows the FuPE:PCBM blend film with enhanced electron mobility (0.183 cm2 V-1 s-1), lower trap density, more uniform film morphology, and superior defect-passivation ability, compared to the PCBM pristine one. Consequently, PSCs employing FuPE:PCBM achieve reduced trap-assisted recombination, enhanced charge carrier extraction, and thus a remarkable power conversion efficiency exceeding 26% alongside improved operational stability. This work highlights an effective strategy for optimizing fullerene-based ETLs, advancing the development of highly efficient and durable PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"33 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672723","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}
Xiyue Dong, Hao Zhang, Jiangnan Li, Liu Yang, Yuting Ma, Hang Liu, Ziyang Hu, Yongsheng Liu
Two dimensional (2D) Ruddlesden–Popper (RP) perovskites have emerged as promising photovoltaic materials. However, their further improvement in photovoltaic efficiency is hindered by the large dielectric mismatch and high exciton binding energy caused by the insulating spacers. Herein, two semiconductor spacers, namely MeBThMA and CNBThMA, were developed for 2D RP perovskite solar cells. In contrast to MeBThMA, the CNBThMA spacer, which features a donor-acceptor (D-A) structure, exhibits a larger dipole moment and adopts a face-to-face molecular stacking arrangement in the single crystal. The unique D-A structure effectively eliminates the dielectric mismatch between the organic and inorganic layers, contributing the formation of energy levels, adjusting the anisotropic charge transport properties, and improving the film quality of layered RP perovskites. Consequently, the devices based on CNBThMA (nominal n = 5) achieved a champion efficiency of 20.82%, which is a record efficiency for 2D RP PSCs using semiconductor spacers to the best of our knowledge. Our work pioneers a novel way to design organic semiconductor spacers using D-A structure for highly efficient 2D PSCs.
{"title":"Semiconductor Spacers with Donor-Acceptor Structure Drive 2D Ruddlesden-Popper Perovskite Solar Cells Beyond 20% Efficiency","authors":"Xiyue Dong, Hao Zhang, Jiangnan Li, Liu Yang, Yuting Ma, Hang Liu, Ziyang Hu, Yongsheng Liu","doi":"10.1002/anie.202501210","DOIUrl":"https://doi.org/10.1002/anie.202501210","url":null,"abstract":"Two dimensional (2D) Ruddlesden–Popper (RP) perovskites have emerged as promising photovoltaic materials. However, their further improvement in photovoltaic efficiency is hindered by the large dielectric mismatch and high exciton binding energy caused by the insulating spacers. Herein, two semiconductor spacers, namely MeBThMA and CNBThMA, were developed for 2D RP perovskite solar cells. In contrast to MeBThMA, the CNBThMA spacer, which features a donor-acceptor (D-A) structure, exhibits a larger dipole moment and adopts a face-to-face molecular stacking arrangement in the single crystal. The unique D-A structure effectively eliminates the dielectric mismatch between the organic and inorganic layers, contributing the formation of energy levels, adjusting the anisotropic charge transport properties, and improving the film quality of layered RP perovskites. Consequently, the devices based on CNBThMA (nominal n = 5) achieved a champion efficiency of 20.82%, which is a record efficiency for 2D RP PSCs using semiconductor spacers to the best of our knowledge. Our work pioneers a novel way to design organic semiconductor spacers using D-A structure for highly efficient 2D PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672721","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}
Samantha L. Le, Christopher R. O'Connor, Taek-Seung Kim, Christian Reece
Metastable surface states play a crucial yet poorly understood role in catalysis. However, they are difficult to isolate and even harder to identify. In their Communication (e202423880), Christian Reece et al. successfully isolate and identify a highly active metastable surface state over Pt nanoparticles, which forms after CO desorbs from well-coordinated Pt sites. The cover image is a stylised representation of how this state emerges following CO desorption.
{"title":"Outside Front Cover: A Metastable State Facilitates Low Temperature CO Oxidation over Pt Nanoparticles","authors":"Samantha L. Le, Christopher R. O'Connor, Taek-Seung Kim, Christian Reece","doi":"10.1002/anie.202505562","DOIUrl":"https://doi.org/10.1002/anie.202505562","url":null,"abstract":"Metastable surface states play a crucial yet poorly understood role in catalysis. However, they are difficult to isolate and even harder to identify. In their Communication (e202423880), Christian Reece et al. successfully isolate and identify a highly active metastable surface state over Pt nanoparticles, which forms after CO desorbs from well-coordinated Pt sites. The cover image is a stylised representation of how this state emerges following CO desorption.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666567","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}
Kartick Chandra Majhi, Hongjiang Chen, Asma Batool, Qi Zhu, Yangxin Jin, Shengqin Liu, Patrick H.-L. Sit, Jason Chun-Ho Lam
Nitrate electrocatalytic reduction to ammonia occurs with exceptional performance on ultrathin-sheet-assembled Fe80Ni20 nanoflowers, as described by Jason Lam et al. in their Research Article (e202500167). Mechanistic studies revealed that NO3<M-> preferentially adsorbs and is reduced to NO2<M-> on the Fe surface. Subsequently, NO2<M-> is efficiently hydrogenated to NH3 on the Ni surface. This in-tandem mechanism between Fe and Ni significantly enhances the electrocatalytic reduction of NO3<M-> to NH3.
{"title":"Outside Back Cover: In-tandem Electrochemical Reduction of Nitrate to Ammonia on Ultrathin-Sheet-Assembled Iron–Nickel Alloy Nanoflowers","authors":"Kartick Chandra Majhi, Hongjiang Chen, Asma Batool, Qi Zhu, Yangxin Jin, Shengqin Liu, Patrick H.-L. Sit, Jason Chun-Ho Lam","doi":"10.1002/anie.202505571","DOIUrl":"https://doi.org/10.1002/anie.202505571","url":null,"abstract":"Nitrate electrocatalytic reduction to ammonia occurs with exceptional performance on ultrathin-sheet-assembled Fe<sub>80</sub>Ni<sub>20</sub> nanoflowers, as described by Jason Lam et al. in their Research Article (e202500167). Mechanistic studies revealed that NO<sub>3</sub><sup><M-></sup> preferentially adsorbs and is reduced to NO<sub>2</sub><sup><M-></sup> on the Fe surface. Subsequently, NO<sub>2</sub><sup><M-></sup> is efficiently hydrogenated to NH<sub>3</sub> on the Ni surface. This in-tandem mechanism between Fe and Ni significantly enhances the electrocatalytic reduction of NO<sub>3</sub><sup><M-></sup> to NH<sub>3</sub>.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666569","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}
Yue Han, Pingxia Zhang, Heng Zhou, Tong Zhao, Karin Odelius, Minna Hakkarainen
A dual circularity concept to prevent plastic waste accumulation is presented by Yue Han and co-workers in their Research Article (e202421431). The concept is exemplified for triarylmethane-containing polyesters and their facile closed-loop recyclability via complementary mechanical and chemical routes. For the polymers with dual circularity, it is recommended to proceed with mechanical recycling when we can, and switch to chemical recycling when we must.
{"title":"Inside Front Cover: Molecular Design for Dual Circularity: Polyester with Complementary Mechanical and Chemical Recyclability under Mild Conditions","authors":"Yue Han, Pingxia Zhang, Heng Zhou, Tong Zhao, Karin Odelius, Minna Hakkarainen","doi":"10.1002/anie.202505568","DOIUrl":"https://doi.org/10.1002/anie.202505568","url":null,"abstract":"A dual circularity concept to prevent plastic waste accumulation is presented by Yue Han and co-workers in their Research Article (e202421431). The concept is exemplified for triarylmethane-containing polyesters and their facile closed-loop recyclability via complementary mechanical and chemical routes. For the polymers with dual circularity, it is recommended to proceed with mechanical recycling when we can, and switch to chemical recycling when we must.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666570","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}
Qia-Chun Lin, Wei-Ming Liao, Jiayu Li, Bowei Ye, Da-Tang Chen, Xiao-Xiang Zhou, Peng-Hui Li, Meng Li, Ming-De Li, Jun He
In their Research Article (e202423070), Jun He, Wei-Ming Liao et al. report the construction of metal-organic frameworks (MOFs) using carbazole linker and trinuclear clusters, which facilitate photoinduced ligand-to-cluster charge transfer (LCCT). The study reveals that the photocatalytic performance for overall water splitting (OWS) via a direct LCCT pathway surpassed that of an indirect LCCT pathway. The direct LCCT mechanism is pivotal in maximizing photon utilization efficiency and ensuring broad-spectrum OWS.
{"title":"Inside Front Cover: High-Performance Overall Water Splitting Dominated by Direct Ligand-to-Cluster Photoexcitation in Metal−Organic Frameworks","authors":"Qia-Chun Lin, Wei-Ming Liao, Jiayu Li, Bowei Ye, Da-Tang Chen, Xiao-Xiang Zhou, Peng-Hui Li, Meng Li, Ming-De Li, Jun He","doi":"10.1002/anie.202505566","DOIUrl":"https://doi.org/10.1002/anie.202505566","url":null,"abstract":"In their Research Article (e202423070), Jun He, Wei-Ming Liao et al. report the construction of metal-organic frameworks (MOFs) using carbazole linker and trinuclear clusters, which facilitate photoinduced ligand-to-cluster charge transfer (LCCT). The study reveals that the photocatalytic performance for overall water splitting (OWS) via a direct LCCT pathway surpassed that of an indirect LCCT pathway. The direct LCCT mechanism is pivotal in maximizing photon utilization efficiency and ensuring broad-spectrum OWS.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666449","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}
High‐entropy alloys (HEA) are promising catalyst materials for important energy transformations. So far, the focus has been on platinum‐group metals which possess excellent catalytic performance and similar properties, thus being easy to synthesize. However, incorporating more abundant and cheaper elements is preferable for large‐scale applications and is fundamentally more interesting as elements with different properties are expected to greatly affect the structural and electronic characteristics of the resulting alloy. Unfortunately, significant differences in elemental properties greatly complicate the synthesis and require extreme reaction conditions. In this work, we demonstrate the first synthesis of high‐entropy alloy nanoparticles containing the nine neighboring elements used most often in heterogeneous catalysis: all the iron‐group metals (Fe, Co and Ni) and all the platinum‐group metals (Ru, Rh, Pd, Os, Ir and Pt) through a simple low temperature solution process. Remarkably, alloying the iron‐group base metals with the platinum‐group metals results in 50% increase in the catalytic activity for the hydrogen evolution reaction (HER) under acidic conditions (TOF@25mV=1.58 s‐1) compared to the equivalent alloy containing only platinum‐group metals conditions (TOF@25mV=1.2 s‐1). This activity is three times that of a commercial Pt/C catalyst (TOF@25mV=0.58 s‐1) demonstrating simultaneous reduction in precious metal content and performance enhancement of electrocatalysts.
{"title":"All Iron‐Group and Platinum‐Group Elements Metal High‐Entropy Alloy Nanoparticles","authors":"Julien Mahin, Kohei Kusada, Tomokazu Yamamoto, Takaaki Toriyama, Yasukazu Murakami, Osami Sakata, Shogo Kawaguchi, Hirotaka Ashitani, Yoshiki Kubota, Hiroshi Kitagawa","doi":"10.1002/anie.202502552","DOIUrl":"https://doi.org/10.1002/anie.202502552","url":null,"abstract":"High‐entropy alloys (HEA) are promising catalyst materials for important energy transformations. So far, the focus has been on platinum‐group metals which possess excellent catalytic performance and similar properties, thus being easy to synthesize. However, incorporating more abundant and cheaper elements is preferable for large‐scale applications and is fundamentally more interesting as elements with different properties are expected to greatly affect the structural and electronic characteristics of the resulting alloy. Unfortunately, significant differences in elemental properties greatly complicate the synthesis and require extreme reaction conditions. In this work, we demonstrate the first synthesis of high‐entropy alloy nanoparticles containing the nine neighboring elements used most often in heterogeneous catalysis: all the iron‐group metals (Fe, Co and Ni) and all the platinum‐group metals (Ru, Rh, Pd, Os, Ir and Pt) through a simple low temperature solution process. Remarkably, alloying the iron‐group base metals with the platinum‐group metals results in 50% increase in the catalytic activity for the hydrogen evolution reaction (HER) under acidic conditions (TOF@25mV=1.58 s‐1) compared to the equivalent alloy containing only platinum‐group metals conditions (TOF@25mV=1.2 s‐1). This activity is three times that of a commercial Pt/C catalyst (TOF@25mV=0.58 s‐1) demonstrating simultaneous reduction in precious metal content and performance enhancement of electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666040","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}
RETRACTION: M. Franta, J. Gramüller, P. Dullinger, S. Kaltenberger, D Horinek, and R. M. Gschwind, “Brønsted Acid Catalysis—Controlling the Competition between Monomeric Versus Dimeric Reaction Pathways Enhances Stereoselectivities,” Angewandte Chemie International Edition 62, no. 27 (2023): e202301183, https://doi.org/10.1002/anie.202301183.
{"title":"RETRACTION: Brønsted Acid Catalysis—Controlling the Competition between Monomeric Versus Dimeric Reaction Pathways Enhances Stereoselectivities","authors":"","doi":"10.1002/anie.202503912","DOIUrl":"https://doi.org/10.1002/anie.202503912","url":null,"abstract":"<b>RETRACTION</b>: M. Franta, J. Gramüller, P. Dullinger, S. Kaltenberger, D Horinek, and R. M. Gschwind, “Brønsted Acid Catalysis—Controlling the Competition between Monomeric Versus Dimeric Reaction Pathways Enhances Stereoselectivities,” <i>Angewandte Chemie International Edition</i> 62, no. 27 (2023): e202301183, https://doi.org/10.1002/anie.202301183.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666568","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}
Yan Wang, Shuai Xia, Kui Chen, Jianfang Zhang, Cuiping Yu, Jingjie Wu, Peng Wang, Wenjun Zhang, Yucheng Wu
The electrochemical C‐N coupling of CO2 and nitrogenous species provides a promising approach for synthesizing valuable chemicals such as urea, amides, and other C‐N compounds. However, the unbalanced formation of C‐ and N‐intermediates results in slow C‐N coupling kinetics. Herein, we report an atomically Pd‐bridged Cu/Cu2O (Pd1‐Cu/Cu2O) catalyst, synthesized through the in situ electrochemical reconstruction of Pd1‐Cu2Te nanosheets. This catalyst features Pd‐Cu dual sites that significantly enhance C‐N coupling both thermodynamically and kinetically. The reconstructed Pd1‐Cu/Cu2O achieves a urea yield rate of 31.8 mmol h‐1 gcat.‐1 and a Faradaic efficiency (FE) of 42.2%, along with excellent stability over 100 h. In situ spectroscopic examinations and theoretical calculations disclose that the Pd‐Cu dual sites on Pd1‐Cu/Cu2O modulate the reduction kinetics of CO2 and NO3‐, balance the formation of crucial *CO and *NH2 intermediates, and lower the energy barrier for C‐N coupling, thereby facilitating urea synthesis. Furthermore, the Pd1‐Cu/Cu2O enables the unprecedented C‐N coupling of aniline with CO, resulting in a remarkable acetanilide yield rate of 1021.2 mmol h‐1 gcat.‐1 with an FE of 23.7%. This heteroatom bridging strategy offers a new pathway for designing efficient electrocatalyst for the synthesis of C‐N coupled compounds.
{"title":"Balancing Intermediates Formation on Atomically Pd‐Bridged Cu/Cu2O Interfaces for Kinetics‐Matching Electrocatalytic C‐N Coupling Reaction","authors":"Yan Wang, Shuai Xia, Kui Chen, Jianfang Zhang, Cuiping Yu, Jingjie Wu, Peng Wang, Wenjun Zhang, Yucheng Wu","doi":"10.1002/anie.202503011","DOIUrl":"https://doi.org/10.1002/anie.202503011","url":null,"abstract":"The electrochemical C‐N coupling of CO2 and nitrogenous species provides a promising approach for synthesizing valuable chemicals such as urea, amides, and other C‐N compounds. However, the unbalanced formation of C‐ and N‐intermediates results in slow C‐N coupling kinetics. Herein, we report an atomically Pd‐bridged Cu/Cu2O (Pd1‐Cu/Cu2O) catalyst, synthesized through the in situ electrochemical reconstruction of Pd1‐Cu2Te nanosheets. This catalyst features Pd‐Cu dual sites that significantly enhance C‐N coupling both thermodynamically and kinetically. The reconstructed Pd1‐Cu/Cu2O achieves a urea yield rate of 31.8 mmol h‐1 gcat.‐1 and a Faradaic efficiency (FE) of 42.2%, along with excellent stability over 100 h. In situ spectroscopic examinations and theoretical calculations disclose that the Pd‐Cu dual sites on Pd1‐Cu/Cu2O modulate the reduction kinetics of CO2 and NO3‐, balance the formation of crucial *CO and *NH2 intermediates, and lower the energy barrier for C‐N coupling, thereby facilitating urea synthesis. Furthermore, the Pd1‐Cu/Cu2O enables the unprecedented C‐N coupling of aniline with CO, resulting in a remarkable acetanilide yield rate of 1021.2 mmol h‐1 gcat.‐1 with an FE of 23.7%. This heteroatom bridging strategy offers a new pathway for designing efficient electrocatalyst for the synthesis of C‐N coupled compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"50 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666143","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}
Metallic Zn-based aqueous batteries (ZABs) have arisen as one of the most promising safe energy storage solutions, yet practical development, especially for the Ah-level ZABs, is severely plagued by unmanageable side reactions and notorious dendrite proliferation. Here, we propose a cation-in-mesopore (CiM) complex chemistry by confining Zn2+ within single-mesopore cavities to construct a novel paradigm of 20 Ah-level ZABs. Molecule dynamic and X-ray absorption near-edge structure analyses reveal that the single-mesopore SiO2 (smSiO2) traps Zn2+, replacing H2O molecules in the primary sheath and forming Zn2+-smSiO2 complexes. In-situ electrochemical digital holography, in-situ interface Fourier-transform infrared spectroscopy, and H-bonds density analyses clearly confirm that Zn2+-smSiO2 complexes migrate and adhere onto the metallic Zn, facilitating the formation of mesopore weak H-bonds interface by disrupting the aggregation of solvated H2O. Consequently, the Zn anode operates over 800 h under 55% depth of discharge, effectively suppressing H2O degradation and dendrite growth. The Zn//VO2 pouch battery demonstrates capacities of 20.5 Ah at 0.2 A g−1 and 8.59 Ah at 1 A g−1, and energy density of 65 Wh kg−1 and 96 Wh L−1. The proposed cation-in-mesopore complex chemistry may mark a substantial step forward towards more sustainable and reliable ZABs.
{"title":"Cation-in-Mesopore Complex for 20 Ah-Level Aqueous Battery","authors":"Lipeng Wang, Bao Zhang, Wanhai Zhou, Hongpeng Li, Haobo Dong, Hongrun Jin, Zefang Yang, Wei Li, Zaiwang Zhao, Dongyuan Zhao, Dongliang Chao","doi":"10.1002/anie.202501010","DOIUrl":"https://doi.org/10.1002/anie.202501010","url":null,"abstract":"Metallic Zn-based aqueous batteries (ZABs) have arisen as one of the most promising safe energy storage solutions, yet practical development, especially for the Ah-level ZABs, is severely plagued by unmanageable side reactions and notorious dendrite proliferation. Here, we propose a cation-in-mesopore (CiM) complex chemistry by confining Zn2+ within single-mesopore cavities to construct a novel paradigm of 20 Ah-level ZABs. Molecule dynamic and X-ray absorption near-edge structure analyses reveal that the single-mesopore SiO2 (smSiO2) traps Zn2+, replacing H2O molecules in the primary sheath and forming Zn2+-smSiO2 complexes. In-situ electrochemical digital holography, in-situ interface Fourier-transform infrared spectroscopy, and H-bonds density analyses clearly confirm that Zn2+-smSiO2 complexes migrate and adhere onto the metallic Zn, facilitating the formation of mesopore weak H-bonds interface by disrupting the aggregation of solvated H2O. Consequently, the Zn anode operates over 800 h under 55% depth of discharge, effectively suppressing H2O degradation and dendrite growth. The Zn//VO2 pouch battery demonstrates capacities of 20.5 Ah at 0.2 A g−1 and 8.59 Ah at 1 A g−1, and energy density of 65 Wh kg−1 and 96 Wh L−1. The proposed cation-in-mesopore complex chemistry may mark a substantial step forward towards more sustainable and reliable ZABs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672724","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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