Weina Zhao, Yihui Huang, Zhanhao Liang, Wencai Liu, Chang Shen, Bin Liao, Jiajun Zeng, Bo Yan, Shufen Chen, Hong Bin Yang, Dingshan Yu, Guowei Yang, Zhiping Zeng, Taicheng An
Methanol oxidation reaction (MOR) is an essential anode reaction in direct methanol fuel cells (DMFCs). However, current catalysts often suffer from low activity, poor stability, and CO poisoning. Here, a single‐atom‐tailored ternary alloy, PdCoNi/Cr‐SAC, distinguished by single‐atom‐induced strain, was successfully fabricated. The resulting catalyst delivered a high specific activity of 49.32 mA cm −2 , representing 9.2‐fold enhancements over Pd/C. Theoretical calculations and experimental analysis unveil that the outstanding MOR activity of PdCoNi/Cr‐SAC is ascribed to the SAC‐tailored nanoalloy configuration, which induce a downward shift in the d‐band center, strong d‐orbital coupling, weakened CO binding, and reduced MOR energy barrier. In situ surface‐enhanced Raman spectroscopy (SERS) and attenuated total reflectance surface‐enhanced infrared spectroscopy (ATR‐SEIS) verified the PdCoNi/Cr‐SAC promotes a CO‐free MOR pathway with enhanced hydroxyl‐groups formation. This study progresses the design of single‐atom‐tailored ternary nanoalloy with intrinsic strain, opening a promising route for the development of CO‐tolerance MOR electrocatalysts.
{"title":"D‐Orbital Coupling and Intrinsic Strain Engineering in Single Atom Tailored Ternary Nanoalloys for Enhanced Methanol Electro‐Oxidation","authors":"Weina Zhao, Yihui Huang, Zhanhao Liang, Wencai Liu, Chang Shen, Bin Liao, Jiajun Zeng, Bo Yan, Shufen Chen, Hong Bin Yang, Dingshan Yu, Guowei Yang, Zhiping Zeng, Taicheng An","doi":"10.1002/adfm.75035","DOIUrl":"https://doi.org/10.1002/adfm.75035","url":null,"abstract":"Methanol oxidation reaction (MOR) is an essential anode reaction in direct methanol fuel cells (DMFCs). However, current catalysts often suffer from low activity, poor stability, and CO poisoning. Here, a single‐atom‐tailored ternary alloy, PdCoNi/Cr‐SAC, distinguished by single‐atom‐induced strain, was successfully fabricated. The resulting catalyst delivered a high specific activity of 49.32 mA cm <jats:sup>−2</jats:sup> , representing 9.2‐fold enhancements over Pd/C. Theoretical calculations and experimental analysis unveil that the outstanding MOR activity of PdCoNi/Cr‐SAC is ascribed to the SAC‐tailored nanoalloy configuration, which induce a downward shift in the d‐band center, strong d‐orbital coupling, weakened CO binding, and reduced MOR energy barrier. In situ surface‐enhanced Raman spectroscopy (SERS) and attenuated total reflectance surface‐enhanced infrared spectroscopy (ATR‐SEIS) verified the PdCoNi/Cr‐SAC promotes a CO‐free MOR pathway with enhanced hydroxyl‐groups formation. This study progresses the design of single‐atom‐tailored ternary nanoalloy with intrinsic strain, opening a promising route for the development of CO‐tolerance MOR electrocatalysts.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"12 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
So-Huei Kang, So-Dam Sohn, Kyung Min Lee, Seok-Kyu Cho, Byongkyu Lee, Ji Eun Lee, Sang-Young Lee, Sang Kyu Kwak, Hyung-Joon Shin, Changduk Yang
Guanine (G) is a fascinating molecular tool because of its ability to create supramolecular self-assemblies; thus, G is usable in a wide range of applications. Although the shape of G self-assemblies is an important factor governing supramolecular structures and properties, its control is challenging. Herein, we demonstrate that the shapes of G self-assemblies can be tuned by introducing alkyl (G8), fluoroalkyl (G8f), and oligoether (G8g) side chains into the G moiety. Consequently, we observe an unordered scaffold for G and G8g, quartet-based assemblies for G8, and hexads-based assemblies for G8f, as evidenced by scanning tunneling microscopy and molecular mechanics calculations. In addition, the shape-varying G self-assemblies show promise as artificial solid–electrolyte interphases (SEI) for lithium (Li) metal battery electrodes, revealing enhanced mechanochemical stability and reduced SEI resistance and activation energy for charge transport, particularly for G8f-Li cells, which might result from favorable self-assembling ability and improved structural integrity. We expect the side–chain engineering of G self-assemblies may provide a useful strategy for designing artificial SEIs for Li metal batteries and related supramolecular systems because of its simplicity and versatility.
{"title":"Shape-Controlled Guanine Self-Assemblies for Stable and Fast-Ion Solid–Electrolyte Interphases in Sustainable Li Metal Batteries","authors":"So-Huei Kang, So-Dam Sohn, Kyung Min Lee, Seok-Kyu Cho, Byongkyu Lee, Ji Eun Lee, Sang-Young Lee, Sang Kyu Kwak, Hyung-Joon Shin, Changduk Yang","doi":"10.1002/adfm.202532135","DOIUrl":"https://doi.org/10.1002/adfm.202532135","url":null,"abstract":"Guanine (G) is a fascinating molecular tool because of its ability to create supramolecular self-assemblies; thus, G is usable in a wide range of applications. Although the shape of G self-assemblies is an important factor governing supramolecular structures and properties, its control is challenging. Herein, we demonstrate that the shapes of G self-assemblies can be tuned by introducing alkyl (G8), fluoroalkyl (G8f), and oligoether (G8g) side chains into the G moiety. Consequently, we observe an unordered scaffold for G and G8g, quartet-based assemblies for G8, and hexads-based assemblies for G8f, as evidenced by scanning tunneling microscopy and molecular mechanics calculations. In addition, the shape-varying G self-assemblies show promise as artificial solid–electrolyte interphases (SEI) for lithium (Li) metal battery electrodes, revealing enhanced mechanochemical stability and reduced SEI resistance and activation energy for charge transport, particularly for G8f-Li cells, which might result from favorable self-assembling ability and improved structural integrity. We expect the side–chain engineering of G self-assemblies may provide a useful strategy for designing artificial SEIs for Li metal batteries and related supramolecular systems because of its simplicity and versatility.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"313 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High polarity of Mg2+ results in unsatisfied interactions with the cathode host lattice, giving rise to sluggish Mg2+ diffusion and thus surface “self-passivation” caused by irreversible insertion/extraction of Mg2+, impeding development of magnesium metal batteries (MMBs). Herein, we pioneer a Defect Chemistry-Inspired synergistic strategy of synchronously Spin-State Modulation and Adaptive Microstructural Reformation, thereby resolving the inherent thermodynamic–kinetic conflict to improve Mg2+ storage. Combining first-principles calculations with advanced characterization, the intrinsic inertness of the V-3d0 orbital in Cu3VS4 was activated by filling electrons to induce a spin state change after introducing Na+, which enhanced the electron hopping process for rapid charge compensation to unlock Mg2+ storage ability. Furthermore, the cathode undergoes a self-driven structural evolution into a microcrystalline/amorphous hybrid, improved the cathode-electrolyte interface and Internal reaction site to balance subsequent Mg2+ adsorption and mobility. The optimized material, C@A-N-0.5, delivers a high specific capacity of 140 mAh g−1 at 40 mA g−1 (92% of capacity over rarely reported 300 cycles), and it had over 100 mAh g−1 at 200 mA g−1 for 1000 cycles, far outperforming the unmodified Cu3VS4 with negligible Mg2+ storage. This work provides mechanistic insights and materials design pathways for high-performance MMBs cathodes based on transition metal sulfides.
Mg2+的高极性导致与阴极主体晶格的相互作用不理想，导致Mg2+扩散缓慢，从而导致Mg2+的不可逆插入/提取引起表面“自钝化”，阻碍了镁金属电池（MMBs）的发展。在此，我们开创了一种缺陷化学启发的同步自旋态调制和自适应微观结构改造的协同策略，从而解决了固有的热力学-动力学冲突，以提高Mg2+的存储。结合第一性原理计算和高级表征，在引入Na+后，通过填充电子诱导自旋态变化来激活Cu3VS4中v - 30轨道的固有惰性，从而增强了电子跳变过程，实现了快速电荷补偿，从而解锁了Mg2+的存储能力。此外，阴极经历了自驱动结构演变为微晶/非晶杂化，改善了阴极-电解质界面和内部反应位点，以平衡随后的Mg2+吸附和迁移率。优化后的材料C@A-N-0.5在40 mA g - 1时提供了140 mAh g - 1的高比容量（很少报道的300次循环容量的92%），并且在200 mA g - 1时超过100 mAh g - 1 1000次循环，远远优于未修饰的Cu3VS4， Mg2+存储可以忽略。这项工作为基于过渡金属硫化物的高性能mmb阴极提供了机理见解和材料设计途径。
{"title":"Unlocking Inert Material to Durable Cathode for Magnesium Storage Inspired via Synergistic Spin-Orbital Reconfiguration and Adaptive Crystal Transformation","authors":"Wenwei Zhang, Zenan Xu, Xiaobin Liao, Junjun Wang, Feiyang Chao, Jianyong Zhang, Shaohua Zhu, Lianmeng Cui, Jiang Liang, Huiqing Zhou, Xinran Chen, Min Zhou, Jinghao Li, Chen Tang, Congli Sun, Qinyou An","doi":"10.1002/adfm.75028","DOIUrl":"https://doi.org/10.1002/adfm.75028","url":null,"abstract":"High polarity of Mg<sup>2+</sup> results in unsatisfied interactions with the cathode host lattice, giving rise to sluggish Mg<sup>2+</sup> diffusion and thus surface “self-passivation” caused by irreversible insertion/extraction of Mg<sup>2+</sup>, impeding development of magnesium metal batteries (MMBs). Herein, we pioneer a Defect Chemistry-Inspired synergistic strategy of synchronously Spin-State Modulation and Adaptive Microstructural Reformation, thereby resolving the inherent thermodynamic–kinetic conflict to improve Mg<sup>2+</sup> storage. Combining first-principles calculations with advanced characterization, the intrinsic inertness of the V-3d<sup>0</sup> orbital in Cu<sub>3</sub>VS<sub>4</sub> was activated by filling electrons to induce a spin state change after introducing Na<sup>+</sup>, which enhanced the electron hopping process for rapid charge compensation to unlock Mg<sup>2+</sup> storage ability. Furthermore, the cathode undergoes a self-driven structural evolution into a microcrystalline/amorphous hybrid, improved the cathode-electrolyte interface and Internal reaction site to balance subsequent Mg<sup>2+</sup> adsorption and mobility. The optimized material, C@A-N-0.5, delivers a high specific capacity of 140 mAh g<sup>−1</sup> at 40 mA g<sup>−1</sup> (92% of capacity over rarely reported 300 cycles), and it had over 100 mAh g<sup>−1</sup> at 200 mA g<sup>−1</sup> for 1000 cycles, far outperforming the unmodified Cu<sub>3</sub>VS<sub>4</sub> with negligible Mg<sup>2+</sup> storage. This work provides mechanistic insights and materials design pathways for high-performance MMBs cathodes based on transition metal sulfides.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"312 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chenxuan Xu, Tao Su, Yan Lai, Zhimeng Hao, Xiujuan Zhuang, Jianmin Ma
Fast charging of high-energy lithium metal batteries is fundamentally limited by sluggish Li+ desolvation kinetics and the instability of electrode–electrolyte interfaces under high current densities. Here, an anion-centric weakly solvating electrolyte is developed via an anion–solvent–anion mutual-exclusion strategy to simultaneously accelerate Li+ transport and stabilize interfacial chemistry in Li||NCM811 batteries. This cooperative exclusion effect significantly lowers the Li+ desolvation activation energy to ∼34 kJ mol−1 while maintaining a favorable ion-pair distribution with minimal aggregation, enabling a high ionic conductivity of ∼2.8 mS cm−1. Benefiting from the optimized solvation environment, inorganic-rich and mechanically robust SEI/CEI layers are formed in situ, facilitating fast interfacial charge transfer and uniform lithium deposition. Consequently, Li||NCM811 cells exhibit outstanding high-rate performance, delivering high specific capacities at 5 C and 10 C with prolonged cycling stability, demonstrating significant fast-charging potential. This work elucidates a solvation-structure-driven kinetic mechanism critical for fast charging and provides a general electrolyte design paradigm beyond conventional weakly solvating strategies.
高能锂金属电池的快速充电受到高电流密度下Li+溶解动力学缓慢和电极-电解质界面不稳定的限制。本研究通过阴离子-溶剂-阴离子互排斥策略制备阴离子中心弱溶剂化电解质，同时加速Li+在Li||NCM811电池中的输运和稳定界面化学。这种协同排斥效应显著降低Li+脱溶活化能至~ 34 kJ mol−1，同时保持有利的离子对分布和最小的聚集，使离子电导率达到~ 2.8 mS cm−1。受益于优化的溶剂化环境，在原位形成了无机丰富且机械坚固的SEI/CEI层，促进了快速的界面电荷转移和均匀的锂沉积。因此，Li||NCM811电池表现出出色的高倍率性能，在5℃和10℃下具有高比容量和长周期稳定性，显示出显著的快速充电潜力。这项工作阐明了对快速充电至关重要的溶剂化结构驱动的动力学机制，并提供了一种超越传统弱溶剂化策略的通用电解质设计范式。
{"title":"Regulating Li+ Desolvation Kinetics via Dual-Anion Solvation for High-Rate Lithium Metal Batteries With Fast-Charging Capability","authors":"Chenxuan Xu, Tao Su, Yan Lai, Zhimeng Hao, Xiujuan Zhuang, Jianmin Ma","doi":"10.1002/adfm.75017","DOIUrl":"https://doi.org/10.1002/adfm.75017","url":null,"abstract":"Fast charging of high-energy lithium metal batteries is fundamentally limited by sluggish Li<sup>+</sup> desolvation kinetics and the instability of electrode–electrolyte interfaces under high current densities. Here, an anion-centric weakly solvating electrolyte is developed via an anion–solvent–anion mutual-exclusion strategy to simultaneously accelerate Li<sup>+</sup> transport and stabilize interfacial chemistry in Li||NCM811 batteries. This cooperative exclusion effect significantly lowers the Li<sup>+</sup> desolvation activation energy to ∼34 kJ mol<sup>−1</sup> while maintaining a favorable ion-pair distribution with minimal aggregation, enabling a high ionic conductivity of ∼2.8 mS cm<sup>−1</sup>. Benefiting from the optimized solvation environment, inorganic-rich and mechanically robust SEI/CEI layers are formed in situ, facilitating fast interfacial charge transfer and uniform lithium deposition. Consequently, Li||NCM811 cells exhibit outstanding high-rate performance, delivering high specific capacities at 5 C and 10 C with prolonged cycling stability, demonstrating significant fast-charging potential. This work elucidates a solvation-structure-driven kinetic mechanism critical for fast charging and provides a general electrolyte design paradigm beyond conventional weakly solvating strategies.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"59 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuqing Yin, Mengshuo Shen, Fusheng Liu, Junwen Zhang, Penghe Yin, Bo Liu, Dong Chen, Xiaoying Yan, Li Chen, Chong Liu, Jingmin Li
Nanopillar arrays (NAs) are widely employed as versatile nanostructures for biological applications. Cells on NAs adopt three adhesion states—“top”, “middle”, and “bottom”—each corresponding to distinct biological functions. Although these adhesion states are influenced by NAs geometry, existing models overlook the role of the membrane reservoir—an intrinsic cellular property—in regulating membrane tension during cell settling, resulting in an incomplete mechanistic understanding and limited predictive capability. In this work, a reservoir-guided nano-bio interface (RG-NBI) model is introduced to quantitatively describe the adhesion process and the resulting adhesion states of cells on NAs. An automated design platform, NAs Designer, is developed to predict adhesion states based solely on geometric parameters, achieving 97.22% accuracy across 36 experimental cases. Nanopillar microelectrode arrays (NMEAs) with optimized geometries are fabricated, exhibiting enlarged effective electrode surface area and enhanced cell adhesion. The adhesion states of cells on NMEAs directly influence sensing performance: the “top” state supports highly sensitive electrochemical detection (353.86 nA/µM/mm2), whereas the “bottom” state enables high-signal-to-noise electrophysiological recordings (7.97). These NMEAs allow precise monitoring of dopamine release from dopaminergic neurons and choline consumption by glioblastoma cells. Overall, this integrated approach provides a coherent foundation for nanostructure-mediated cell regulation and the engineering of advanced nano-bio interfaces.
{"title":"Predicting Cell Adhesion States on Nanopillar Arrays with a Nano-Bio Interface Model: From Modeling to Functional Device Design","authors":"Shuqing Yin, Mengshuo Shen, Fusheng Liu, Junwen Zhang, Penghe Yin, Bo Liu, Dong Chen, Xiaoying Yan, Li Chen, Chong Liu, Jingmin Li","doi":"10.1002/adfm.202532074","DOIUrl":"https://doi.org/10.1002/adfm.202532074","url":null,"abstract":"Nanopillar arrays (NAs) are widely employed as versatile nanostructures for biological applications. Cells on NAs adopt three adhesion states—“top”, “middle”, and “bottom”—each corresponding to distinct biological functions. Although these adhesion states are influenced by NAs geometry, existing models overlook the role of the membrane reservoir—an intrinsic cellular property—in regulating membrane tension during cell settling, resulting in an incomplete mechanistic understanding and limited predictive capability. In this work, a reservoir-guided nano-bio interface (RG-NBI) model is introduced to quantitatively describe the adhesion process and the resulting adhesion states of cells on NAs. An automated design platform, NAs Designer, is developed to predict adhesion states based solely on geometric parameters, achieving 97.22% accuracy across 36 experimental cases. Nanopillar microelectrode arrays (NMEAs) with optimized geometries are fabricated, exhibiting enlarged effective electrode surface area and enhanced cell adhesion. The adhesion states of cells on NMEAs directly influence sensing performance: the “top” state supports highly sensitive electrochemical detection (353.86 nA/µM/mm<sup>2</sup>), whereas the “bottom” state enables high-signal-to-noise electrophysiological recordings (7.97). These NMEAs allow precise monitoring of dopamine release from dopaminergic neurons and choline consumption by glioblastoma cells. Overall, this integrated approach provides a coherent foundation for nanostructure-mediated cell regulation and the engineering of advanced nano-bio interfaces.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"6 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An innovative strategy of aggregation-induced stabilization is presented to achieve highly stable boron-containing organic diradicaliods by forming different π–π stacking aggregates through cooperative π bridge and hydrogen bond regulation. Herein, three D-π-A-π-D crossover shaped molecules (PPCy-Ph, PPCy-Th, and PPCy-Fu) are synthesized with π-bridge engineering from phenyl-, thienyl-to furyl for precisely modulating molecular conformation and aggregation state. As the most stable boron-containing π-radicals to date, they all display unprecedentedly stable ESR signals at harsh conditions (300°C in air for 2 h and boiling water for 2 h) and superior photo-, chemical- and thermal stability due to synergistic effect of hydrogen bonding interactions. In particular, PPCy-Th exhibited best photothermal conversion efficiency, reaching 275°C under 808 nm laser irradiation (1.0 W cm2), superior solar-driven water evaporation rate of 1.42 kg m−2 h−1 and evaporation efficiencies (η) of 98.37%, thermoelectric power generation (256 mV) under 1 sun illumination. The multiple applications in cogeneration of water and electricity, seawater desalination, sewage treatment, laser ignition, and driving electric fan are demonstrated. Moreover, PPCy-Fu NPs display efficient photothermal & photodynamic synergistic cancer cell killing under hypoxia. This study highlights a novel strategy for developing stable boron-containing diradicaloids with excellent photo-thermal conversion efficiency.
提出了一种创新的聚集诱导稳定化策略，通过π桥和氢键调节形成不同的π -π堆叠聚集体，从而获得高稳定性的含硼有机二自由基。本文通过苯基、噻基到呋喃基之间的π桥工程，合成了3个D-π- a -π-D交叉型分子PPCy-Ph、PPCy-Th和PPCy-Fu，以精确调节分子的构象和聚集状态。作为迄今为止最稳定的含硼π自由基，它们在恶劣条件下（300°C空气中2 h和沸水中2 h）均表现出前所未有的稳定ESR信号，并且由于氢键相互作用的协同作用，具有优异的光、化学和热稳定性。其中，PPCy-Th光热转换效率最高，在808 nm激光照射（1.0 W cm2）下达到275°C，太阳驱动的水分蒸发速率为1.42 kg m−2 h−1，蒸发效率（η）为98.37%，在1个太阳照射下产生的热电功率为256 mV。演示了其在水电热电联产、海水淡化、污水处理、激光点火、驱动电风扇等方面的多种应用。此外，PPCy-Fu NPs在缺氧条件下表现出高效的光热和光动力协同杀伤癌细胞。本研究强调了一种开发具有优异光热转换效率的稳定含硼二根碱的新策略。
{"title":"Aggregation-Induced Stabilization of Boron-Containing Organic Diradicaliods via π-Bridge toward Highly Efficient Light-to-Thermal-Electric Conversion","authors":"Bingli Lu, Fenghui Lu, Xueguang Ran, Derong Cao, Xiting Zhang, Yuan Li, Lingyun Wang","doi":"10.1002/adfm.74984","DOIUrl":"https://doi.org/10.1002/adfm.74984","url":null,"abstract":"An innovative strategy of aggregation-induced stabilization is presented to achieve highly stable boron-containing organic diradicaliods by forming different π–π stacking aggregates through cooperative π bridge and hydrogen bond regulation. Herein, three D-π-A-π-D crossover shaped molecules (PPCy-Ph, PPCy-Th, and PPCy-Fu) are synthesized with π-bridge engineering from phenyl-, thienyl-to furyl for precisely modulating molecular conformation and aggregation state. As the most stable boron-containing π-radicals to date, they all display unprecedentedly stable ESR signals at harsh conditions (300°C in air for 2 h and boiling water for 2 h) and superior photo-, chemical- and thermal stability due to synergistic effect of hydrogen bonding interactions. In particular, PPCy-Th exhibited best photothermal conversion efficiency, reaching 275°C under 808 nm laser irradiation (1.0 W cm<sup>2</sup>), superior solar-driven water evaporation rate of 1.42 kg m<sup>−2</sup> h<sup>−1</sup> and evaporation efficiencies (η) of 98.37%, thermoelectric power generation (256 mV) under 1 sun illumination. The multiple applications in cogeneration of water and electricity, seawater desalination, sewage treatment, laser ignition, and driving electric fan are demonstrated. Moreover, PPCy-Fu NPs display efficient photothermal & photodynamic synergistic cancer cell killing under hypoxia. This study highlights a novel strategy for developing stable boron-containing diradicaloids with excellent photo-thermal conversion efficiency.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"6 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrolysis catalyzed by metal oxides is an effective approach for removing carbonyl sulfide (COS) from blast furnace gas, but constructing highly active catalytic sites that function efficiently under low–temperature conditions remains a fundamental challenge. In this work, perovskite–type niobate catalysts (KNbO 3 , NaNbO 3 , and LiNbO 3 ) are synthesized via a sol–gel method and subsequently modified under a strongly reducing NH 3 atmosphere at elevated temperatures to simultaneously generate oxygen vacancies and nitrogen dopants (both substitutional and interstitial), thereby significantly enhancing their catalytic performance and H 2 S selectivity for COS hydrolysis. Among them, NH 3– treated N–KNbO 3 achieves 100% COS conversion and 100% H 2 S selectivity at 100 °C. Comprehensive physicochemical characterizations and density functional theory (DFT) calculations indicate that NH 3 treatment achieves a “four–in–one” effect: oxygen vacancy engineering, nitrogen doping, morphology engineering, and modulation of surface active sites. This study systematically elucidates the structure–activity relationship underlying the synergistic interplay between nitrogen doping and oxygen vacancies in KNbO 3 , demonstrates the cooperative promotional role of oxygen vacancies and interstitial nitrogen during hydrolysis, and underscores the critical importance of surface reactive oxygen species and weakly basic sites. These findings provide both a theoretical foundation and practical design strategies for developing high–performance catalysts for low–temperature COS hydrolysis.
{"title":"Structure–Activity Relationship of NH 3 –Treated Spherical KNbO 3 in Catalytic Carbonyl Sulfide Hydrolysis: Oxygen Vacancy Engineering vs. Nitrogen Doping","authors":"Jian Gao, Xiubiao Ma, Peng Wu, Kai Shen, Yaping Zhang, Tingyu Zhu, Wenqing Xu","doi":"10.1002/adfm.74999","DOIUrl":"https://doi.org/10.1002/adfm.74999","url":null,"abstract":"Hydrolysis catalyzed by metal oxides is an effective approach for removing carbonyl sulfide (COS) from blast furnace gas, but constructing highly active catalytic sites that function efficiently under low–temperature conditions remains a fundamental challenge. In this work, perovskite–type niobate catalysts (KNbO <jats:sub>3</jats:sub> , NaNbO <jats:sub>3</jats:sub> , and LiNbO <jats:sub>3</jats:sub> ) are synthesized via a sol–gel method and subsequently modified under a strongly reducing NH <jats:sub>3</jats:sub> atmosphere at elevated temperatures to simultaneously generate oxygen vacancies and nitrogen dopants (both substitutional and interstitial), thereby significantly enhancing their catalytic performance and H <jats:sub>2</jats:sub> S selectivity for COS hydrolysis. Among them, NH <jats:sub>3–</jats:sub> treated N–KNbO <jats:sub>3</jats:sub> achieves 100% COS conversion and 100% H <jats:sub>2</jats:sub> S selectivity at 100 °C. Comprehensive physicochemical characterizations and density functional theory (DFT) calculations indicate that NH <jats:sub>3</jats:sub> treatment achieves a “four–in–one” effect: oxygen vacancy engineering, nitrogen doping, morphology engineering, and modulation of surface active sites. This study systematically elucidates the structure–activity relationship underlying the synergistic interplay between nitrogen doping and oxygen vacancies in KNbO <jats:sub>3</jats:sub> , demonstrates the cooperative promotional role of oxygen vacancies and interstitial nitrogen during hydrolysis, and underscores the critical importance of surface reactive oxygen species and weakly basic sites. These findings provide both a theoretical foundation and practical design strategies for developing high–performance catalysts for low–temperature COS hydrolysis.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"136 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yalin Yang, Hanlin Huang, Zheyan Chen, Xuejiao Wang, Hao Sun, Jingjing Hui, Wei Lu, Lyuzhou Ye, Xiaolong Yang, Zhigang Zou
The application of halide perovskites in photocatalysis is severely limited by structural instability in polar solvents, such as dissolution and lattice degradation. Herein, we investigate the intrinsic stability in ethanol polar solvent of heterovalent metal cation-substituted perovskite derivative Cs2AgBiBr6 via density functional theory (DFT) calculations, exhibiting the suppressed ethanol-induced bond relaxation with a smaller Cs-Br bond length variation compared to that of CsPbBr3. Substantial interfacial electron transfer in CsPbBr3-ethanol promotes Pb-Br bond dissociation, whereas Cs2AgBiBr6 exhibits negligible electronic perturbation. Moreover, experimental evidences demonstrate better stability of Cs2AgBiBr6 after long-term exposing to ethanol, light, and Ar/air atmospheres. Based on this, we construct Cs2AgBiBr6/CdS heterojunction for photocatalytic ethanol dehydrogenation reaction. Through modification with Rh cocatalyst, which achieves a hydrogen evolution rate of 49.15 mmol·g−1·h−1, AQY of 22.5%, and TOF of 197.5 h−1 over 60 h. At 60 °C, the ethanol dehydrogenation rate further increase to 277.35 mmol·g−1·h−1 and TOF of 1114.5 h−1. Mechanistically, the Rh sites and heterojunction interface synergistically govern hydrogen evolution and ethanol oxidation pathways, facilitating C-H/O-H bond activation and regulating product selectivity. Our work not only provides new insights into perovskite stability but also expands their applicability in polar solvent-based photocatalysis.
{"title":"Unveiling the Polar-Solvent Stability of Heterovalent Metal Cation-Substituted Perovskite Derivative for Promoting Photocatalytic Ethanol Dehydrogenation","authors":"Yalin Yang, Hanlin Huang, Zheyan Chen, Xuejiao Wang, Hao Sun, Jingjing Hui, Wei Lu, Lyuzhou Ye, Xiaolong Yang, Zhigang Zou","doi":"10.1002/adfm.75007","DOIUrl":"https://doi.org/10.1002/adfm.75007","url":null,"abstract":"The application of halide perovskites in photocatalysis is severely limited by structural instability in polar solvents, such as dissolution and lattice degradation. Herein, we investigate the intrinsic stability in ethanol polar solvent of heterovalent metal cation-substituted perovskite derivative Cs<sub>2</sub>AgBiBr<sub>6</sub> via density functional theory (DFT) calculations, exhibiting the suppressed ethanol-induced bond relaxation with a smaller Cs-Br bond length variation compared to that of CsPbBr<sub>3</sub>. Substantial interfacial electron transfer in CsPbBr<sub>3</sub>-ethanol promotes Pb-Br bond dissociation, whereas Cs<sub>2</sub>AgBiBr<sub>6</sub> exhibits negligible electronic perturbation. Moreover, experimental evidences demonstrate better stability of Cs<sub>2</sub>AgBiBr<sub>6</sub> after long-term exposing to ethanol, light, and Ar/air atmospheres. Based on this, we construct Cs<sub>2</sub>AgBiBr<sub>6</sub>/CdS heterojunction for photocatalytic ethanol dehydrogenation reaction. Through modification with Rh cocatalyst, which achieves a hydrogen evolution rate of 49.15 mmol·g<sup>−1</sup>·h<sup>−1</sup>, AQY of 22.5%, and TOF of 197.5 h<sup>−1</sup> over 60 h. At 60 °C, the ethanol dehydrogenation rate further increase to 277.35 mmol·g<sup>−1</sup>·h<sup>−1</sup> and TOF of 1114.5 h<sup>−1</sup>. Mechanistically, the Rh sites and heterojunction interface synergistically govern hydrogen evolution and ethanol oxidation pathways, facilitating C-H/O-H bond activation and regulating product selectivity. Our work not only provides new insights into perovskite stability but also expands their applicability in polar solvent-based photocatalysis.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"189 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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