Noble metal nanoclusters(MNCs),intrinsically possessing atomically precise structures and tunable compositions,have emerged as promising candidates for advanced catalysis,sensing,and energy-related applications.Howeve...Noble metal nanoclusters(MNCs),intrinsically possessing atomically precise structures and tunable compositions,have emerged as promising candidates for advanced catalysis,sensing,and energy-related applications.However,their practical utilization is severely hampered by rapid oxidation-induced structural degradation and ligand detachment under ambient conditions,leading to inevitable aggregation into larger particles during storage or catalytic process.Here,we developed a redox-mediated stabilization strategy by integrating ultrasmall Au_(25)NCs with amine-functionalized metal-organic frameworks(MOF).The abundant and uniformly dispersed amine groups as reductive reagents to suppress the oxidation of Au atoms while simultaneously reinforcing thiol-terminated ligands anchoring through dynamic coordination processes.The dual stabilization strategy enables Au_(25)NCs to maintain their initial ultrasmall particle sizes and structural integrity under ambient storage and light irradiation processes.Furthermore,the engineered type-II heterojunction between Au_(25)NCs and UiO-66-NH_(2)significantly enhances visible-light harvesting capacity and charge separation efficiency,thus achieving efficient activation of O_(2)to form reactive oxygen species(ROS).The Au_(25)/UiO-66-NH_(2)composites exhibit outstanding photocatalytic antibacterial activity and durability,achieving 99.999%bacterial inactivation efficiency against Escherichia coli(E.coli)within 40 min under visible light while retaining the high efficacy after five reuse cycles.The integration of Au_(25)/UiO-66-NH_(2)into wearable fabrics underscores its significant potential to provide continuous antibacterial protection.This work establishes amine-functionalized MOFs as universal redox-active supports for stabilizing metastable MNCs and provides a versatile platform for designing durable photocatalytic systems in environmental and biomedical applications.展开更多
Layered polymer suffers from a transfer barrier of photogenerated carriers resulting from the lack of interlamellar connection channels and intralayer disorder.Herein,a layer-stacked crystalline carbon nitride nanorod...Layered polymer suffers from a transfer barrier of photogenerated carriers resulting from the lack of interlamellar connection channels and intralayer disorder.Herein,a layer-stacked crystalline carbon nitride nanorod resembling an accordion(A-CNR)grafted abundant interlamellar oxygen-containing groups is ingeniously designed to break through the transfer barrier between layers without inserting any extra impurities.Density functional theory reveals that electrons are enriched near the oxygencontaining groups,promoting the extension and coupling of interlayer electron clouds.This reduces the interlamellar electrostatic potential barrier from 5.38 to 2.74 e V.Remarkably,the groups not only establish interlayer bridges but also guide carriers to the bridge entrance,further enhancing interlayer carrier transfer.Additionally,the intralayer carrier separation and transfer are also improved,profiting from the asymmetrical charge distribution and high crystallinity.A-CNR exhibits impressive photoelectric properties and photocatalytic water disinfection capability.Within 18 min irradiation,over 10~6 colony-forming units(CFU)/mL of bacteria are completely inactivated.Moreover,A-CNR can be dispersed in water over a long period benefiting from the introduced oxygen-containing groups,making it suitable for photocatalysis in the aqueous phase.The work provides a feasible and effective strategy to overcome the inherent barrier of layered polymeric photocatalysts.展开更多
基金supported by the National Key Research and Development Program of China(2024YFB3612500,2024YFB3612600,2023YFB3608900)the National Natural Science Foundation of China(21835003,22205104,22305127)+5 种基金the Basic Research Program of Jiangsu Province(BK20243057)the Natural Science Foundation of Jiangsu Province(BE2019120,BK20140060,BM2012010)the Foundation of Key Laboratory of Flexible Electronics of Zhejiang Province(2023FE002)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(NY222078,NY222079)the Project of State Key Laboratory of Organic Electronics and Information Displays(GZR2023010031,GZR2023010053)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23-0925).
文摘Noble metal nanoclusters(MNCs),intrinsically possessing atomically precise structures and tunable compositions,have emerged as promising candidates for advanced catalysis,sensing,and energy-related applications.However,their practical utilization is severely hampered by rapid oxidation-induced structural degradation and ligand detachment under ambient conditions,leading to inevitable aggregation into larger particles during storage or catalytic process.Here,we developed a redox-mediated stabilization strategy by integrating ultrasmall Au_(25)NCs with amine-functionalized metal-organic frameworks(MOF).The abundant and uniformly dispersed amine groups as reductive reagents to suppress the oxidation of Au atoms while simultaneously reinforcing thiol-terminated ligands anchoring through dynamic coordination processes.The dual stabilization strategy enables Au_(25)NCs to maintain their initial ultrasmall particle sizes and structural integrity under ambient storage and light irradiation processes.Furthermore,the engineered type-II heterojunction between Au_(25)NCs and UiO-66-NH_(2)significantly enhances visible-light harvesting capacity and charge separation efficiency,thus achieving efficient activation of O_(2)to form reactive oxygen species(ROS).The Au_(25)/UiO-66-NH_(2)composites exhibit outstanding photocatalytic antibacterial activity and durability,achieving 99.999%bacterial inactivation efficiency against Escherichia coli(E.coli)within 40 min under visible light while retaining the high efficacy after five reuse cycles.The integration of Au_(25)/UiO-66-NH_(2)into wearable fabrics underscores its significant potential to provide continuous antibacterial protection.This work establishes amine-functionalized MOFs as universal redox-active supports for stabilizing metastable MNCs and provides a versatile platform for designing durable photocatalytic systems in environmental and biomedical applications.
基金supported by the National Natural Science Foundation of China(52103315)the Natural Science Foundation of Jiangsu(BK20221270)+3 种基金the Science and Technology Program of Suzhou(SS202113)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_0703)the Open Project of Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province(CSPC202310)the Industrial Guided Development Project of Suzhou Yangcheng Lake。
文摘Layered polymer suffers from a transfer barrier of photogenerated carriers resulting from the lack of interlamellar connection channels and intralayer disorder.Herein,a layer-stacked crystalline carbon nitride nanorod resembling an accordion(A-CNR)grafted abundant interlamellar oxygen-containing groups is ingeniously designed to break through the transfer barrier between layers without inserting any extra impurities.Density functional theory reveals that electrons are enriched near the oxygencontaining groups,promoting the extension and coupling of interlayer electron clouds.This reduces the interlamellar electrostatic potential barrier from 5.38 to 2.74 e V.Remarkably,the groups not only establish interlayer bridges but also guide carriers to the bridge entrance,further enhancing interlayer carrier transfer.Additionally,the intralayer carrier separation and transfer are also improved,profiting from the asymmetrical charge distribution and high crystallinity.A-CNR exhibits impressive photoelectric properties and photocatalytic water disinfection capability.Within 18 min irradiation,over 10~6 colony-forming units(CFU)/mL of bacteria are completely inactivated.Moreover,A-CNR can be dispersed in water over a long period benefiting from the introduced oxygen-containing groups,making it suitable for photocatalysis in the aqueous phase.The work provides a feasible and effective strategy to overcome the inherent barrier of layered polymeric photocatalysts.
