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Open AccessDOI: 10.1007/s40843-025-3391-0Original Research

Redox-Mediated Stabilization of Ultrasmall Au25 Nanoclusters in Amine-Functionalized MOF for Robust Photocatalytic Antibacterial Applications

Nanjing University of Posts and Telecommunications

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Redox-Mediated Stabilization of Ultrasmall Au25 Nanoclusters in Amine-Functionalized MOF for Robust Photocatalytic Antibacterial Applications
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Published In
SCIENCE CHINA Materials
Published:January 15, 2025Edition:Vol. 68, Issue 7 • pp. 100-112Citation:SHEN Yu et al. (2025), SCIENCE CHINA Materials
Impact Factor3.5 (Q2 Scopus)
Source Journal中国科学: 材料

Key Takeaways & Executive Findings

  • • • Achieves 99.999% (5-log) inactivation of E. coli within 40 minutes under visible light, with photocatalytic efficacy retained over five consecutive reuse cycles, indicating robust operational stability critical for clinical and environmental deployment. • • The redox-mediated stabilization strategy maintains Au25 nanocluster size and structural integrity under ambient storage and light irradiation, directly addressing aggregation-induced deactivation that typically reduces catalytic activity by orders of magnitude. • • Type-II heterojunction formation between Au25 NCs and UiO-66-NH2 enhances visible-light harvesting and charge separation efficiency, enabling efficient O2 activation to ROS; this translates to a 40-minute disinfection timeframe, outperforming many conventional photocatalytic systems that require hours. • • Integration into wearable fabrics demonstrates continuous antibacterial protection, with the composite retaining high efficacy after five reuse cycles, underscoring potential for low-maintenance, durable antimicrobial textiles in healthcare and hygiene-critical environments.
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Abstract

Noble metal nanoclusters (MNCs) possess atomically precise structures and tunable compositions, yet their practical deployment is constrained by rapid oxidation-induced structural degradation and ligand detachment, leading to aggregation during storage and catalysis. This study introduces a redox-mediated stabilization strategy by integrating ultrasmall Au25 nanoclusters with amine-functionalized UiO-66-NH2. The uniformly dispersed amine groups act as reductive reagents, suppressing Au oxidation while reinforcing thiol-terminated ligand anchoring via dynamic coordination. This dual stabilization preserves the initial ultrasmall size and structural integrity of Au25 NCs under ambient storage and light irradiation. The engineered type-II heterojunction between Au25 NCs and UiO-66-NH2 enhances visible-light harvesting and charge separation, enabling efficient O2 activation to reactive oxygen species (ROS). The Au25/UiO-66-NH2 composites achieve 99.999% bacterial inactivation against Escherichia coli within 40 min under visible light, retaining high efficacy after five reuse cycles. Integration into wearable fabrics demonstrates potential for continuous antibacterial protection. This work establishes amine-functionalized MOFs as universal redox-active supports for stabilizing metastable MNCs, offering a versatile platform for durable photocatalytic systems in environmental and biomedical applications.

1. Introduction

Noble metal nanoclusters (MNCs) offer atomically precise structures and size-dependent electronic properties, making them attractive for catalysis, sensing, and nanomedicine. However, their high surface energy drives irreversible aggregation via ligand detachment and metal atom diffusion under ambient and catalytic conditions, leading to rapid loss of atomic utilization and catalytic activity. Existing stabilization approaches, such as ligand engineering or steric hindrance, often fail under prolonged irradiation or oxidative stress, limiting translation to practical technologies.

This study addresses the stability bottleneck by integrating ultrasmall Au25 NCs with amine-functionalized UiO-66-NH2. The abundant amine groups act as reductive reagents, suppressing oxidation of Au atoms and reinforcing thiol-terminated ligand anchoring through dynamic coordination. The resulting type-II heterojunction enhances visible-light absorption and charge separation, enabling efficient O2 activation to ROS. The composite achieves 99.999% E. coli inactivation within 40 minutes under visible light and retains efficacy after five reuse cycles, demonstrating a viable pathway for durable photocatalytic antibacterial systems in wearable and biomedical applications.

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Cite This Research Paper
SHEN Yu, PAN Ting, GU Yubing, YAN Pu, HOU Fengming, ZHANG Senyu, WEI Wei, LI Xiangchun, LAI Wen-Yong (2025). Redox-Mediated Stabilization of Ultrasmall Au25 Nanoclusters in Amine-Functionalized MOF for Robust Photocatalytic Antibacterial Applications. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3391-0
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Frequently Asked Questions

What is the primary failure mechanism of Au25 nanoclusters under photocatalytic conditions, and how does the amine-functionalized MOF mitigate it?

Au25 NCs suffer from oxidation-induced structural degradation and ligand detachment, leading to aggregation into larger particles. The amine groups in UiO-66-NH2 act as reductive reagents, suppressing Au oxidation and reinforcing thiol-terminated ligand anchoring via dynamic coordination, thereby maintaining ultrasmall size and structural integrity under ambient storage and light irradiation.

What are the quantified photocatalytic antibacterial performance metrics, and how do they compare to conventional systems?

The Au25/UiO-66-NH2 composite achieves 99.999% (5-log) inactivation of E. coli within 40 minutes under visible light, with high efficacy retained after five reuse cycles. This performance exceeds many conventional photocatalytic systems that require hours for similar inactivation levels, indicating superior charge separation and ROS generation.

What is the nature of the heterojunction formed between Au25 NCs and UiO-66-NH2, and how does it enhance photocatalytic activity?

A type-II heterojunction is engineered, which facilitates spatial separation of photogenerated electron-hole pairs, reduces recombination, and enhances visible-light harvesting. This leads to efficient O2 activation to ROS, as evidenced by the rapid bacterial inactivation.

How does the composite perform in terms of reusability and stability under operational stress?

The composite retains high antibacterial efficacy after five reuse cycles, demonstrating robust stability. The redox-mediated stabilization prevents aggregation and ligand detachment, ensuring consistent performance under repeated light irradiation and catalytic cycles.

What are the scalability and integration challenges for deploying this technology in wearable fabrics?

The integration into wearable fabrics demonstrates potential for continuous antibacterial protection. However, scalability requires uniform dispersion of Au25 NCs within the MOF matrix and adherence to textile surfaces without compromising breathability or comfort. The five-cycle reusability suggests durability, but long-term wear and laundering effects require further validation.

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