兼具荧光可视化的含银钙钛矿抗菌涂层研究

Silver-containing Perovskite Antimicrobial Coatings with Fluorescence Visualization

摘要

细菌在公共环境中的生长可能对人类健康及设施安全带来潜在风险，而其在材料表面的附着是细菌传播的主要途径，因此，保护材料表面免受细菌污染仍然是一项重要挑战。涂层抗菌功能化作为解决上述问题的有效策略，相比传统的表面清洁或直接添加抗菌剂的方法，能够在材料表面实现持久且均匀的抗菌效果，同时兼顾安全性与操作简便性。本文制备了含银的Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光材料，通过与环氧‒聚酯粉末涂料结合，利用粉末喷涂技术制备多功能复合涂层，进一步对该复合涂层的结构形貌、发光性能和抗菌性能进行系统表征。结果表明：200 ℃固化制得的环氧‒聚酯荧光复合涂层具有与标准Cs₂NaInCl₆一致的晶体结构，且各种元素分布均匀，样品在365 nm紫外线激发下，表现出发射峰值在630 nm的荧光发射，发光强度和紫外‒可见吸收能力随荧光粉比例的增加而增强；该复合涂层对大肠杆菌的抗菌率达到99.53%。此外，涂层耐水性（水中浸泡30 d）和紫外老化（365 nm紫外光照射5 d）测试结果表明，涂层样品在浸泡和紫外照射后表面均无起泡、开裂或者脱落等情况，且荧光强度保持在初始强度约80%，表明该涂层具有较好的耐水性和紫外稳定性。基于目前市面上的抗菌涂层，其抗菌性能通常只能通过仪器检测，普通消费者难以直观判断效果。本文所研究的荧光抗菌复合涂层将荧光性能与抗菌效果结合，有望通过观察发光强度对抗菌能力进行可视化评估，从而为判断涂层抗菌效果和使用寿命提供参考。研究结果为开发直观、可视化的抗菌性能评估方法提供了新思路。

Abstract

Objective The growth of bacteria in public environments poses potential risks to human health and facility safety. Bacterial adhesion to material surfaces represents a primary route of transmission. Therefore, protecting material surfaces against bacterial contamination remains a significant challenge. The antimicrobial functionalization of coatings provides an effective strategy for addressing these issues. Compared to traditional methods, such as surface cleaning or the direct addition of antimicrobial agents, this approach provides long-lasting and uniform antimicrobial effects on surfaces while ensuring safety and ease of use. In this study, a silver-containing Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺ fluorescent material is prepared and combined with an epoxy-polyester powder coating to form a multifunctional composite coating. Its structural morphology, luminescent properties, antibacterial performance, and the effects of water immersion and UV irradiation on these properties are investigated. This multifunctional composite coating exhibits highly efficient antimicrobial capabilities and good luminescent properties. It also demonstrates superior stability under water immersion and UV irradiation, providing a new strategy for developing safe and highly effective antimicrobial materials. Methods Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺ fluorescent perovskite powders were synthesized using a mechanochemical method, incorporated into an epoxy-polyester powder coating matrix, and fabricated into multifunctional composite coatings using powder coating technology. This method stabilized silver ions within the perovskite lattice and achieved sustained release. This approach not only prolonged the duration of the antibacterial effect but also reduced environmental risks. Bacterial cell walls, proteins, and DNA were disrupted by released Ag⁺ ions, directly inhibiting bacterial growth. Simultaneously, under illumination, the perovskite absorbed photons and generated photo-induced electrons and holes, which produced reactive oxygen species (ROS) that acted synergistically with silver ions to enhance antibacterial efficiency. The crystal structure of the composite coating was characterized using X-ray diffraction (XRD). Surface morphology and elemental distribution were analyzed using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). Optical properties were investigated using photoluminescence (PL), photoluminescence excitation (PLE), and ultraviolet-visible (UV-vis) spectroscopy. Antibacterial performance against Escherichia coli was evaluated by measuring CFU after a specified exposure time. Durability tests, including water immersion and UV aging, were also conducted to assess coating stability. Results and Discussions XRD analysis confirmed that the Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺ powder retained a crystal structure consistent with that of standard Cs₂NaInCl₆ even after it was embedded in the polymer matrix. Characteristic diffraction peaks remained detectable even when the phosphor content in the coating was as low as 10%, which indicated good crystallinity and phase stability. Scanning electron microscopy (SEM) images showed that the fluorescent particles were approximately 2 µm in size, with no obvious cracks or pores observed between the particles, while the overall surface remained smooth, which indicated good coating uniformity. EDS results indicated a uniform elemental distribution, with no significant segregation observed. Optical measurements indicated that all experimental samples were excited by 365 nm UV light and exhibited an emission peak at 630 nm. Both luminescence intensity and UV-visible absorption increased with the proportion of phosphor. Because of the local energy levels introduced by the added Ag⁺ and Bi³⁺ ions, the composite coating exhibited a new absorption peak at 380‒450 nm. This behavior not only preserved the main band absorption of the perovskite but also introduced additional excited states, which further enhanced the material's photoluminescence efficiency. Observations under a metallographic microscope at 20× and 50× magnification revealed a uniform fluorescence distribution across the coating under UV irradiation. After 30 days of water immersion and 5 days of UV aging, respectively, the composite coating showed no blistering, cracking, or peeling on its surface, and the PL intensity remained at approximately 80%, which indicated that the coating exhibited good weather resistance and stability. Antibacterial testing showed that, compared to the control group of pure epoxy-polyester coatings, the fluorescent composite coating exhibited a significantly reduced colony-forming unit (CFU) count. Calculations indicated that the antibacterial rate against Escherichia coli reached 99.53%, which demonstrated that the composite coating effectively inhibited the growth of Escherichia coli. Conclusions The results indicate that the phosphors in the coating exhibit good crystallinity and uniform distribution, while the coating demonstrates stable photoluminescence under UV irradiation and during water immersion. In addition, the silver-doped coating effectively inhibits Escherichia coli, demonstrating excellent antimicrobial efficacy. This method provides a balance among material safety, ease of use, and versatility, providing a viable approach for developing functional antimicrobial coatings. Currently, the antibacterial performance of commercially available coatings can typically be evaluated only through instrumental testing, making it difficult for ordinary consumers to assess their effectiveness. The fluorescent antibacterial composite coating investigated in this study combines fluorescence properties with antibacterial performance, providing the potential for the visual evaluation of antibacterial activity based on fluorescence intensity: higher fluorescence intensity corresponds to stronger antibacterial effects, whereas a decrease in fluorescence intensity over time can indicate reduced antibacterial performance, providing a reference for assessing the service life of the coating. This approach offers a potential strategy for developing intuitive and visual methods for evaluating antibacterial capability in the future.

Graphical abstract

关键词

抗菌涂层 / 粉末涂料 / 荧光涂层 / 钙钛矿材料

Key words

antibacterial coating / powder coating / fluorescent coating / perovskite material

本刊网刊

细菌的积累和繁殖会带来潜在的卫生和健康风险^[1]。在日常生活中，细菌常见于水管、厨房等家庭环境表面^[2]；在公共场所，它们也容易附着在医疗器械及各种设施上^[3]。细菌在各种涂层材料表面的附着和生长不仅会导致材料表面被腐蚀、性能下降^[4]，还会增加交叉污染的风险^[5]。因此，提升材料的抗菌能力对延长材料寿命^[6]和降低维护成本^[7]具有重要意义。高效的抗菌涂层能够主动抑制细菌生长，减少微生物对材料和环境的危害^[8]，从而在工业^[9]、医疗^[10]和公共设施^[11]等领域发挥重要作用。

目前，市面上常用的抗菌策略主要包括3类：一是，通过添加有机抗菌剂实现抗菌^[12]，但这类抗菌剂易随使用时间增加而失效或被洗脱^[13]；二是，在材料表面进行修饰或涂层覆盖以实现抗菌^[14]，但此类方法操作复杂且工艺成本较高^[15]；三是，掺杂金属离子（如金、铜、锌、银）^[16]，其中银离子因其广谱抗菌性能成为金属离子抗菌的核心选择。例如，Sambhy等^[17]通过在材料中直接加入溴化银纳米颗粒，使银离子释放到材料表面，与细菌接触后破坏细胞壁并抑制代谢活动，从而抑制细菌生长。这类方法虽然能够有效发挥抗菌作用，但通常存在银纳米颗粒易团聚^[18]、银盐释放速度难以控制、长期稳定性差或对环境有潜在毒性^[19]等问题。因此，开发一种兼具高效抗菌能力、长期稳定性和低环境毒性的新型抗菌策略显得尤为重要。

为此，本文将银离子复合到双钙钛矿的稳定结构中制备了无铅荧光钙钛矿材料Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺，并将其均匀分散在环氧-聚酯粉末涂料中制备功能性涂层。银离子在双钙钛矿晶格中的稳定存在，为涂层提供了银基抗菌活性来源，同时避免了游离银盐快速释放带来的环境风险^[20]。已有研究表明，银离子具有广谱抗菌能力，可通过破坏细菌细胞膜结构、与蛋白活性基团结合影响关键代谢过程，并干扰遗传物质复制等途径抑制细菌生长^[21]。此外，钙钛矿材料具有优异的光吸收和光生载流子产生能力，在光照条件下可能产生电子-空穴对促进活性氧（ROS）的形成^[22]，进一步诱导氧化损伤。因此，该复合涂层的抗菌性能可能来源于Ag活性组分作用与光诱导氧化过程的共同贡献。

钙钛矿材料因其独特的三维晶体结构和优异的电子能带特性，具有很强的光吸收和光转化能力，使其在发光领域表现出优异性能。利用其光致发光特性，本研究制备的涂层不仅拥有出色的光学性能，还能够实现抗菌功能的可视化：荧光信号可以直观反映活性成分的分布和均匀性，同时间接显示抗菌活性区域，从而将光学性能与抗菌效果有效耦合。该多功能复合涂层不仅具备高效抗菌能力和良好发光性能，还在水浸泡及紫外照射条件下表现出优异稳定性，为开发安全、高效的抗菌材料提供了一种新策略。

1 实验部分

1.1 实验原料

氯化铯（分析纯，山东科源生化有限公司）；氯化银（分析纯，上海阿拉丁生化科技股份有限公司）；氯化钠（分析纯，广东光华科技股份有限公司）；氯化铟（99.99%，上海麦克林生化科技股份有限公司）；氯化铋（99.99%，上海麦克林生化科技股份有限公司公司）；乙醇（分析纯，广东广试试剂科技有限公司）；环氧‒聚酯粉末涂料，广东西敦千江粉漆科学研究有限公司。所有材料均未经任何处理直接使用。

1.2 合成方法

以制备10 g Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺为例，首先，分别称取5.02 g CsCl、1.28 g AgCl、0.35 g NaCl、3.16 g InCl₃、0.19 g BiCl₃放入研钵；然后，加入乙醇多次研磨，直至均匀，磨干后放入80 ℃烘箱干燥12 h，最终获得Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺前驱体。

称取不同比例的Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺样品与环氧‒聚酯树脂混合，先用研钵研磨30 min，再用咖啡机混合15 min，然后将混合后的样品通过静电喷涂在铝板上，最后在200 ℃烘箱固化10 min。最终得到Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺环氧‒聚酯复合涂层。具体配方见表1，合成路线如图1所示。

1.3 材料表征

1.3.1 形貌与结构表征

扫描电子显微镜（SEM）测试：将样品放置在扫描电子显微镜（型号TM3030，Hitache，日本）样品架上，在10 kV的加速电压下进行表面形貌扫描。

能量色散X射线光谱（EDS）测试：光电子能谱仪（型号Escalab.250Xi，Thermo Fishere，美国）中的EDS探测器能够识别样品表面的元素成分，并通过能量分辨的X射线谱线，得到元素的定性和定量信息。

X射线衍射（XRD）测试：样品粉末经过压片处理后，通过衍射仪（型号D8·ADVANCE，Bruker，德国）进行扫描，测试其衍射图谱。通过比较实验数据与标准PDF数据库中钙钛矿结构衍射峰，确定材料相组成及其晶体结构。

1.3.2 光谱性能表征

光致发光光谱（PL）和光致发光激发光谱（PLE）测试：在PL测试中，涂层样品通过荧光光谱仪（型号FLS1000，Edinburgh Instruments，英国）中的365 nm的激发光激发。此外，固定发射波长为630 nm，记录激发光谱的变化，从而分析材料的激发发射光学性能。

紫外‒可见光谱（UV‒vis）测试：样品通过紫外‒可见分光光度计（型号Cary 5000，Varian，美国）进行扫描，记录其紫外到可见光波段吸收率的变化。

1.3.3 抗菌性能表征

不同荧光粉含量会影响复合涂层的荧光性能、颗粒分散状态以及涂层结构稳定性。综合考虑荧光响应、抗菌活性、涂层成膜性能及制备成本，本研究选取质量分数为10%的Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺复合涂层作为代表性样品进行抗菌性能评价。

菌落形成单位（CFU）测试：通过将大肠杆菌菌液放置在涂层上，经过1 h的培养，计算其表面上生长的细菌菌落数量。

1.4 实验方法

为评价复合涂层的环境稳定性，选取质量分数为10%的Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光粉的涂层样品，分别进行耐水性能测试和耐紫外光性能测试。

1.4.1 耐水性能

耐水测试：将涂层样品制成小板，并将其浸泡在装有自来水的塑料杯中浸泡30 d。在这个过程中每隔5 d取出样品进行一次光致发光光谱（PL）检测。通过比较不同时间点的PL强度，评估涂层在水浸泡条件下的光学稳定性。

此外，在测试结束后，取出样品并观察其表面形貌变化，观察涂层表面是否发生起泡、开裂或者脱落等情况，进一步评估涂层在长时间水浸泡中的耐水性和结构稳定性。

1.4.2 耐紫外光性能测试

将涂层样品暴露于光功率为440 mW/cm²、波长为365 nm紫外灯下，紫外光源与样品之间的距离保持为28 cm，并持续照射5 d。在测试过程中，每隔1 d取出，使用光致发光光谱（PL）测试其发光强度，并记录强度的变化。通过比较不同照射时间点的PL强度，评估涂层在紫外光照射下的光学稳定性，并判断材料是否出现了性能退化。

2 结果和讨论

2.1 形貌与结构分析

通过扫描电子显微镜对Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺含量为10 %的复合涂层的表面形貌进行观察，结果如图2所示。由图2可知，荧光粉颗粒能够有效嵌入环氧-聚酯基体中，但局部区域存在一定聚集现象。这主要归因于无机颗粒较高的表面能以及其与有机聚合物基体之间较弱的界面相互作用，同时颗粒与树脂之间的密度差异也可能促进固化过程中的局部富集。颗粒之间未见明显的裂纹或孔隙，整体表面平整，说明该涂层材料具有较好的均匀性。

图3为涂层的EDS分析结果。通过EDS测试，可确认涂层中主要元素的分布情况。EDS结果显示，Cs、Ag、Na、In、Cl等元素均存在于涂层区域内，证明荧光粉成功引入复合涂层。虽然元素分布存在局部差异，但未观察到明显的大尺度团聚，说明荧光颗粒仍保持有效分布。因此，该复合结构仍能够保证荧光组分在涂层中的有效存在，为后续光致发光和抗菌性能提供活性来源。

图4为金相显微镜下的涂层荧光分布。

通过20倍和50倍的放大观察，在紫外光激发下，涂层表面呈现连续的荧光响应，虽然局部区域存在亮度差异，但整体荧光信号覆盖整个测试区域，说明荧光粉能够赋予涂层稳定的光学响应。

图5展示了涂层在不同荧光粉比例下，分别在日光和紫外光照射下的形态变化。图6为不同荧光粉含量涂层的归一化PL强度。在日光照射下，荧光粉比例的增加并未导致明显的颜色变化；而在紫外光照射下，从荧光粉质量分数为1%的复合涂层开始就出现黄色发光，随着荧光粉含量从1%增加至40%，涂层的PL发射强度整体呈增强趋势。

2.2 晶体结构分析

图7给出了Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺钙钛矿晶体结构。加入Ag⁺、Bi³⁺有利于该材料的晶体结构。其中，Ag⁺通过同价替换^[23]的方式替代了Na⁺。由于Na⁺直径为1.02 Å，而Ag⁺直径为1.26 Å，两者直径相近，所以Ag⁺可以很好地取代Na⁺的位置^[24]。这种同价替换（Ag⁺替代Na⁺）不会破坏晶体的电荷平衡^[25]，因为两者的电荷相同，在此过程中也不会对晶体结构产生显著的负面影响^[26]。此外，Bi³⁺也以类似方式替代了In³⁺，因其电荷和半径与In³⁺相似^[27]。Ag⁺和Bi³⁺加入不仅能对晶格起到一定程度优化，而且明显改善了其光学性能，特别是光致发光性能和稳定性^[28]。

图8展示了Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺与环氧‒聚酯粉末涂料复合后的X射线衍射（XRD）谱图。通过将复合涂层的XRD图谱与Cs₂NalnCl₆的PDF卡片比较可以证明，Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺与环氧‒聚酯透明粉的复合涂层保留了Cs₂NalnCl₆的结构，表明该材料在涂层中并未发生相变。相比于更高比例的涂层，10%荧光粉比例的衍射峰强度略低，但结构特征清楚，仍然可以清晰观察到主要衍射峰，说明该比例下的荧光粉已经形成稳定晶体。

2.3 荧光光谱分析

图9展示了涂层的光致发光（PL）光谱和光致发光激发光谱（PLE）曲线。随着Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光粉比例的增加，涂层的PL强度逐渐增强。纯环氧‒聚酯涂层，在发射光谱中几乎没有显著的发光信号，而随着荧光粉的加入，涂层的发光强度逐渐增强，在40%荧光复合涂层时，发射强度达到最大。这表明，随着荧光粉比例的增加，涂层的光致发光性能得到显著增强。在PLE光谱方面，随着荧光粉比例的增加，激发光谱也呈现出相同的增强趋势。

图10展示了不同荧光粉比例下涂层的漫反射吸收光谱。随着荧光粉比例的增加，涂层在紫外‒可见光范围内的吸收显著增强。以10%荧光复合涂层为例，主要吸收峰对应钙钛矿材料的带间跃迁，表现出良好的光吸收能力，表明荧光粉在涂层中有效吸收光子，为光致发光提供能量^[29]。与纯环氧‒聚酯涂层相比，复合涂层在380～450 nm处有一个新的吸收峰，这通常与掺杂的Bi³⁺或加入的Ag⁺引入的局部能级相关。该峰源于晶体中杂化能级产生的额外光吸收^[30]，使材料在特定波长范围内增强了光吸收能力，也与荧光峰的激发波长（PLE）对应。该现象说明新元素的加入不仅保持了钙钛矿的主带吸收，还引入了额外的激发态，进一步增强了材料的光致发光效率。

2.4 抗菌效果分析

图11展示了纯环氧‒聚酯涂层（对照组）和复合涂层的抗菌性能比较。上排为纯环氧‒聚酯涂层，下排为含10% Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光粉的环氧‒聚酯复合涂层。实验中使用的菌种为大肠杆菌，将灭菌后的涂层样品置于无菌培养皿中，滴加100 μL浓度约为10⁶ CFU/mL的大肠杆菌菌液，使菌液均匀覆盖样品表面。在37 ℃恒温条件下共培养1 h，使细菌与涂层充分接触并发生抗菌作用，固化后的涂层暴露表面作为抗菌测试界面，细菌通过直接接触涂层表面进行抗菌评价。共培养结束后，采用无菌移液枪收集涂层表面的菌液，并进行梯度稀释（10、100、1 000和10 000倍）。随后，取100 μL稀释后的菌液均匀涂布于LB固体培养基平板上，并在37 ℃条件下培养24 h。培养结束后，对平板上的菌落数量进行统计，并根据菌落形成单位（CFU）计算涂层的抗菌性能。

在对照组中，菌落数量在所有稀释倍数下都较为密集，表明环氧‒聚酯涂层几乎没有抗菌效果。特别是在10、100和1 000稀释倍数下，培养皿表面有大量细菌生长，说明该涂层未能有效抑制细菌的生长。相比之下，含Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光粉的环氧‒聚酯复合涂层在各稀释倍数下均表现出明显的抗菌效果。菌落数在涂层表面显著减少，尤其是在1 000和10 000稀释倍数下，细菌存活率仅为0.47%，显示该涂层具有较强的抗菌作用。根据计算，该涂层抗菌率达到99.53%，表明材料能够有效抑制大肠杆菌生长。

上述结果表明，掺入Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光粉的环氧‒聚酯复合涂层显著提高了涂层的抗菌能力，10% Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺复合涂层表现出优异的抗菌性能，对大肠杆菌具有明显抑制作用，说明该体系具有作为功能化抗菌涂层的应用潜力。在实际应用中，这类荧光抗菌涂层可用于公共空间或医疗环境中，能提供有效的抗菌保护。

2.5 环境稳定性测试分析

图12展示了涂层在自来水中浸泡30 d期间光致发光（PL）强度的变化趋势。实验结果显示，涂层在浸泡过程中PL强度逐渐下降，但整体衰减幅度较小。从图12可以看出，初始PL强度经过30 d浸泡后仍保持约78%，说明涂层在水中具有良好的光学稳定性。

同时，图12中插图展示了浸泡前和浸泡30 d后的涂层实物情况。可以看到，涂层在泡水后未出现开裂、剥落或膨胀，进一步说明涂层的结构稳定性良好，具有一定的耐水性。

图13展示了涂层在365 nm紫外灯下照射5 d期间PL强度的变化。在经过5 d的紫外照射后，PL强度轻微下降，最终保持在约80%左右。图13中插图展示了紫外照射前和照射5 d后的涂层实物情况。由此可见，该涂层表面未出现明显的开裂、褪色或损伤，表明涂层在短期紫外光照射下仍能保持良好的光学性能和结构完整性。

3 结 论

本文通过在Cs₂NalnCl₆中引入Ag⁺和Bi³⁺的化学合成方式成功制备了Cs₂Ag_0.6Na_0.4InCl₆:Bi³⁺荧光材料，并将其均匀分散在环氧‒聚酯涂层中制备功能涂层，实现了光学性能、稳定性与抗菌性能的多功能协同。该涂层主要用于需要表面抗菌和功能识别的环境，如公共设施表面、设备防护层以及具有可视化需求的功能涂层领域。研究结果表明，涂层中的荧光粉保持良好的结晶性和均匀分布，涂层在紫外光和水浸泡条件下表现出稳定的光致发光性能，同时含Ag⁺的荧光涂层能够高效抑制大肠杆菌，抗菌率达到99.53%。该方法兼顾了材料的安全性、可操作性和多功能性，为功能性抗菌涂层的开发提供了可行方案。

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基金资助

广东省重点领域研发计划项目(2025B0101030002)

国家自然科学基金项目(52572159)

广东省科学技术协会项目(SKXRC2025191)

广州医科大学附属中医医院‒广东工业大学医工融合科研项目（GDUT‒GZTCM‒2026004）