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    三嗪化木碳点赋能木纹无损可视紫外屏蔽耐光PVA膜

    Triazine wood-derived carbon dots deliver photostable PVA films with visible wood grain and UV shielding

    • 摘要:
      目的 紫外光(200 ~ 400 nm)触发木材表面木质素和抽提物生成醌类发色体,引起不可逆变色与力学衰减,已成为制约木材高端应用的瓶颈。现行防护策略常以牺牲木纹美感为代价,或因分散性差、透明性不足而难以兼顾审美与长效屏蔽,亟需开发“高紫外屏蔽−高可见透明”的一体化新材料。为此,本研究提出以三嗪功能化木源碳点(CDs)为核心构建聚乙烯醇(PVA)复合薄膜,旨在保持木材天然纹理的同时,提升其耐光变色的稳定性。
      方法 以富含萜类抽提物、耐腐抗虫的速生杉木粉为碳源,150 ℃水热预抽提富集碳水化合物后,加富氮三肼三嗪(THT)为表面修饰剂,高温水热碳化制得THT-CDs;再与PVA共混,流延成PVA@THT-CDs复合薄膜。TEM、FTIR、XPS、XRD、荧光光谱和UV-Vis分光光度计联合表征 THT-CDs的形貌、化学结构及光学性能,并量化复合薄膜的紫外屏蔽效率,以无机 ZnO 和有机UV-384涂层为参照。随后,将薄膜覆于薄木表面,在高功率紫外灯下加速老化,定期测定CIE Lab色度参数,评估其抑色性能。借助光纤光谱仪采集薄膜在370 nm单波长及模拟日光下的透射光谱,对比两束光透过后的谱图差异,解析木材表面的光传输行为及黄变机制。
      结果 THT-CDs呈类石墨球形,平均粒径5.53 nm,在水中分散性优异;在372 nm激发下,THT-CDs发出445 nm明亮蓝光,荧光量子产率达21.4%,显示出高效的光致发光性能。当添加量仅为2%时,PVA@THT-CDs复合薄膜可屏蔽90.3%以上的紫外光,380 nm与400 nm处透过率分别降至0.3%和9.7%,而800 nm可见光透过率仍保持82.4%,其紫外−可见选择性分离效率显著优于ZnO和UV-384对照膜。CIE色度轨迹进一步证实,该复合薄膜在加速紫外老化过程中能有效抑制基材色差增大,展现出卓越的光学稳定性。
      结论 本研究通过三嗪功能化木材衍生碳点,成功解决了传统材料的紫外吸收弱、屏蔽效率低、透明性不足的技术瓶颈:借助 THT-CDs 的广谱紫外吸收−可见光转换机制,实现了“高紫外屏蔽与高透明”的协同效应,在木材表面构筑了一层透明、长效且保留天然木纹的耐光老化薄膜。该策略不仅突破了传统屏蔽材料透明性不足的局限,也为速生杉木的高值化利用开辟了新路径,对推动木质家居、展陈制品及室外景观材的绿色升级具有现实可行性。

       

      Abstract:
      Purpose UV light (200-400 nm) converts wood lignin and extractives into quinone chromophores, causing irreversible discoloration and strength loss that limit high-end applications. Existing coatings either hide the grain or lack transparency and long-term UV protection. Here, we report a transparent poly(vinyl alcohol) (PVA) film armed with triazine-functionalized wood-derived carbon dots (CDs) that blocks UV while keeping the natural texture visible.
      Method Fast-growing, terpene-rich and decay-resistant Cunninghamia lanceolata sawdust was used as the carbon source. After pre-extraction at 150 ℃ to enrich carbohydrates, nitrogen-rich triaminotriazine (THT) was added as a surface modifier and the mixture was subjected to high-temperature hydrothermal carbonization to yield THT-CDs. The dots were then blended with PVA and cast into PVA@THT-CDs composite films. TEM, FTIR, XPS, XRD, fluorescence and UV-Vis spectroscopy were combined to image the morphology, chemistry and optical response of THT-CDs, and to quantify the UV-shielding efficiency of the composite film, using inorganic ZnO and organic UV-384 coatings as comparison. The film was laid over veneer and aged under high-power UV light. CIE Lab* values were recorded at intervals to rate color suppression. A fiber-optic spectrometer collected the transmission spectra of the film under 370 nm monochromatic light and simulated solar irradiation; comparison of the two spectra revealed the light-transport behavior at the wood surface and the mechanism of UV-induced yellowing.
      Results THT-CDs exhibit a graphitic spherical morphology with an average diameter of 5.53 nm and excellent dispersibility in water. Upon excitation at 372 nm, they emit bright blue light at 445 nm with a photoluminescence quantum yield of 21.4%, indicating highly efficient light emission. When incorporated at only 2 wt%, the PVA@THT-CDs composite film blocks over 90.3% of UV radiation; transmittance drops to 0.3% at 380 nm and 9.7% at 400 nm, while 82.4% of visible light at 800 nm is still transmitted. This UV-vis selective separation efficiency is markedly superior to that of ZnO and UV-384 reference coatings. CIE color trajectory analysis further confirms that the composite film effectively suppresses color change of the underlying wood during accelerated UV ageing, demonstrating outstanding optical stability.
      Conclusion Triazine-functionalized, wood-derived carbon dots were used to overcome the weak UV absorption, low shielding efficiency, and poor transparency of conventional additives. The broad-spectrum UV-vis conversion of THT-CDs delivers high UV blocking without sacrificing transparency. A clear, durable, grain-preserving anti-aging film was formed on wood. The approach bypasses the poor clarity of conventional UV blockers and upgrades fast-grown fir into a high-value material, offering a green route for furniture, displays and outdoor timber.

       

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