当前位置:首页>南京>AS | 南京工业李长霞、王川,柏林工业大学Arne Thomas:调控共价有机框架/石墨烯水凝胶的电荷异质性以实现耐盐

AS | 南京工业李长霞、王川,柏林工业大学Arne Thomas:调控共价有机框架/石墨烯水凝胶的电荷异质性以实现耐盐

  • 2026-03-24 06:29:49
AS | 南京工业李长霞、王川,柏林工业大学Arne Thomas:调控共价有机框架/石墨烯水凝胶的电荷异质性以实现耐盐

研究背景:

全球淡水短缺问题持续加剧,目前已有约20亿人口面临清洁水资源紧缺。太阳能驱动界面蒸发技术因可持续、环境友好成为海水淡化研究热点,但盐积累导致光热效率下降、蒸发焓升高,使盐水中蒸发速率低于纯水,限制其实际应用。因此,开发抗盐高效的光热材料,成为解决复杂环境水处理难题的核心需求。尽管已有多种策略用于提升光热蒸发效率,但在真实海水环境中,盐离子易在蒸发界面富集并结晶,导致性能衰减。尤其随着海水浓缩,这一问题更为突出。在前期双区域水凝胶设计(J. Am. Chem. Soc. 2022, 144, 3083−3090)的基础上,本工作聚焦水凝胶电荷微环境的精细调控,旨在开发兼具抗盐性与高效蒸发性能的新型材料,破解高盐环境下的效率衰减困境。

文章概述:

南京工业大学李长霞教授、王川教授,柏林工业大学Arne Thomas教授合作,通过精准调控COF在石墨烯水凝胶中的电荷分布,提出了全新的“异质电荷性增强蒸发”的策略。该设计不仅实现了盐水蒸发速率超越纯水的反常现象,还展现出广谱废水处理能力,揭示了电荷异质性在调控离子-水相互作用中的关键作用,为下一代水处理材料的设计提供了全新思路。

亮点 1:绿色可控合成,实现电荷微环境设计

本工作延续了团队此前工作中的绿色水热合成路线,无需高沸点有机溶剂,成功制备出高结晶度的带电 COF 材料。通过引入不同带电特性的 COF 单体,成功构建了四类电荷可调的 COF/石墨烯复合水凝胶体系:异质电荷型(HCG)、两性离子型(ZCG)、阳离子型(CCG)与阴离子型(ACG)。其中,在ZCG 中,阴、阳离子单体在分子尺度均匀混合;在HCG中,阴、阳离子 COF在纳米尺度保持分离,并可精准调控其比例,构建出独特的“电荷异质性”结构,实现了水凝胶表面分子级电荷微环境设计。

亮点 2:结构协同优化,显著提升蒸发效率

在石墨烯的支撑下,COF 在纳米尺度形成高度分散的三维多级孔结构,既实现 90% 的宽带光吸收效率,又构建高效连续的水传输通道,为光热转换与水分供给提供双重保障。更关键的是,异质电荷区域通过与盐离子的选择性相互作用,破坏刚性水合壳层,促进中间水形成,大幅降低液-气相变能量消耗。在 1 个太阳光强(1 kW・m-²)照射下,HCG-1 在 3.5 wt.% 盐水中的蒸发速率达 3.23 kg m-² h-¹,较纯水提升 12%。打破传统材料盐水蒸发效率低于纯水的固有局限。

亮点3:空间电荷调控,高效抑制盐积累

HCG-1通过精准设计异质电荷结构,实现对离子迁移的高效调控。其中,带负电的A-COF选择性吸附Na⁺,带正电的C-COF捕获Cl⁻,有效解耦Na⁺与Cl⁻的共迁移路径。这种“空间离子分离”机制防止了离子在蒸发界面局部富集和过饱和,从根本上抑制了盐结晶。实验表明,HCG-1 在 20 wt.% 高盐溶液中连续 12 小时蒸发无盐沉积,还具备自清洁能力,解决了传统太阳能蒸发器易盐堵、效率衰减的难题,为高盐环境下的长期稳定运行提供了可靠保障。

亮点 4:广谱适配复杂场景,实用价值突出

不仅在黄海真实海水中实现 2.97 kg m-² h-¹ 的稳定蒸发速率,还能高效处理含 Cr³⁺、Ni⁺等重金属离子的废水及甲基橙、亚甲基蓝等工业染料废水,净化效率接近 100%。更能耐受 1 M 强酸(H₂SO₄)和强碱(NaOH)环境,处理后水质 pH 接近中性,离子浓度降低三个数量级,完全符合 WHO 饮用水标准,适配多元化水处理需求。

图文导读:

图1.a)具有不同电荷类型的COF/石墨烯水凝胶(CGs)的结构示意图。b)异质电荷COF/石墨烯水凝胶(HCG)蒸发器的示意图。石墨烯网络中非均相分布的C-COF和A-COF促进了选择性离子相互作用,这种空间离子调节增强了IW的形成,减少了盐的结晶,并促进了盐分环境中稳定、高效的蒸发

图2.a) C-COF、A-COF和Z-COF的合成方案。b) C-COF、A-COF和Z-COF的XRD图谱,c) FTIR 光谱和d) zeta电位

图3.a) COF/石墨烯水凝胶(CGs)的实物照片。b) HCG-1的SEM图像和c) TEM图像。d) HCG-1的SEM图像及相应的EDS能谱图。e, f) HCG-1的AFM图像及相应的高度分布图。g) CGs的FTIR 光谱图,h) zeta电位和 i) UV–vis- NIR 光谱图

图4.a) 水蒸发实验装置示意图。b, c) CGs在1个太阳光照下, 3.5 wt.% 盐水中随时间变化的温度与质量变化曲线。d) CGs在1个太阳光照下的水蒸发速率与能量效率。e) HCG-1在纯水与3.5 wt.% 盐水中的蒸发速率与已有研究报道材料的对比。f) 差示扫描量热法(DSC)测定的CGs蒸发焓数值学

图5.a) HCG-1在纯水和3.5 wt.% 盐水中的拉曼光谱。b) 水凝胶网络中水分子存在形态的示意图。c) 不同CGs中中间水(IW)与自由水(FW)的比例。d) HCG-1在3.5 wt.% 盐水中的12天稳定性测试。e) HCG-1在1个太阳光照下在真实海水中的蒸发速率。f) HCG-1表面盐颗粒随时间溶解的照片。g) 在1个太阳光照下,ACG 、CCG、 ZCG 和HCG-1在20 wt.%盐水中连续蒸发12小时后的照片

图6.a) A-COF、C-COF和Z-COF的ESP分布图。 b) A-COF、C-COF和Z-COF对Na⁺/Cl⁻吸附能。 c) ACG 、CCG、 ZCG 和HCG-1的抗盐机理示意图

图7.a) 水收集装置的实物照片。 b) 海水淡化前后的离子浓度变化。 c) 污水净化前后的重金属离子浓度变化。 d) 染料污染水与净化水的紫外-可见光谱及实物照片。 e) 强酸性与强碱性水溶液的净化能力对比

结论:

本工作针对太阳能界面蒸发技术在高盐环境中面临的盐积累、蒸发效率衰减等关键问题,创新提出异质电荷 COF/石墨烯水凝胶设计。通过将阳离子 COF(C-COF)与阴离子 COF(A-COF)以精准比例在石墨烯网络中实现纳米尺度空间分离,构建出电荷分布可控的异质电荷水凝胶(HCG),既解决了传统 COF 粉末加工性差、缺乏宏观连通性的缺陷,又突破了两性离子水凝胶电荷调控精度不足的局限,借助空间离子选择性作用促进中间水形成、降低蒸发焓,实现高盐环境下更优异的蒸发性能与抗盐稳定性。

论文信息

Engineering Charge Heterogeneity in COF/Graphene Hydrogels for Salt‐Resistant Solar Evaporation

Shuwen Jia, Yanrui Li, Guangyu He, Xinda Nan, Xiao Xiao, Chuan Wang*, Arne Thomas*, and Changxia Li*

Advanced Science 

DOI:10.1002/advs.202519171

原文链接

 https://doi.org/10.1002/advs.202519171

期刊简介

Advanced Science是 Wiley旗舰期刊 Advanced 系列中的一种完全开放获取的跨学科科学期刊,发表材料科学、物理、化学、医学、生命科学、环境科学、工程和社会科学等领域的前沿基础和应用研究。我们的使命是通过开放获取出版,使前沿创新的科学研究具有更广泛的可访问性。Wiley 的 Advanced 系列是全球公认的高影响力期刊系列,传播来自资深和青年研究人员的科学成果,帮助他们实现使命并扩大科学发现的影响力。

Advanced Science最新2024影响因子(JIF)为 14.1,五年平均影响因子为 15.6,JCI 引文指标为1.90,CiteScore 为 18.2。在 2025年中国科学院院文献情报中心期刊分区表中,Advanced Science入选综合类期刊一区TOP。

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  1. CONNECT:[ UseTime:0.000351s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000575s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000229s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000249s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000493s ]
  6. SELECT * FROM `set` [ RunTime:0.000190s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000494s ]
  8. SELECT * FROM `article` WHERE `id` = 488942 LIMIT 1 [ RunTime:0.000428s ]
  9. UPDATE `article` SET `lasttime` = 1775450078 WHERE `id` = 488942 [ RunTime:0.000586s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000213s ]
  11. SELECT * FROM `article` WHERE `id` < 488942 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.000426s ]
  12. SELECT * FROM `article` WHERE `id` > 488942 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000352s ]
  13. SELECT * FROM `article` WHERE `id` < 488942 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.010585s ]
  14. SELECT * FROM `article` WHERE `id` < 488942 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.007168s ]
  15. SELECT * FROM `article` WHERE `id` < 488942 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.006416s ]
0.100552s