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郑州大学臧双全/刘仲毅/张文垒Angew | 通过单原子聚合物涂层调控金属-载体相互作用:高性能催化剂的通用策略

  • 2026-05-02 00:05:14
郑州大学臧双全/刘仲毅/张文垒Angew | 通过单原子聚合物涂层调控金属-载体相互作用:高性能催化剂的通用策略

负载型金属催化剂在选择性加氢等重要反应中应用广泛,但传统载体结构刚性,对金属纳米颗粒的电子与几何微环境调控能力有限,金属掺杂改性方法存在灵活性不足、易破坏载体结构等问题,聚合物涂层具有优异界面适配性,将原子级分散金属位点引入聚合物涂层构建多功能界面层,实现金属-载体相互作用精准定制并拓展催化体系普适性的研究仍亟待突破。

郑州大学臧双全/刘仲毅/张文垒团队创建单原子聚合物涂层调控金属-载体相互作用的通用方法,实现选择性加氢催化性能的大幅提升,并成功拓展至多种催化体系,为高性能多相催化剂的界面精准设计提供全新通用范式。相关成果发表于《Angewandte Chemie International EditionIF 17 ,新锐期刊分区:1区 Top)

研究团队开发原子分散金属掺杂聚合物涂层策略,以聚多巴胺掺杂铜为界面修饰层,在二氧化硅与铂纳米颗粒之间构筑功能界面,制备得到 Pt/SiO₂@PDA-Cu 催化剂,高分辨透射电镜显示铂纳米颗粒尺寸约 2.8 nm 且均匀分布,球差校正高角环形暗场扫描透射电镜直接观测到原子级分散的铜位点,元素面分布证明硅、氧、碳、氮、铜、铂元素均匀分布(图 1b-1f)。射线光电子能谱显示铜通过聚多巴胺的氨基与羟基稳定配位,氮与氧元素结合能发生特征位移,同时存在氯元素作为平衡离子(图 1g-1i),粉末 X 射线衍射与红外光谱证实聚多巴胺涂层成功包覆且载体晶相保持完整。

 4-硝基苯乙烯选择性加氢反应中,Pt/SiO₂@PDA-Cu 催化剂实现 99% 以上转化率与 98% 以上的 4-氨基苯乙烯选择性,远高于原始 Pt/SiO₂与无铜掺杂的 Pt/SiO₂@PDA 催化剂,延长反应时间仍不发生过度加氢,循环使用六次后活性与选择性无明显衰减,结构保持高度稳定(图 2a-2g)。射线光电子能谱与原位一氧化碳漫反射红外光谱证明,铜掺杂聚多巴胺涂层诱导电子从铂纳米颗粒向界面转移,降低铂表面电子密度,提升二价铂物种比例,削弱对碳碳双键的吸附与活化能力(图 3a-3f)。密度泛函理论计算表明,缺电子铂活性中心更有利于硝基吸附活化,同时提高乙烯基加氢能垒,促进产物脱附,从而实现高选择性(图 4a-4d)。

该策略具备优异通用性,可将铁、钴、镍、铜等单原子分别掺杂聚多巴胺涂层,适配二氧化硅、氧化铈、SBA-15COF-300、氧化铋、氧化铜、分子筛等多种载体,也可拓展至聚吡咯、壳聚糖、聚乙烯醇等聚合物体系,成功制备十余种新型催化剂,所有改性催化剂在选择性加氢反应中选择性均得到显著提升(图 5a-5m)。

该工作提出原子分散金属掺杂聚合物涂层的通用策略,在金属纳米颗粒与载体之间构筑可设计的功能界面层,精准调控金属-载体电子相互作用,显著提升硝基芳烃选择性加氢的催化活性、选择性与稳定性,该方法不破坏载体本征结构,可灵活组合金属、聚合物与载体,为多种高效负载型催化剂的理性设计提供模块化平台,拓展界面工程在多相催化中的应用范围。

文献参考:(点击左下角可阅读原文)

W.Lang, F.Chen, X.Du, et al. "“Tailoring Metal-Support Interactions With Single-Atom Polymer Coatings: A Universal Strategy for High-Performance Catalysts," Angewandte Chemie International Edition. (2026): e9654585. https://doi.org/10.1002/anie.9654585

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  1. CONNECT:[ UseTime:0.001133s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001725s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.001378s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000701s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001434s ]
  6. SELECT * FROM `set` [ RunTime:0.000658s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001603s ]
  8. SELECT * FROM `article` WHERE `id` = 509215 LIMIT 1 [ RunTime:0.001041s ]
  9. UPDATE `article` SET `lasttime` = 1778038227 WHERE `id` = 509215 [ RunTime:0.002389s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000701s ]
  11. SELECT * FROM `article` WHERE `id` < 509215 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.001253s ]
  12. SELECT * FROM `article` WHERE `id` > 509215 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001106s ]
  13. SELECT * FROM `article` WHERE `id` < 509215 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.002026s ]
  14. SELECT * FROM `article` WHERE `id` < 509215 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.002293s ]
  15. SELECT * FROM `article` WHERE `id` < 509215 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.002026s ]
0.137616s