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南京大学发马年首篇顶刊!

  • 2026-03-17 22:34:04
南京大学发马年首篇顶刊!

稳定的超大孔沸石分子筛在大分子催化和分离领域具有重要应用价值,但目前大多数材料仍局限于微孔尺度,从而限制了其在大分子底物中的应用。南京大学化学学院黎建特聘研究员团队通过构筑大体积的双季磷盐结构导向剂,成功创制本征全结晶介孔孔道的36元环硅铝/硅钛沸石分子筛NJU120-6

相关成果以“A 36-ring zeolite with intrinsic cylindrical mesopores”为题,于2026年2月20日在线发表于《科学》期刊,标志着稳定全结晶介孔沸石分子筛的设计与构筑迈入新阶段为重质油高效转化和大分子精细化学品催化转化提供了全新材料平台

研究背景

沸石分子筛因其规则微孔结构和优异的热稳定性,在石油炼制和精细化工中发挥着不可替代的作用。然而,传统工业沸石分子筛多为12元环微孔结构,孔径通常小于0.75纳米,在处理多环芳烃、树脂及沥青质等大分子时面临严重扩散限制。尽管近年来已报道若干16元环、20元环甚至22元环的超大孔沸石分子筛,但仍处于微孔范围。另一方面,早期发展的MCM-41等介孔分子筛虽具大孔径,却因无定形骨架而热稳定性不足。如何在保持沸石晶态骨架稳定性的同时,实现规则、有序的本征介孔结构材料的构筑,长期以来被视为材料化学与催化领域的重要挑战。

研究成果概览

近日,南京大学黎建研究员团队在前期开发的双金刚烷基磷结构导向剂的基础上(Li, J*, et al., Science, 2025, 388, 1417-1421),发展了双季磷盐结构导向剂,成功创制了目前已知孔口直径最大的36元环全结晶的介孔沸石分子筛NJU120-6,其自由孔径达25.71 Å × 19.12 Å,成功将晶态沸石分子筛由传统微孔推向了介孔范畴。NJU120-6具有高度开放的三维骨架,其骨架密度仅为9.39 Si/nm³,为已知四配位氧化物框架中最低的骨架密度,孔体积高达0.66 cm³/g,材料密度甚至低于水,在1173 K高温下保持结构稳定。利用团队自主搭建的微晶电子衍射(MicroED)平台(Sci. China Chem., 2024, 67, 4158–4166)对纳米级晶体实现原子分辨结构测定,成功解析了原子分辨结构。

图1 NJU120-6的孔道及拓扑结构

NJU120-6不仅可在较宽Si/Al范围内引入铝元素,形成Brønsted酸中心还可通过一锅法将钛掺入骨架,实现氧化催化活性位点构筑。在重质油真空瓦斯油(VGO)催化裂解测试中(与中石化石科院林伟教授合作完成),铝掺杂的NJU120-6表现出高汽柴油选择性(约44.7%)、低气体副产物和近零积碳的优异性能,显著优于USY、Beta及Al-MCM-41等对比材料。其较弱而均匀的酸性配合超大有序介孔结构,有效抑制过度裂解和积碳生成,实现更优产物分布。在液相大分子环辛烯环氧化反应中(与南京工业大学徐乐教授合作完成),钛掺杂的Ti-NJU120-6在转化率和周转数方面同样优于Ti-Beta及含钛介孔材料,体现出超大有序孔道在大分子扩散与活化中的独特优势。

图2 NJU120-6的孔结构分析及催化性能评价

论文信息

该工作第一通讯单位为南京大学配位化学全国重点实验室、化学学院。化院2025级博士研究生孙嘉政(2024年9月加入黎建课题组从事科研助理)、2024级博士生田旭东为共同第一作者。

中国石化石油化工科学研究院林伟教授,南京工业大学徐乐教授为论文的共同通讯作者;黎建特聘研究员为最后通讯作者。该工作中重质油催化裂解由林伟教授团队完成,液相大分子环辛烯环氧化评价反应由徐乐教授团队完成。该工作得到了国家重点研发计划项目(2024YFA1510301, 2024YFA1510000),国家自然科学基金项目(22371121, U25D9013, 22403080 and 22272079)、江苏省自然科学基金项目(BK20230772, BG2024018)、中央高校基本科研业务费专项基金项目(0205-14380334),北京分子科学国家研究中心开放基金(BNLMS202402),苏州国家实验室自研项目等项目的支持。同时感谢南京大学配位化学全国重点实验室段春迎教授,左景林教授和南京大学亚原子分辨电镜中心邓昱教授在课题组建设和微晶电子衍射技术平台建设中提供的支持。

论文链接

https://www.science.org/doi/10.1126/science.aec4882

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  1. CONNECT:[ UseTime:0.000570s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000765s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000330s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000282s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000491s ]
  6. SELECT * FROM `set` [ RunTime:0.000195s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000548s ]
  8. SELECT * FROM `article` WHERE `id` = 490129 LIMIT 1 [ RunTime:0.000758s ]
  9. UPDATE `article` SET `lasttime` = 1775299631 WHERE `id` = 490129 [ RunTime:0.001185s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000233s ]
  11. SELECT * FROM `article` WHERE `id` < 490129 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.000720s ]
  12. SELECT * FROM `article` WHERE `id` > 490129 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000437s ]
  13. SELECT * FROM `article` WHERE `id` < 490129 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000762s ]
  14. SELECT * FROM `article` WHERE `id` < 490129 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.001525s ]
  15. SELECT * FROM `article` WHERE `id` < 490129 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.001505s ]
0.079504s