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南京林业大学/清华大学,最新Angew!

  • 2026-04-17 13:42:33
南京林业大学/清华大学,最新Angew!

研究背景

环己醇是尼龙-6和尼龙-66等聚酰胺材料的关键前体,全球市场规模预计将从2023年的115亿美元增长至2032年的189亿美元。然而,传统工业生产高度依赖化石燃料路线:从原油催化重整制得苯,再经高压加氢生成环己烷,最后通过部分氧化反应得到环己醇。这一路径不仅步骤冗长、能耗巨大,更面临一个根本性的技术瓶颈——环己烷氧化步骤需在约2兆帕高压下进行,单程转化率却不足5%,导致大量原料循环、碳排放居高不下。与此同时,全球每年产生数千万吨塑料废弃物,其中聚碳酸酯(PC)富含氧元素和芳香结构,本可作为潜在的化学原料,但传统回收技术往往将其彻底脱氧转化为低级烃类,造成原子经济性的巨大浪费。如何在温和条件下将塑料废弃物中的氧功能团"变废为宝",直接转化为高附加值含氧化学品,成为绿色化学与循环经济领域亟待解决的科学难题。

成果简介

南京林业大学蒋剑春院士、清华大学王定胜教授和张泽栋博士、加州大学伯克利分校Shule Wang(共同通讯作者)等人提出了一种"以废制宝"的双原子催化策略,巧妙利用聚碳酸酯塑料自身的氧原子作为羟基来源,跳过传统氧化步骤,直接将塑料垃圾转化为环己醇。研究团队设计了一种钌-镧双原子催化剂(RuLa-DA),通过氢溢流机制实现温和条件下的高效加氢。该工艺采用两段式固定床反应器:第一段在550°C下将塑料热解为酚类中间体,第二段在200°C、仅0.25兆帕的低压下完成气相加氢,整个流程仅需4.2秒停留时间。实验结果显示,环己醇产率达69.9%,选择性超过95%,且催化剂在100次循环后性能稳定。生命周期评估表明,相比传统石油路线,该技术可减少三倍碳排放并降低35%生产成本,为塑料升级再造和低碳化工开辟了切实可行的原子经济新路径。

图文导读

图1.比较传统化石燃料和短流量废物制备环己醇路线

图2. CoAl混合氧化物上RuLa-DA催化剂的结构表征

图3. RuLa-DA催化剂中Ru和La的电子结构和配位环境

图4.废PC在不同催化剂上的气相加氢

图5. RuLa-DA催化剂上的双中心氢活化和溢出机理

总结展望

本研究开发了一种RuLa双原子催化剂,通过串联氢解-气相加氢工艺实现了聚碳酸酯废弃物向环己醇的高效转化,产率达69.9%、选择性超过95%,在100次循环中保持性能稳定。该策略巧妙利用塑料自身的氧官能团作为羟基来源,完全规避了传统环己烷氧化工艺中高压低效的瓶颈,将碳排放降低三倍、生产成本减少35%。从学术层面看,这项工作揭示了双原子位点协同氢溢流机制——钌负责氢气活化与芳环吸附,镧作为氢 relay 促进氢物种迁移——为设计高效单原子催化体系提供了新范式;从应用角度,该技术为富氧塑料废弃物的原子经济性升级再造开辟了新途径,契合循环化学与低碳制造的战略需求。未来研究可进一步拓展至其他含氧聚合物体系(如PET、PU),开发连续流工业化装置,并探索可再生能源驱动的绿氢耦合工艺,以推动塑料循环经济从实验室走向规模化产业应用。

文献信息

Selective Upcycling of Polycarbonate Waste to Cyclohexanol via RuLa Dual-Atom Catalysis. Angew. Chem. Int. Ed., 2026, https://doi.org/10.1002/anie.202524681.

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  1. CONNECT:[ UseTime:0.000375s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000651s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.003463s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000476s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000527s ]
  6. SELECT * FROM `set` [ RunTime:0.000723s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000538s ]
  8. SELECT * FROM `article` WHERE `id` = 495584 LIMIT 1 [ RunTime:0.007231s ]
  9. UPDATE `article` SET `lasttime` = 1777168025 WHERE `id` = 495584 [ RunTime:0.003907s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000889s ]
  11. SELECT * FROM `article` WHERE `id` < 495584 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.012261s ]
  12. SELECT * FROM `article` WHERE `id` > 495584 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.002493s ]
  13. SELECT * FROM `article` WHERE `id` < 495584 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.002582s ]
  14. SELECT * FROM `article` WHERE `id` < 495584 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.003678s ]
  15. SELECT * FROM `article` WHERE `id` < 495584 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.015965s ]
0.216305s