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厦大黄小青,苏州纳米所徐勇等JACS丨创纪录!光驱动乙烷脱氢制乙烯:低温、高效、稳定运行152小时!

  • 2026-02-04 09:52:56
厦大黄小青,苏州纳米所徐勇等JACS丨创纪录!光驱动乙烷脱氢制乙烯:低温、高效、稳定运行152小时!

温和条件下实现乙烷高效转化,光催化技术迈出关键一步

近日,厦门大学、中科院苏州纳米所等单位的研究团队在JACS发表题为《蒸汽辅助光驱动乙烷脱氢实现稳定、高收率的乙烯生产》的重要论文。该研究通过设计新型Pd/ZnO-TiO₂界面催化剂,结合水蒸气辅助策略,在常温常压下实现了光驱动乙烷高效、高选择性脱氢制乙烯,并展现出长达152小时的优异稳定性,为低碳烯烃绿色合成提供了新思路。

01 文章信息

标题Stable, High-Yield Ethylene Production from Vapor-Assisted Light-Driven Ethane Dehydrogenation期刊Journal of the American Chemical Society作者Huiping Peng, Yingchen Peng, Fei Xue, Yuting He, Xia Lv, Ye Yang, Xuan Huang, Yue Cheng, Nanjun Chen, Xiaoqing Huang,* Yong Xu*DOIhttps://doi.org/10.1021/jacs.5c21432发表时间2026关键词:光催化、乙烷脱氢、乙烯、界面工程、水蒸气辅助、稳定性

02 全文速览

乙烯是化工领域最重要的基础化学品之一,传统生产依赖高温蒸汽裂解,能耗高、碳排放量大。乙烷直接脱氢制乙烯是一种理想路线,但需在>600℃下进行,易导致催化剂积碳和失活。

光催化乙烷脱氢可在温和条件下利用太阳能驱动反应,但长期以来受限于产物收率低、稳定性差

本研究提出了一种界面工程+水蒸气辅助的双重策略:构建具有Ti-O-Zn界面Pd/ZnO-TiO₂异质结催化剂,利用水蒸气提供·OH物种并抑制积碳,实现了在连续流动反应器中1640.9 μmol·h⁻¹C₂H₄产率、98.7%的选择性以及152小时的超长稳定运行,性能远超当前报道的光催化体系。

03 文章亮点

  1. 创纪录的催化性能C₂H₄产率达1640.9 μmol·h⁻¹,是现有最好催化剂的7倍以上,选择性达98.7%
  2. 超长稳定性:在含水和空气的连续流动体系中稳定运行152小时,显著超越文献报道的<12小时水平。
  3. 水蒸气双重功能机制揭示:水不仅提供·OH促进脱氢,还能原位去除积碳,实现催化剂自清洁
  4. 界面电荷定向分离:通过Ti-O-Zn界面设计,实现光生电子-空穴的有效空间分离,提升光利用效率。
  5. 可拓展的太阳能驱动工艺:使用菲涅尔透镜聚焦太阳光也可实现反应,具备工业化应用潜力。

04 图文解析

催化剂结构设计:Ti-O-Zn界面工程

研究团队通过两步法合成Pd/ZnO-TiO₂催化剂:先水热法制备ZnO-TiO₂载体,再浸渍沉积Pd纳米团簇。核心创新在于在ZnO表面构建了保形的TiO₂覆盖层,形成原子级紧密接触的Ti-O-Zn界面(图1a)。

1|催化剂结构表征

  • 拉曼光谱(图1b)显示Pd/ZnO-TiO₂310742 cm⁻¹出现特征峰,归属为Ti-O-Zn界面振动,证实界面形成。
  • HAADF-STEMEELS mapping(图1d–f)直观显示TiO₂均匀覆盖在ZnO表面,Pd团簇高度分散。
  • XPSXANES(图1g–h)表明Pd呈氧化态,电子从PdTiO₂转移,增强界面电荷传输。

光催化性能:产率与稳定性双突破

在连续流动光反应器中,以C₂H₆/空气/H₂O(g)=25/1/6.4为原料气,600 mW·cm⁻²光照下测试性能(图2)。

2|光催化乙烷脱氢性能

  • Pd/ZnO-TiO₂表现出卓越性能C₂H₄产率1640.9 μmol·h⁻¹,选择性98.7%,远超Pd/ZnOPd/TiO₂及物理混合样品(图2a)。
  • 水蒸气关键作用:无水时反应迅速衰减,重新引入水蒸气后活性恢复,且CO₂生成增加,说明水能去除积碳(图2b)。
  • 可扩展性良好:催化剂载量从2 mg增至6 mgC₂H₄产率线性提升至273.4 mmol·g⁻¹·h⁻¹(图2c)。
  • 长期稳定性测试:在152小时内保持稳定,结构未发生明显变化(图2e)。

机制研究:电荷分离与水蒸气作用

光生电荷行为:通过PLEIS、光电流等测试(图3a–c),发现Pd/ZnO-TiO₂具有更强的电荷分离与传输能力。原位XPSEPR(图3d–f)进一步证实光照下电子向ZnO迁移(Zn²⁺→Zn⁺),空穴向TiO₂迁移(Ti³⁺→Ti⁴⁺),实现定向分离。

3|光生电荷分离行为研究

反应路径与积碳抑制

  • 原位DRIFTS(图4a–b)检测到CH₃CH₂CH₂=CH₂中间体,证实乙烷逐步脱氢路径。
  • 同位素实验(图4c–e)表明水参与形成·OH,氧分子参与水的生成与积碳氧化。
  • 水蒸气双重功能(图4f):提供·OH,促进C₂H₆脱氢;氧化去除积碳,维持催化剂活性。

4|反应机理与积碳抑制机制

05 总结与展望

本研究成功构建了一种具有Ti-O-Zn界面的Pd/ZnO-TiO₂光催化剂,结合水蒸气辅助策略,实现了高效、高选择性、超稳定的光驱动乙烷脱氢制乙烯。系统机理研究表明,界面电荷定向分离水蒸气的双重作用是性能突破的关键。

该工作不仅为温和条件下低碳烷烃转化提供了新催化体系,也为太阳能驱动化工过程的工业化应用提供了重要借鉴。未来可通过优化催化剂组成、反应器设计与光源利用方式,进一步提升能效与经济性。

06 通讯作者简介

徐勇,中国科学院苏州纳米所创新实验室研究员,博士生导师。长期从事功能纳米催化剂的实际与开发、新型清洁能源转化和催化原位表征方面的研究。迄今已发表论文130余篇,近五年来以一作或通讯作者在高水平学术期刊上发表SCI论文近80篇,其中包括Nature SynthesisScience AdvancesNature CommunicationsAdvanced MaterialsJournal of the American Chemical SocietyAngewandte Chemie International EditionAdvanced MaterialsEnergy & Environmental Science等。入选江苏省双创人才,广东省自然科学基金杰出青年基金、姑苏领军人才等计划支持。

黄小青,厦门大学教授。2005年于西南师范大学(现西南大学)获理学学士学位。2011年于厦门大学获理学博士学位,导师为郑南峰教授、郑兰荪院士。2011-2014年在美国加州大学洛杉矶分校黄昱教授、段镶锋教授课题组从事的博士后研究工作。2014年至今先后于苏州大学材料与化学化工学部、厦门大学化学化工学院担任特聘教授,博士生导师。2020年获国家杰出青年科学基金资助,课题:贵金属纳米材料合成化学。目前兼职:Science BulletinRare MetalScience China Materials客座编辑或编委。研究兴趣:贵金属纳米材料的精准制备及其电、热、光催化应用研究。

文章链接https://doi.org/10.1021/jacs.5c21432

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  1. CONNECT:[ UseTime:0.000982s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001302s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.005018s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.002303s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000547s ]
  6. SELECT * FROM `set` [ RunTime:0.001631s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000588s ]
  8. SELECT * FROM `article` WHERE `id` = 475776 LIMIT 1 [ RunTime:0.000417s ]
  9. UPDATE `article` SET `lasttime` = 1770177861 WHERE `id` = 475776 [ RunTime:0.001069s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.003109s ]
  11. SELECT * FROM `article` WHERE `id` < 475776 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.002565s ]
  12. SELECT * FROM `article` WHERE `id` > 475776 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000425s ]
  13. SELECT * FROM `article` WHERE `id` < 475776 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.016932s ]
  14. SELECT * FROM `article` WHERE `id` < 475776 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.004671s ]
  15. SELECT * FROM `article` WHERE `id` < 475776 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.001588s ]
0.217682s