Wang Zhouzhou, Chen Yiqing, Sheng Bowen, Li Jinglin, Yao Lin, Yu Ying, Song Jun, Yu Tianqi, Li Yixin, Pan Hu, Wang Ping, Wang Xinqiang, Zhu Lei, Zhou Baowen
Key Laboratory for Power Machinery and Engineering of Ministry of Education, Research Center for Renewable Synthetic Fuel, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079, China.
Angew Chem Int Ed Engl. 2024 Apr 15;63(16):e202400011. doi: 10.1002/anie.202400011. Epub 2024 Mar 14.
Light-driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air-promoted strategy is explored for efficient and durable light-driven hydrogen production from ethanol over a core/shell CrO@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the CrO@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H evolution by photogenerated electrons. Afterward, O can be evolved into active oxygen species and promote the deprotonation and C-C cleavage of the key C intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H per gram CrO@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H per mole CrO over a long-term operation of 180 hours. Notably, an unprecedented light-to-hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising.
利用生物质衍生物进行光驱动制氢为实现碳中和提供了一条途径。然而，该过程通常受到动力学缓慢和严重积碳的限制。在此，我们探索了一种突破性的空气促进策略，用于在核壳结构的CrO@GaN纳米结构上高效且持久地实现乙醇光驱动制氢。相关的计算和实验研究表明，乙醇在能量上有利于吸附在CrO@GaN界面上，随后通过光生空穴脱氢生成乙醛和质子。释放出的质子随后被光生电子消耗以产生氢气。之后，氧可以转化为活性氧物种，促进关键碳中间体的去质子化和碳 - 碳键断裂，从而显著降低析氢反应的能量势垒，并抑制过氧化作用去除碳残留。因此，仅通过供给乙醇和空气并光照，就能以每克CrO@GaN每小时76.9摩尔氢气的高速率产生氢气，在180小时的长期运行中实现了每摩尔CrO的周转数为266,943,000摩尔氢气。值得注意的是，在聚光照明下实现了前所未有的17.6%的光 - 氢转化效率。乙醇脱氢同时生成醛使得该过程在经济上更具前景。
