Zhan Chao, Wang Qiu-Xiang, Yi Jun, Chen Liang, Wu De-Yin, Wang Ye, Xie Zhao-Xiong, Moskovits Martin, Tian Zhong-Qun
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005, China.
Department of Chemistry, University of California, Santa Barbara, Santa Barbara, CA 93106, USA.
Sci Adv. 2021 Mar 5;7(10). doi: 10.1126/sciadv.abf0962. Print 2021 Mar.
Optimizing product selectivity and conversion efficiency are primary goals in catalysis. However, efficiency and selectivity are often mutually antagonistic, so that high selectivity is accompanied by low efficiency and vice versa. Also, just increasing the temperature is very unlikely to change the reaction pathway. Here, by constructing hierarchical plasmonic nanoreactors, we show that nanoconfined thermal fields and energetic electrons, a combination of attributes that coexist almost uniquely in plasmonic nanostructures, can overcome the antagonism by regulating selectivity and promoting conversion rate concurrently. For propylene partial oxidation, they drive chemical reactions by not only regulating parallel reaction pathways to selectively produce acrolein but also reducing consecutive process to inhibit the overoxidation to CO, resulting in valuable products different from thermal catalysis. This suggests a strategy to rationally use plasmonic nanostructures to optimize chemical processes, thereby achieving high yield with high selectivity at lower temperature under visible light illumination.
优化产物选择性和转化效率是催化领域的主要目标。然而，效率和选择性往往相互对立，即高选择性伴随着低效率，反之亦然。此外，仅仅提高温度很难改变反应路径。在此，通过构建分级等离子体纳米反应器，我们表明纳米受限热场和高能电子（这两种属性几乎仅在等离子体纳米结构中共存）可以通过同时调节选择性和提高转化率来克服这种对立关系。对于丙烯部分氧化反应，它们不仅通过调节平行反应路径选择性地生成丙烯醛，还通过减少连续反应过程抑制其过度氧化为一氧化碳，从而得到与热催化不同的有价值产物。这表明了一种合理利用等离子体纳米结构来优化化学过程的策略，从而在可见光照射下于较低温度实现高选择性和高产率。
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