Jin Yiran, Fu Wenlong, Wen Zhihao, Tan Lili, Chen Zhi, Wu Hao, Wang Peng-Peng
State Key Laboratory for Mechanical Behavior of Materials, Shaanxi International Research Center for Soft Matter, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
J Am Chem Soc. 2024 Jan 31;146(4):2798-2804. doi: 10.1021/jacs.3c12965. Epub 2023 Dec 25.
The combination of the chiral concept and inorganic nanostructures holds great potential for significantly impacting catalytic processes and products. However, the synthesis of inorganic nanomaterials with engineered chiroptical activity and identical structure and size presents a substantial challenge, impeding exploration of the relationship between chirality (optical activity) and catalytic efficiency. Here, we present a facile wet-chemical synthesis for achieving intrinsic and tunable chiroptical activity within colloidal copper oxide nanostructures. These nanostructures exhibit strong spin-polarization selectivity compared with their achiral counterparts. More importantly, the ability to engineer chiroptical activity within the same type of chiral nanostructures allows for the manipulation of spin-dependent catalysis, facilitating a study of the connection between the chiroptical magnitude (asymmetric factor) and catalytic performance in inorganic nanostructures. Specifically, using these materials as model catalysts in a proof-of-concept catalytic reaction, we reveal a linear correlation between the asymmetric factor of chiral nanomaterials and the efficiency of the catalytic reaction. This work paves the way for the development of chiral inorganic nanosystems and their application in catalysis through chiroptical engineering.
手性概念与无机纳米结构的结合在显著影响催化过程和产物方面具有巨大潜力。然而,合成具有工程化手性光学活性且结构和尺寸相同的无机纳米材料面临重大挑战,这阻碍了对手性(光学活性)与催化效率之间关系的探索。在此,我们展示了一种简便的湿化学合成方法,可在胶体氧化铜纳米结构中实现内在且可调的手性光学活性。与非手性对应物相比,这些纳米结构表现出强烈的自旋极化选择性。更重要的是,在同一类型的手性纳米结构中设计手性光学活性的能力允许对自旋依赖性催化进行调控,有助于研究无机纳米结构中手性光学强度(不对称因子)与催化性能之间的联系。具体而言,在一个概念验证催化反应中使用这些材料作为模型催化剂,我们揭示了手性纳米材料的不对称因子与催化反应效率之间的线性相关性。这项工作为通过手性光学工程开发手性无机纳米系统及其在催化中的应用铺平了道路。