Park Jihye, Chen Zhihua, Flores Raul A, Wallnerström Gustaf, Kulkarni Ambarish, Nørskov Jens K, Jaramillo Thomas F, Bao Zhenan
Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
ACS Appl Mater Interfaces. 2020 Sep 2;12(35):39074-39081. doi: 10.1021/acsami.0c09323. Epub 2020 Aug 19.
Catalytic systems whose properties can be systematically tuned via changes in synthesis conditions are highly desirable for the next-generation catalyst design and optimization. Herein, we present a two-dimensional (2D) conductive metal-organic framework consisting of M-N units (M = Ni, Cu) and a hexaaminobenzene (HAB) linker as a catalyst for the oxygen reduction reaction. By varying synthetic conditions, we prepared two Ni-HAB catalysts with different crystallinities, resulting in catalytic systems with different electric conductivities, electrochemical activity, and stability. We show that crystallinity has a positive impact on conductivity and demonstrate that this improved crystallinity/conductivity improves the catalytic performance of our model system. Additionally, density functional theory simulations were performed to probe the origin of M-HAB's catalytic activity, and they suggest that M-HAB's organic linker acts as the active site with the role of the metal being to modulate the linker sites' binding strength.
对于下一代催化剂的设计和优化而言，那些其性质可通过合成条件的改变而系统调节的催化体系是非常理想的。在此，我们展示了一种由M-N单元（M = Ni、Cu）和六氨基苯（HAB）连接体组成的二维（2D）导电金属有机框架作为氧还原反应的催化剂。通过改变合成条件，我们制备了两种具有不同结晶度的Ni-HAB催化剂，从而得到了具有不同电导率、电化学活性和稳定性的催化体系。我们表明结晶度对电导率有积极影响，并证明这种改善的结晶度/电导率提高了我们模型体系的催化性能。此外，进行了密度泛函理论模拟以探究M-HAB催化活性的起源，结果表明M-HAB的有机连接体充当活性位点，而金属的作用是调节连接体位点的结合强度。
