Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
Xingjie Wang, Xuan Zhang, Riddhish Pandharkar, Jiafei Lyu, Debmalya Ray, Ying Yang, Satoshi Kato, Jian Liu, Megan C. Wasson, Timur İslamoğlu, Zhong Li, Joseph T. Hupp, Christopher J. Cramer, Laura Gagliardi, Omar K. Farha
Abstract
Solid supports play an indispensable role in heterogeneous catalysis, as they can directly affect the catalytic activity and selectivity of supported catalysts. However, the specific roles of such supports remain to be demystified owing to the difficulties in obtaining precise structural information on supported catalysts. To understand the effects of MOF topology, pore environment, and metal identity of node supports on the catalytic activity, a Ni catalyst was supported on eight Zr- or Hf-MOFs based on 8-connected nodes: namely M-NU-1200, M-NU-1000, M-NU-1008, and M-NU-1010 (M = Zr, Hf). Single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the supported catalyst structures. To investigate the support effects on their activities, the supported Ni catalysts were evaluated by using ethylene hydrogenation as a model reaction. The results revealed that all Hf-based-MOF-supported Ni catalysts exhibited higher catalytic reactivity with TOF (turnover frequency) values at least double of those isostructural Zr counterparts. Additionally, MOFs with less congested metal anchoring sites, as a result of the topology and surrounding pore environment, yielded higher TOFs, suggesting the importance of supports in dictating both the catalyst accessibility and activity. Computational analysis complemented the experimental observations and provided insights into reaction barrier differences and their performance variation. This study demonstrates the essential role of the supports and provides a thought for selecting/designing suitable supports in heterogeneous catalysis.