Electronic coupling enhanced PtCo/CeO2 hybrids as highly active catalysts for the key dehydrogenation step in conversion of bio-derived polyols. (16th January 2021)

• Record Type: Journal Article
• Authors: Zhang, Guangyu; Jin, Xin; Li, Xiaokun; Meng, Kexin; Wang, Jinyao; Zhang, Quanxing; Chen, Xiaobo; Liu, Yibin; Feng, Xiang; Yang, Chaohe
• Is Part Of: Chemical engineering science. Volume 229(2021)
• Publication Date: 2021-01-16
• Subjects: Glycerol -- Dehydrogenation -- Lattice strain -- Electronic coupling -- d bond center -- OH– insertion; Chemical engineering -- Periodicals; Génie chimique -- Périodiques; Chemical engineering; Periodicals; Electronic journals; 660
• DOI: 10.1016/j.ces.2020.116060
• Languages: English
• ISSNs: 0009-2509

Abstract

Highlights: Remarkable activity (TOF: 10, 735 h −1 ) for C-H cleavage of glycerol at 200 °C. Strong electron coupling effect in Pt-support induced wide d band center and rich electron density of Pt species. Metal catalyzed H extraction from oxygenates, and direct OH – insertion. Abstract: Dehydrogenation, involving C-H bond activation, is one of the key reactions for biomass conversion. We report a unique design principle for electronically coupled metal-ceria hybrids as novel catalysts to demonstrate improved performance of C-H bond cleavage in conversion of polyols. Using PtCo clusters as a model catalyst system, we found that CeO2 with (1 0 0) and (1 1 1) facets display unusual d band modulation for Pt sites. TEM, XPS, Raman and UV–Vis analysis confirmed that, such strong electronic coupling effect contributes to a record high TOF of 10, 735 h −1 for C-H cleavage of glycerol at 200 °C, approximately seven-fold higher compared to literature results. Based on kinetic analysis, it was further confirmed that C-H cleavage follows two alternative pathways: metal catalyzed H extraction from oxygenates, and direct OH – insertion promoted by Pt-O-Ce sites. The outcome of this work provides new insights on innovative design of selective dehydrogenation catalysts for other industrial applications.