期刊
ACS APPLIED MATERIALS & INTERFACES
卷 13, 期 40, 页码 47465-47477出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c11521
关键词
metal-organic framework; heterogeneous catalysts; ammonia borane; dehydrogenation; metal hydride; hydrogen evolution reaction
资金
- Ministry of Science and Technology, Taiwan [MOST 110-2113-M-033-009]
- National Tsing Hua University, Taiwan [109Q2711E1, 110Q2711E1, 110Q2513E1]
The study explored the use of ZIF67-derived fcc-Co@porous carbon nano/microparticles as a catalyst for the hydrolytic dehydrogenation of ammonia borane, with insights into the reaction mechanism provided by kinetic and computational studies. Experimental evidence supported Co-mediated activation of AB and formation of a Co-H intermediate, suggesting potential applications in the generation of H-2(g) for various purposes, including the treatment of inflammatory diseases, with further investigations warranted.
Regarding dihydrogen as a clean and renewable energy source, ammonia borane (NH3BH3, AB) was considered as a chemical H-2-storage and H-2-delivery material due to its high storage capacity of dihydrogen (19.6 wt %) and stability at room temperature. To advance the development of efficient and recyclable catalysts for hydrolytic dehydrogenation of AB with parallel insight into the reaction mechanism, herein, ZIF67-derived fcc-Co@porous carbon nano/microparticles (cZIF-67_nm/cZIF-67_mu m) were explored to promote catalytic dehydrogenation of AB and generation of H-2(g). According to kinetic and computational studies, zero-order dependence on the concentration of AB, first-order dependence on the concentration of cZIF-67_nm (or cZIF-67_mu m), and a kinetic isotope effect value of 2.45 (or 2.64) for H2O/D2O identify the Co-catalyzed cleavage of the H-OH bond, instead of the H-BH2NH3 bond, as the rate-determining step in the hydrolytic dehydrogenation of AB. Despite the absent evolution of H-2(g) in the reaction of cZIF-67 and AB in the organic solvents (i.e., THF or CH3OH) or in the reaction of cZIF-67 and water, Co-mediated activation of AB and formation of a Co-H intermediate were evidenced by theoretical calculation, infrared spectroscopy in combination with an isotope-labeling experiment, and reactivity study toward CO2-to-formate/H2O-to-H-2 conversion. Moreover, the computational study discovers a synergistic interaction between AB and the water cluster (H2O)(9) on fcc-Co, which shifts the splitting of water into an exergonic process and lowers the thermodynamic barrier for the generation and desorption of H-2(g) from the Co-H intermediates. With the kinetic and mechanistic study of ZIF-67-derived Co@porous carbon for catalytic hydrolysis of AB, the spatiotemporal control on the generation of H-2(g) for the treatment of inflammatory diseases will be further investigated in the near future.
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