Metastable intermetallic compound Zn3Co alloying from porous coordination polymer pyrolysis

Parameswaran Rajamanickam, Yi Sheng Ou, Lun Xin Chang, Chung Kai Chang, Yu Chun Chuang, Che Min Chou, Cheng Si Tsao, Cheng Yu Wang*


研究成果: Article同行評審


MOF- or ZIF-derived carbon (MDC/ZDC) has attracted significant attention especially in catalysis applications, because well-dispersed metal or oxide nanoparticles over the MDC/ZDC matrix with retained MOF/ZIF porosity can be obtained with direct pyrolysis. Although it seems to be a facile approach, pyrolysis parameters could significantly alter the MDC/ZDC properties. However, an in-depth study on the pyrolytic factors has not been discussed. Herein, we manipulated ZIF structure, pyrolytic atmosphere, temperature, incubation time, and ramping/cooling rates for ZDC structural analyses. Compared to pure ZIF-67 derived carbon with only Co metal nanoparticles, it was observed that the carbonization process in core-shell ZIF-8@ZIF-67 (Z8@Z67) initiated the interdiffusion of reduced metal ions at the core-shell interface, which triggered the unique Zn-Co alloying behavior forming Zn3Co when they were in close proximity. The resultant intermetallic Zn3Co compound is unstable and has never been experimentally observed. By employing the in situ powder X-ray diffraction (PXRD) technique, we observed the fast-heating plus cooling process arrested or circumvented the phase segregation, and kept the metastable intermetallic Zn3Co. For the first time, we report a method to maintain it at ambient conditions, protected by the porous MOF derivative from ZIF pyrolysis.

期刊Journal of Alloys and Compounds
出版狀態Published - 15 12月 2023


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