Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 120, Issue 35, Pages 19686-19697Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.6b05205
Keywords
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Funding
- Vidyasirimedhi Institute of Science and Technology
- National Science and Technology Development Agency (NSTDA Chair Professor)
- National Science and Technology Development Agency (NANOTEC Center of Excellence)
- Thailand Research Fund
- Kasetsart University Research and Development Institute (KURDI)
- Ministry of Education (the National Research University Project of Thailand (NRU))
- Ministry of Education (Postgraduate Education and Research Programs in Petroleum and Petrochemicals and Advanced Materials)
- Commission on Higher Education
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The selective oxidation of carbon monoxide (CO) remains a challenge in many research areas. Here we propose using porous hybrid organic-inorganic frameworks as tunable single-metal site catalysts which can be utilized for the oxidation reaction. Low-valent zinc ions were embedded on ZSM-5 zeolite and metal organic framework (MOF) supports to be used as nonprecious metal catalysts. Unlike the case with ionic compensation between the metal and zeolite, linker-functionalized MOFs exhibit a delocalized electron of the metal residing on both the organic linker and the metal atom. This electron delocalization plays a crucial role in the catalytic activity by assisting charge transfer of the metal site to break the O-O bond. By adding electron-donating groups to the linker, we found the activation energy to be dramatically decreased to similar to 4 kcal/mol compared with 18 kcal/mol for the zeolite. This is essential for oxidation at low temperature. Moreover, the donating groups result in a more stable Zn active site on the supports. We also show relationships between activation energy and (a) charge, (b) ionization energy of Zn atom, and (c) the highest occupied molecular orbital energy. Those parameters can therefore be related to how well the electron transfer from Zn to the 02 molecule proceeds and can be used to construct a model for activation energy prediction which is useful for catalyst design and screening. We believe that such a customizable platform of catalysts could open a new avenue for optimizing both activity and selectivity of catalysts for low-temperature preferential CO oxidation applications.
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