Computational Discovery of Codoped Single-Atom Catalysts
for Methane-to-Methanol Conversion
Posted on 2024-02-13 - 08:03
The
absence of a synthetic catalyst that can selectively oxidize
methane to methanol motivates extensive study of single-site catalysts
that possess a high degree of tunability in their coordination environments
and share similarities with natural enzymes that can catalyze this
reaction. Single-atom catalysts (SACs), in particular doped graphitic
SACs, have emerged as a promising family of materials due to their
high atom economy and scalability, but SACs are yet to be exhaustively
screened for methane-to-methanol conversion. Modulating the coordination
environment near single metal sites by means of codopants, we carry
out a large-scale high-throughput virtual screen of 2048 transition
metal (i.e., Mn, Fe, Co, and Ru) SACs codoped with various elements
(i.e., N, O, P, and S) in numerous spin and oxidation (i.e., M(II)/M(III))
states for the challenging conversion of methane to methanol. We identify
that the ground-state preference is metal- and oxidation-state-dependent.
We observe a weak negative correlation between the oxo formation energy
(ΔE(oxo)) and the energy of hydrogen atom transfer
(ΔE(HAT)), thanks to the high variability in
the coordination environment. Therefore, codoped SACs demonstrate
flexible tunability that disrupts linear free energy relationships
in a manner similar to that of homogeneous catalysts without losing
the scalability of heterogeneous catalysts. We identify energetically
favorable catalyst candidates along the Pareto frontier of ΔE(oxo) and ΔE(HAT). Further kinetic
analysis reveals an intermediate-spin Fe(II) SAC and a low-spin Ru(II)
SAC as promising candidates that merit further experimental exploration.
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Jia, Haojun; Duan, Chenru; Kevlishvili, Ilia; Nandy, Aditya; Liu, Mingjie; Kulik, Heather J. (2024). Computational Discovery of Codoped Single-Atom Catalysts
for Methane-to-Methanol Conversion. ACS Publications. Collection. https://doi.org/10.1021/acscatal.3c05506