Cha Janghwan, Lee Hoonkyung, Hong Suklyun
Department of Physics, Graphene Research Institute, Quantum Information Science and Technology Center, and KUU Quantum Materials·Devices International Research Center, Sejong University, Seoul 05006, Korea.
Antlinesoft, Seoul 08503, Korea.
ACS Omega. 2025 Aug 26;10(35):40668-40674. doi: 10.1021/acsomega.5c07919. eCollection 2025 Sep 9.
We have investigated the adsorption of CO and O on transition-metal (TM)-incorporated porphyrin. Our calculations show that one or more CO molecules can be adsorbed on the Sc-, Ti-, V-, Cr-, or Mn-incorporated porphyrin, while only one CO molecule is adsorbed on the Fe- or Co-incorporated porphyrin. In the case of O, only one O molecule prefers to adsorb on the TM-incorporated porphyrin, regardless of TM. Moreover, O is strongly bound to the Sc-, Ti-, V-, Cr-, or Mn-incorporated porphyrin compared with that of CO, while it is weakly bound to the Fe- or Co-incorporated porphyrin compared with that of CO. Such different binding behaviors can be explained by variations of the highest occupied molecular orbital (HOMO) level in the d-orbitals of TM-incorporated porphyrin. We find that the HOMO levels are shifted downward in the cases of O adsorption on the Sc-, Ti-, and V-incorporated porphyrin and CO adsorption on the Fe- and Co-incorporated porphyrin, indicating the stronger binding energies between them. These studies can be useful to understand the capture of CO and O by the TM-incorporated porphyrin.
我们研究了一氧化碳（CO）和氧气（O）在掺入过渡金属（TM）的卟啉上的吸附情况。我们的计算表明，一个或多个CO分子可以吸附在掺入Sc、Ti、V、Cr或Mn的卟啉上，而只有一个CO分子吸附在掺入Fe或Co的卟啉上。对于O而言，无论TM为何种元素，只有一个O分子倾向于吸附在掺入TM的卟啉上。此外，与CO相比，O与掺入Sc、Ti、V、Cr或Mn的卟啉结合紧密，而与掺入Fe或Co的卟啉结合较弱。这种不同的结合行为可以通过掺入TM的卟啉d轨道中最高占据分子轨道（HOMO）能级的变化来解释。我们发现，在O吸附于掺入Sc、Ti和V的卟啉以及CO吸附于掺入Fe和Co的卟啉的情况下，HOMO能级向下移动，这表明它们之间的结合能更强。这些研究有助于理解掺入TM的卟啉对CO和O的捕获作用。
