Theoretical insights into B-site homonuclear dual-atom doping in LaMnO3 for CO chemical looping combustion
Abstract
Perovskite oxides have emerged as promising oxygen carriers (OCs) for chemical looping combustion (CLC), where their catalytic behaviour can be effectively regulated through compositional engineering. In this work, a first-principles-based strategy was developed to uncover the role of B-site homonuclear dual-atom incorporation in modulating the CO oxidation activity of LaMnO3. Twenty-four doped configurations were systematically screened, leading to the identification of eight energetically favourable structures for subsequent catalytic investigation. Detailed electronic-structure analyses revealed that dual-atom doping alters CO adsorption characteristics and facilitates surface oxidation processes. Kinetic evaluation demonstrated that four doped systems, namely V2–LaMnO3(O1), V2–LaMnO3(O2), Ni2–LaMnO3(O1), and Ni2–LaMnO3(O2), outperform pristine LaMnO3, with Ni2–LaMnO3(O2) achieving the lowest CO oxidation barrier of 0.666 eV, corresponding to a 67% reduction. The structural stability of these highly active catalysts under CLC operating temperatures was further verified by ab initio molecular dynamics (AIMD) simulations. Furthermore, descriptor analysis established that dopant-induced charge-transfer energy and Bader charge transfer provide reliable criteria for predicting catalytic performance. These findings elucidate the electronic origin of enhanced CO oxidation induced by B-site homonuclear dual-atom doping and offer a rational framework for designing advanced perovskite OCs for efficient CLC.
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BibTeX
@misc{bai2026theoretical,
title = {{Theoretical insights into B-site homonuclear dual-atom doping in LaMnO3 for CO chemical looping combustion}},
author = {Zhongze Bai and Kai H. Luo},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008945/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008945/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Theoretical insights into B-site homonuclear dual-atom doping in LaMnO3 for CO chemical looping combustion
AU - Zhongze Bai
AU - Kai H. Luo
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008945/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008945/v1
AB - Perovskite oxides have emerged as promising oxygen carriers (OCs) for chemical looping combustion (CLC), where their catalytic behaviour can be effectively regulated through compositional engineering. In this work, a first-principles-based strategy was developed to uncover the role of B-site homonuclear dual-atom incorporation in modulating the CO oxidation activity of LaMnO3. Twenty-four doped configurations were systematically screened, leading to the identification of eight energetically favourable structures for subsequent catalytic investigation. Detailed electronic-structure analyses revealed that dual-atom doping alters CO adsorption characteristics and facilitates surface oxidation processes. Kinetic evaluation demonstrated that four doped systems, namely V2–LaMnO3(O1), V2–LaMnO3(O2), Ni2–LaMnO3(O1), and Ni2–LaMnO3(O2), outperform pristine LaMnO3, with Ni2–LaMnO3(O2) achieving the lowest CO oxidation barrier of 0.666 eV, corresponding to a 67% reduction. The structural stability of these highly active catalysts under CLC operating temperatures was further verified by ab initio molecular dynamics (AIMD) simulations. Furthermore, descriptor analysis established that dopant-induced charge-transfer energy and Bader charge transfer provide reliable criteria for predicting catalytic performance. These findings elucidate the electronic origin of enhanced CO oxidation induced by B-site homonuclear dual-atom doping and offer a rational framework for designing advanced perovskite OCs for efficient CLC.
ER -