TY - JOUR
T1 - Harnessing frontier Pt d-orbital alignment to break performance limits in single-atom catalysis
AU - Chen, Jia
AU - Yu, Xi Yang
AU - Huang, Zhiwei
AU - Chang, Chun Ran
AU - Lin, Yilong
AU - Liao, Xinlong
AU - Chen, Junhong
AU - Gan, Shuangning
AU - Tian, Mingshuo
AU - Liu, Haoran
AU - Sun, Chang
AU - Wu, Xiaomin
AU - Shen, Huazhen
AU - Zhao, Huawang
AU - Jing, Guohua
N1 - Publisher Copyright:
© 2025 Elsevier B.V.
PY - 2026/5
Y1 - 2026/5
N2 - Electronic metal-support interaction (EMSI) critically influences the electronic structure and catalytic efficiency of single-atom catalysts (SACs), yet its role in volatile organic compound (VOC) combustion remains underexplored. This study investigates Pt SACs anchored on narrow-bandgap Fe2O3 and wide-bandgap CeO2 to reveal how support bandgap modulates EMSI to enhance benzene oxidation performance. Combining density functional theory (DFT) calculations, atomic-resolution HAADF-STEM imaging, in situ spectroscopy, and kinetic analyses, we find that Fe2O3’s narrow bandgap promotes stronger charge transfer, shifting Pt d-band centers upward (−1.29 eV for Pt1/Fe2O3 vs. −2.56 eV for Pt1/CeO2). This upward shift, in conjunction with the proximity of the catalyst's unoccupied d-band centroid to the Fermi level (0.89 eV for Pt1/Fe2O3 vs. 2.02 eV for Pt1/CeO2), strengthens orbital overlap with benzene π* orbitals, facilitating C–H bond activation while also promoting O2 dissociation. By contrast, Pt1/CeO2’s downshifted d-band and higher-lying unoccupied d-band centroid hinder efficient activation. Pt1/Fe2O3 achieves 90 % benzene conversion at 237 °C, significantly outperforming Pt1/CeO2 (T90 > 410 °C). Experimental and theoretical results confirm Pt1/Fe2O3’s superior redox activity, optimized intermediate decomposition, and strong Pt–Fe2O3 synergy, highlighting EMSI-driven support design as a critical strategy for high-performance environmental catalysts. These findings advance the rational design of sustainable catalysts for efficient VOC abatement.
AB - Electronic metal-support interaction (EMSI) critically influences the electronic structure and catalytic efficiency of single-atom catalysts (SACs), yet its role in volatile organic compound (VOC) combustion remains underexplored. This study investigates Pt SACs anchored on narrow-bandgap Fe2O3 and wide-bandgap CeO2 to reveal how support bandgap modulates EMSI to enhance benzene oxidation performance. Combining density functional theory (DFT) calculations, atomic-resolution HAADF-STEM imaging, in situ spectroscopy, and kinetic analyses, we find that Fe2O3’s narrow bandgap promotes stronger charge transfer, shifting Pt d-band centers upward (−1.29 eV for Pt1/Fe2O3 vs. −2.56 eV for Pt1/CeO2). This upward shift, in conjunction with the proximity of the catalyst's unoccupied d-band centroid to the Fermi level (0.89 eV for Pt1/Fe2O3 vs. 2.02 eV for Pt1/CeO2), strengthens orbital overlap with benzene π* orbitals, facilitating C–H bond activation while also promoting O2 dissociation. By contrast, Pt1/CeO2’s downshifted d-band and higher-lying unoccupied d-band centroid hinder efficient activation. Pt1/Fe2O3 achieves 90 % benzene conversion at 237 °C, significantly outperforming Pt1/CeO2 (T90 > 410 °C). Experimental and theoretical results confirm Pt1/Fe2O3’s superior redox activity, optimized intermediate decomposition, and strong Pt–Fe2O3 synergy, highlighting EMSI-driven support design as a critical strategy for high-performance environmental catalysts. These findings advance the rational design of sustainable catalysts for efficient VOC abatement.
KW - Catalyst design
KW - Catalytic oxidation
KW - Electronic metal-support interactions
KW - Single-atom catalysts
UR - https://www.scopus.com/pages/publications/105022685533
U2 - 10.1016/j.apcatb.2025.126237
DO - 10.1016/j.apcatb.2025.126237
M3 - 文章
AN - SCOPUS:105022685533
SN - 0926-3373
VL - 384
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 126237
ER -