TY - JOUR
T1 - Non-bonding interaction of dual atom catalysts for enhanced oxygen reduction reaction
AU - Tamtaji, Mohsen
AU - Peng, Qiuming
AU - Liu, Tongchao
AU - Zhao, Xue
AU - Xu, Zhihang
AU - Galligan, Patrick Ryan
AU - Hossain, Md Delowar
AU - Liu, Zhenjing
AU - Wong, Hoilun
AU - Liu, Hongwei
AU - Amine, Khalil
AU - Zhu, Ye
AU - Goddard, William A.
AU - Wu, Wenting
AU - Luo, Zhengtang
N1 - Funding Information:
Z.L. acknowledge supports by RGC ( 16304421 ), and the IER foundation ( HT-JD-CXY-201907 ), “International science and technology cooperation projects” of Science and Technological Bureau of Guangzhou Huangpu District ( 2019GH06 ), Guangdong Science and Technology Department (Project#: 2020A0505090003 ), Research Fund of Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology (No. 2020B1212030010 ). Technical assistance from the Materials Characterization and Preparation Facilities of HKUST is greatly appreciated. Q.P. thanks the Natural Science Foundation of Hebei Province for Innovation Groups Program ( C2022203003 ). Y.Z. thanks the financial support from the Hong Kong Polytechnic University (Grant No. ZVRP ). WAG thanks the US National Science Foundation ( CBET-2005250 ) for support.
Funding Information:
Z.L. acknowledge supports by RGC (16304421), and the IER foundation (HT-JD-CXY-201907), “International science and technology cooperation projects” of Science and Technological Bureau of Guangzhou Huangpu District (2019GH06), Guangdong Science and Technology Department (Project#: 2020A0505090003), Research Fund of Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology (No. 2020B1212030010). Technical assistance from the Materials Characterization and Preparation Facilities of HKUST is greatly appreciated. Q.P. thanks the Natural Science Foundation of Hebei Province for Innovation Groups Program (C2022203003). Y.Z. thanks the financial support from the Hong Kong Polytechnic University (Grant No. ZVRP). WAG thanks the US National Science Foundation (CBET-2005250) for support. Characterization, DFT calculations, Descriptor, and Machine Learning (ML) on Gibbs free energy. These authors declare that there are no conflicts of interest to acknowledge for this research.
Publisher Copyright:
© 2023
PY - 2023/4
Y1 - 2023/4
N2 - We demonstrate the design of graphene-supported dual atom catalysts (DACs) for the four-electron oxygen reduction reaction (ORR), by utilizing the non-bonding interaction of counterpart metals (M) that synergistically tune the electronic properties and catalytic activity of the Fe active site in FeMN6-DAC and FeMN8-DAC systems, where M stands for Fe, Co, Ni, Cu, and Zn. More specifically, for Fe-M distances below 15 Å, the non-bonding interaction is significant, making the system act as the DAC. We predicted that FeNiN6-DAC and FeNiN8-DAC exhibit a low ORR overpotential (ηORR) of 0.28 V and 0.47 V, respectively, which are at the summits of volcano plots. This low ηORR originates from the high Bader charge transfer coupled with high spin density at the Fe site in both the FeNiN6-DAC and FeNiN8-DAC systems, which weakens the adsorption of OH* intermediate while enhancing its desorption to H2O. Guided by these density functional theory (DFT) computational results, we synthesized FeCoN8-DAC and FeNiN8-DAC along with N-doped graphene and confirmed their structures with scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and electron spin resonance (ESR). We verify experimentally the catalytic activities and find that FeNiN8-DAC has the low experimental overpotential of 0.39 V with a Tafel slope of 47 mVdec−1. Based on these results, we propose a DFT-guided strategy to tune the charge transfer and spin population of the active site toward designing DACs for electrochemical ORR.
AB - We demonstrate the design of graphene-supported dual atom catalysts (DACs) for the four-electron oxygen reduction reaction (ORR), by utilizing the non-bonding interaction of counterpart metals (M) that synergistically tune the electronic properties and catalytic activity of the Fe active site in FeMN6-DAC and FeMN8-DAC systems, where M stands for Fe, Co, Ni, Cu, and Zn. More specifically, for Fe-M distances below 15 Å, the non-bonding interaction is significant, making the system act as the DAC. We predicted that FeNiN6-DAC and FeNiN8-DAC exhibit a low ORR overpotential (ηORR) of 0.28 V and 0.47 V, respectively, which are at the summits of volcano plots. This low ηORR originates from the high Bader charge transfer coupled with high spin density at the Fe site in both the FeNiN6-DAC and FeNiN8-DAC systems, which weakens the adsorption of OH* intermediate while enhancing its desorption to H2O. Guided by these density functional theory (DFT) computational results, we synthesized FeCoN8-DAC and FeNiN8-DAC along with N-doped graphene and confirmed their structures with scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and electron spin resonance (ESR). We verify experimentally the catalytic activities and find that FeNiN8-DAC has the low experimental overpotential of 0.39 V with a Tafel slope of 47 mVdec−1. Based on these results, we propose a DFT-guided strategy to tune the charge transfer and spin population of the active site toward designing DACs for electrochemical ORR.
KW - Descriptor
KW - DFT
KW - Electrocatalyst
KW - Overpotential
KW - Spin state
UR - http://www.scopus.com/inward/record.url?scp=85147327338&partnerID=8YFLogxK
U2 - 10.1016/j.nanoen.2023.108218
DO - 10.1016/j.nanoen.2023.108218
M3 - Journal article
AN - SCOPUS:85147327338
SN - 2211-2855
VL - 108
JO - Nano Energy
JF - Nano Energy
M1 - 108218
ER -