Citation: Kaili Wang, Pengcheng Liu, Mingzhe Wang, Tianran Wei, Jitao Lu, Xingling Zhao, Zaiyong Jiang, Zhimin Yuan, Xijun Liu, Jia He. Modulating d-d orbitals coupling in PtPdCu medium-entropy alloy aerogels to boost pH-general methanol electrooxidation performance[J]. Chinese Chemical Letters, ;2025, 36(4): 110532. doi: 10.1016/j.cclet.2024.110532 shu

Modulating d-d orbitals coupling in PtPdCu medium-entropy alloy aerogels to boost pH-general methanol electrooxidation performance

Kaili Wang ^{a, 1} ,
Pengcheng Liu ^{b, 1} ,
Mingzhe Wang ^{b, 1} ,
Tianran Wei ^c ,
Jitao Lu ^a ,
Xingling Zhao ^a ,
Zaiyong Jiang ^a ,
Zhimin Yuan ^{a, *,} ,
Xijun Liu ^{c, *,} ,
Jia He ^{b, *,}

a.
School of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, China
b.
School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China
c.
State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China

yuanzhiminjinan@163.com

xjliu@gxu.edu.cn

hejia1225@126.com

Received Date: 22 June 2024
Revised Date: 29 September 2024
Accepted Date: 8 October 2024
Available Online: 10 October 2024

Figures(5)

Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction (MOR) performance can fundamentally guide high efficient catalyst design. Herein, density functional theory (DFT) calculations were performed at first to study the d–d orbital interaction of metallic PtPdCu, revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms. Under the theoretical guidance, PtPdCu medium entropy alloy aerogels (PtPdCu MEAAs) catalysts have been designed and systematically screened for MOR under acid, alkaline and neutral electrolyte. Furthermore, DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that PtPdCu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO₂. For practical direct methanol fuel cells (DMFCs), the PtPdCu MEAAs-integrated ultra-thin catalyst layer (4–5 µm thickness) as anode exhibits higher peak power density of 35 mW/cm² than commercial Pt/C of 20 mW/cm² (~40 µm thickness) under the similar noble metal loading and an impressive stability retention at a 50-mA/cm² constant current for 10 h. This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
- Medium-entropy alloys aerogels,
- d-d Orbitals coupling,
- pH-general,
- Methanol oxidation reaction,
- Ultra-thin catalyst layer
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