Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal-Electrolyte Interfaces

Liu，Haijun1,2,3; Chen，Ming2,3; Sun，Fengman1,2,3; Zaman，Shahid2,3; Wang，Min3,4; Wang，Haijiang2,3

2021

10.1021/acsami.1c24153

ACS Applied Materials & Interfaces   影响因子和分区

1944-8244

1944-8252

The metal-vacuum models used to analyze the thermodynamics of the oxygen reduction reaction (ORR) completely overlook the role of electrolytes in the electrochemical process and thus cannot reflect the actual kinetic process occurring at the metal-electrolyte interface. Therefore, based on the real experimental process, the current work elucidates the chemical interactions between the electrolyte and the chemical species for the ORR via a novel metal-electrolyte model for the first time by effectively elucidating the correlation between ORR kinetics and polarization curves. Our simulation model analysis comprises the study of all possible ORR mechanisms on different Pt surfaces (Pt(111), Pt(110), and Pt(100)) and PtNi alloys with different compositions (Pt3Ni(111), Pt2Ni2(111), and PtNi3(111)). The obtained results demonstrate that the hydrogenation of adsorbed oxygen to form adsorbed hydroxyl (R8), whose immense control weight is reflected by a coverage of adsorbed oxygen (θO*) of about 1, is the rate-determining step (RDS) in the four-electron-dominated ORR process. A direct correlation has been established by the great fitting of polarization curves from theoretical ORR kinetics obtained via both the metal-electrolyte model and experimental measurement. This study reveals that among the different Pt surfaces and PtNi alloys, Pt3Ni(111) exhibits the highest ORR activity with the lowest free energy barrier of Ea (0.74 eV), the smallest value of |ΔGO*-2.46| (0.80 eV), the highest reaction rate r (9.98 × 105 s-1 per site), and a more positive half-wave potential U1/2 (0.93 V). In contrast to previous model studies, this work provides a more accurate theoretical system for catalyst screening, which will help researchers to better understand the experimental phenomena and will be a guiding piece of work for catalyst design and development.

catalytic activity metal-electrolyte interface ORR kinetics polarization curves PtNi alloy

SCI ; EI

英语

通讯

Ministry of Education Key Laboratory of Energy Conversion and Storage Technologies[Y01406010] ; Guangdong Innovative and Entrepreneurial Research Team Program[2016ZT06N500] ; Guangdong Provincial Key Laboratory of Energy Materials for Electric Power[2018B030322001]

Science & Technology - Other Topics ; Materials Science

Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:000787373300089

AMER CHEMICAL SOC

20221211820255

Binary alloys ; Curve fitting ; Electrolytes ; Electrolytic reduction ; Free energy ; Kinetics ; Metals ; Oxygen ; Platinum alloys ; Polarization

Ore Treatment:533.1 ; Precious Metals:547.1 ; Fluid Flow, General:631.1 ; Thermodynamics:641.1 ; Electric Batteries and Fuel Cells:702 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Numerical Methods:921.6 ; Classical Physics; Quantum Theory; Relativity:931

2-s2.0-85126565689

Scopus

1.Harbin Institute of Technology,Harbin,150001,China
2.Department of Mechanical and Energy Engineering,Southern University of Science and Technology,Shenzhen,518055,China
3.Ministry of Education Key Laboratory of Energy Conversion and Storage Technologies,Southern University of Science and Technology,Shenzhen,518055,China
4.Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen,Guangdong Province,518055,China

Liu，Haijun,Chen，Ming,Sun，Fengman,et al. Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal-Electrolyte Interfaces[J]. ACS Applied Materials & Interfaces,2021,14(11):13891-13903.

Liu，Haijun,Chen，Ming,Sun，Fengman,Zaman，Shahid,Wang，Min,&Wang，Haijiang.(2021).Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal-Electrolyte Interfaces.ACS Applied Materials & Interfaces,14(11),13891-13903.

Liu，Haijun,et al."Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal-Electrolyte Interfaces".ACS Applied Materials & Interfaces 14.11(2021):13891-13903.