TY - JOUR
T1 - Positively Charged P-Assisted Ru-Zn Dual Active Sites Promote Oxygen Radical Coupling Mechanism for Acidic Water Oxidation
AU - Zhang, Guolin
AU - Li, Zijian
AU - Jang, Haeseong
AU - Gao, Guoliang
AU - Gao, Hanyu
AU - Kim, Min Gyu
AU - Cho, Jaephil
AU - Liu, Shangguo
AU - Qin, Qing
AU - Liu, Xien
PY - 2025/3/17
Y1 - 2025/3/17
N2 - The oxygen evolution reaction (OER) mechanism plays a pivotal role for tuning the activity and stability in an acidic medium. However, obtaining a customized reaction pathway through fine manipulation of the catalyst structure still faces considerable challenges. Herein, we incorporate the Zn single atom and positively charged P into a RuO2 lattice to construct a Zn1P-RuO2−δ catalyst, which enables a heterogeneous dual-site dioxygen radical coupling mechanism (OCM) to release O2, breaking the limitations of activity and stability of traditional adsorbed evolution mechanism. In 0.5 M H2SO4, Zn1P-RuO2−δ shows superior catalytic activity with a mere overpotential of 176 mV at 10 mA cm-2 and significantly extended durability compared to Zn1RuO2−δ and commercial RuO2. Experimental and theoretical studies revealed that the incorporation of the single atom Zn creates an asymmetric Ru-Zn dual site with appropriate geometry, facilitating the formation and direct coupling of dioxygen radicals, while P doping optimizes the adsorption strength of Zn active sites to *O and further reduces the reaction energy barrier of the OCM pathway. This novel mechanism manipulation strategy paves up an optimal catalytic reaction pathway, which would fundamentally improve the efficiency of proton exchange membrane water electrolysis. © 2025 American Chemical Society.
AB - The oxygen evolution reaction (OER) mechanism plays a pivotal role for tuning the activity and stability in an acidic medium. However, obtaining a customized reaction pathway through fine manipulation of the catalyst structure still faces considerable challenges. Herein, we incorporate the Zn single atom and positively charged P into a RuO2 lattice to construct a Zn1P-RuO2−δ catalyst, which enables a heterogeneous dual-site dioxygen radical coupling mechanism (OCM) to release O2, breaking the limitations of activity and stability of traditional adsorbed evolution mechanism. In 0.5 M H2SO4, Zn1P-RuO2−δ shows superior catalytic activity with a mere overpotential of 176 mV at 10 mA cm-2 and significantly extended durability compared to Zn1RuO2−δ and commercial RuO2. Experimental and theoretical studies revealed that the incorporation of the single atom Zn creates an asymmetric Ru-Zn dual site with appropriate geometry, facilitating the formation and direct coupling of dioxygen radicals, while P doping optimizes the adsorption strength of Zn active sites to *O and further reduces the reaction energy barrier of the OCM pathway. This novel mechanism manipulation strategy paves up an optimal catalytic reaction pathway, which would fundamentally improve the efficiency of proton exchange membrane water electrolysis. © 2025 American Chemical Society.
KW - acidic oxygen evolution reaction
KW - asymmetric dual sites
KW - metal and nonmetal dual doping
KW - radical coupling mechanism
KW - reaction pathway
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U2 - 10.1021/acssuschemeng.5c01109
DO - 10.1021/acssuschemeng.5c01109
M3 - RGC 21 - Publication in refereed journal
SN - 2168-0485
VL - 13
SP - 4277
EP - 4289
JO - ACS Sustainable Chemistry & Engineering
JF - ACS Sustainable Chemistry & Engineering
IS - 10
ER -