Spontaneous H2O2 Accumulation under O2 Driven by Sacrificial Oxidation of NiS2 without External Electrical/Photonic Input

Although spontaneous H2O2 accumulation by sacrificial oxidation of metal disulfides (FeS2, NiS2, etc.) under oxic conditions without external electrical/photonic input has been observed, the mechanistic understanding of HCO3- on the production of H2O2 is still not clear. In this study, HCO3- apparen...

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Publié dans:Langmuir : the ACS journal of surfaces and colloids. - 1985. - 41(2025), 40 vom: 14. Okt., Seite 27492-27501
Auteur principal: Wang, Yu-Le (Auteur)
Autres auteurs: Wang, Cong, Wu, Song-Hai, Liu, Yong, Han, Xu
Format: Article en ligne
Langue:English
Publié: 2025
Accès à la collection:Langmuir : the ACS journal of surfaces and colloids
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520 |a Although spontaneous H2O2 accumulation by sacrificial oxidation of metal disulfides (FeS2, NiS2, etc.) under oxic conditions without external electrical/photonic input has been observed, the mechanistic understanding of HCO3- on the production of H2O2 is still not clear. In this study, HCO3- apparently accelerates the production of H2O2 on NiS2, and the produced H2O2 increases from 53.85 to 90.12 μM with increasing concentrations of HCO3- from 0 to 0.5 M at pH 9.0. Electrochemical analyses indicate that HCO3- effectively mediates the 2e reduction of O2 to H2O2 on the surface of NiS2. EPR and Raman analyses rule out the primary contributions of soluble •OH and O2•- to the production of H2O2 and reveal the presence of both ≡Ni-OO• superoxo and ≡Ni-OOH peroxo on NiS2, which are important precursors for H2O2. The presence of CO3•- also indicates that HCO3- is an important H-donor during the reduction of O2 to H2O2. DFT calculations further reveal that it is thermodynamically more favorable for ≡Ni-OO• and ≡Ni-OOH to abstract H from HCO3- than from H2O to produce H2O2, confirming that HCO3- is a better H-donor than H2O to produce H2O2 via the H-abstraction pathway. This study provides insight into the importance of HCO3- on spontaneous H2O2 accumulation by sacrificial oxidation of NiS2 under oxic conditions without external electrical/photonic input 
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700 1 |a Wang, Cong  |e verfasserin  |4 aut 
700 1 |a Wu, Song-Hai  |e verfasserin  |4 aut 
700 1 |a Liu, Yong  |e verfasserin  |4 aut 
700 1 |a Han, Xu  |e verfasserin  |4 aut 
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