TY - JOUR
T1 - Effect of Interfacial Action on the Generation and Transformation of Reactive Oxygen Species in Tripolyphosphate-Enhanced Heterogeneous Fe3O4/O2 Systems
AU - Zhang, Chengwu
AU - Kong, Chuipeng
AU - Tratnyek, Paul G.
AU - Qin, Chuanyu
AU - Zhao, Yongsheng
AU - Piao, Yunxian
N1 - Publisher Copyright:
© 2024 American Chemical Society
PY - 2024/1/16
Y1 - 2024/1/16
N2 - It has been reported that tripolyphosphate (TPP) can enhance the oxygenation of natural Fe(II)-containing minerals to produce reactive oxygen species (ROS). However, the molecular structure of the TPP-Fe(II) mineral surface complex and the role of this complex in the generation and transformation of ROS have not been fully characterized. In the present study, a heterogeneous magnetite (Fe3O4)/O2/TPP system was developed for the degradation of p-nitrophenol (PNP). The results showed that the addition of TPP significantly accelerated the removal of PNP in the Fe3O4/O2 system and extended the range of effective pH to neutral. Experiments combined with density functional theory calculations revealed that the activation of O2 mainly occurs on the surface of Fe3O4 induced by a structural Fe(II)-TPP complex, where the generated O2•- (intermediate active species) can be rapidly converted into H2O2, and then the •OH generated by the Fenton reaction is released into the solution. This increases the concentration of •OH produced and the efficiency of •OH produced relative to Fe(II) consumed, compared with the homogeneous system. Furthermore, the binding of TPP to the surface of Fe3O4 led to stretching and even cleavage of the Fe-O bonds. Consequently, more Fe(II)/(III) atoms are exposed to the solvation environment and are available for the binding of active O2 and O2•-. This study demonstrates how common iron minerals and O2 in the natural environment can be combined to yield a green remediation technology.
AB - It has been reported that tripolyphosphate (TPP) can enhance the oxygenation of natural Fe(II)-containing minerals to produce reactive oxygen species (ROS). However, the molecular structure of the TPP-Fe(II) mineral surface complex and the role of this complex in the generation and transformation of ROS have not been fully characterized. In the present study, a heterogeneous magnetite (Fe3O4)/O2/TPP system was developed for the degradation of p-nitrophenol (PNP). The results showed that the addition of TPP significantly accelerated the removal of PNP in the Fe3O4/O2 system and extended the range of effective pH to neutral. Experiments combined with density functional theory calculations revealed that the activation of O2 mainly occurs on the surface of Fe3O4 induced by a structural Fe(II)-TPP complex, where the generated O2•- (intermediate active species) can be rapidly converted into H2O2, and then the •OH generated by the Fenton reaction is released into the solution. This increases the concentration of •OH produced and the efficiency of •OH produced relative to Fe(II) consumed, compared with the homogeneous system. Furthermore, the binding of TPP to the surface of Fe3O4 led to stretching and even cleavage of the Fe-O bonds. Consequently, more Fe(II)/(III) atoms are exposed to the solvation environment and are available for the binding of active O2 and O2•-. This study demonstrates how common iron minerals and O2 in the natural environment can be combined to yield a green remediation technology.
KW - density functional theory
KW - Fe(II)-containing minerals
KW - interfacial action
KW - molecular oxygen activation
KW - ROS transformation
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U2 - 10.1021/acs.est.3c07372
DO - 10.1021/acs.est.3c07372
M3 - Article
C2 - 38179651
AN - SCOPUS:85182003760
SN - 0013-936X
VL - 58
SP - 1378
EP - 1389
JO - Environmental Science and Technology
JF - Environmental Science and Technology
IS - 2
ER -