First principles study of Fenton reaction catalyzed by FeOCl:reaction mechanism and location of active site  

作　　者：Xuan-Xuan Ji Hai-Feng Wang Pei-Jun Hu 

机构地区：[1]Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis and Centre for Computational Chemistry, School of Chemical and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China [2]School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast BT9 5AZ, UK

出　　处：《Rare Metals》2019年第8期783-792,共10页稀有金属（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.21622305 and21333003);the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(No.YESS20150131);"Shu Guang"Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(No.17SG30);the Fundamental Research Funds for the Central Universities(No.WJ1616007)

摘　　要：Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl(100)surface were systematically investigated.It is found that on clean FeOCl(100)surface,the exposed[Fe^3+-Fe^3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe^3+ into Fe^2+.On fully H-covered FeOCl(100),H2O2 can efficiently dissociate at[Fe^2+-Fe^2+]sites into two OH,but OH binds with Fe^2+ so strongly that it cannot desorb as OH radical as easily as that on Fe^3+.Interestingly,FeOCl(100)tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe^2+-Fe^3+].On[Fe^2+-Fe^3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe^2+ couples with the surface H into H2O and finish the catalytic cycle.By comparison,Fe2 O3(012)cannot provide enough [Fe^2+-Fe^3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl（100）surface were systematically investigated.It is found that on clean FeOCl（100）surface,the exposed[Fe3+-Fe3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe3+ into Fe2+.On fully H-covered FeOCl（100）,H2 O2 can efficiently dissociate at[Fe2+-Fe2+]sites into two OH,but OH binds with Fe2+ so strongly that it cannot desorb as OH radical as easily as that on Fe3+.Interestingly,FeOCl（100）tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe2+-Fe3+].On[Fe2+-Fe3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe2+ couples with the surface H into H20 and finish the catalytic cycle.By comparison,Fe2 O3（012）cannot provide enough [Fe2+-Fe3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.

关 键 词：FENTON reaction FeOCl Density functional theory H2O2 Active SITE 

分 类 号：TF[冶金工程]