In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-...In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy(XPS).It is found that the discharge of fluorine containing anions([F]−)on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds,leading to the appearance of—CF_(3)or—C_(2)F_(5)group through six-carbon-ring opening.Elimination of—CF_(3)and—C_(2)F_(5) with F atom could be a likely mechanism of CF_(4) and C_(2)F_(6) formation.XPS results confirm that different types of—CF_(x) group can be formed on anode surface during electrolysis,and the possibility that[F]−discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.展开更多
基金the financial supports from the National Natural Science Foundation of China(Nos.51974373,51874365,62133016)the Major Scientific and Technological Innovation Projects of Shandong Province,China(No.2019JZZY020123)the Fundamental Research Funds for the Central Universities of Central South University,China(No.2019zzts242)。
文摘In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy(XPS).It is found that the discharge of fluorine containing anions([F]−)on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds,leading to the appearance of—CF_(3)or—C_(2)F_(5)group through six-carbon-ring opening.Elimination of—CF_(3)and—C_(2)F_(5) with F atom could be a likely mechanism of CF_(4) and C_(2)F_(6) formation.XPS results confirm that different types of—CF_(x) group can be formed on anode surface during electrolysis,and the possibility that[F]−discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.
