Citation: Yongting Chen, Xing Hu, Shengli Chen. Theoretical study of stability of metal-N₄ macrocyclic compounds in acidic media[J]. Chinese Journal of Catalysis, ;2016, 37(7): 1166-1171. doi: 10.1016/S1872-2067(15)61082-8 shu

Theoretical study of stability of metal-N₄ macrocyclic compounds in acidic media

College of Chemistry and Molecular Sciences, Whuhan University, Whuhan 430072, Hubei, China

Received Date: 2 February 2016
Revised Date: 14 March 2016

Fund Project: This work was supported by the National Basic Research Program of China (973 program, 2012CB215500 and 2012CB932800).

Fe and Co porphyrins and phthalocyanines are excellent catalysts for the oxygen reduction reaction (ORR) and are promising alternatives to Pt in fuel cells. However, the stability of these molecular catalysts in acidic media is poor. This study explores whether demetalation through proton exchange causes these metal macrocyclic catalysts to be unstable in acidic media. We first present a theoretical scheme for investigating exchange reactions of metal ions in metal macrocyclic compounds with protons in acidic media. The equilibrium concentrations of metal ions in solution when various metalloporphyrins (MPs) and metallophthalocyanines (MPcs) are brought into contact with a strongly acidic solution (pH = 1) were then estimated using density functional theory calculations; these values were used to evaluate the stability of these metal macrocyclic compounds against demetalation in acidic media. The results show that Fe, Co, Ni, and Cu phthalocyanines and porphyrins have considerable resistance to exchange with protons, whereas Cr, Mn, and Zn phthalocyanines and porphyrins easily undergo demetalation through ion exchange with protons. This suggests that the degradation in the ORR activity of Fe and Co macrocyclic molecular catalysts and of carbon materials doped with Fe(Co) and nitrogen, which are believed to have metal-nitrogen coordination structures similar to those of macrocyclic molecules as ORR catalytic centers, is not the result of replacement of metal ions by protons. The calculation results show that electron-donating substituents could enhance the stability of Fe and Co phthalocyanines.
- Metalloporphyrin,
- Metallophthalocyanine,
- De-metalation,
- Metal ion-proton exchange,
- DFT calculation,
- Substituent group
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通讯作者: 陈斌, bchen63@163.com

Theoretical study of stability of metal-N₄ macrocyclic compounds in acidic media