Correlations between Mass Activity and Physicochemical Properties of Fe/N/C Catalysts for the ORR in PEM Fuel Cell via 57Fe Mossbauer Spectroscopy and Other Techniques

被引:466
作者
Kramm, Ulrike I. [1 ,1 ]
Lefevre, Michel [2 ]
Larouche, Nicholas [1 ]
Schmeisser, Dieter
Dodelet, Jean-Pol [1 ]
机构
[1] INRS Energie Mat Telecommun, Varennes, PQ J3X 1S2, Canada
[2] Canetique Electrocatalysis Inc, Varennes, PQ J3X 1S2, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
FE-BASED CATALYSTS; OXYGEN-REDUCTION REACTION; CARBON; IRON; ELECTROCATALYSTS; PYROLYSIS; DENSITY; METALLOPORPHYRINS; ELECTROREDUCTION; POLYANILINE;
D O I
10.1021/ja410076f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The aim of this work is to clarify the origin of the enhanced PEM-FC performance of catalysts prepared by the procedures described in Science 2009, 324, 71 and Nat. Commun. 2011, 2, 416. Catalysts were characterized after a first heat treatment in argon at 1050 degrees C (Ar) and a second heat treatment in ammonia at 950 degrees C (Ar + NH3). For the NC catalysts a variation of the nitrogen precursor was also implemented. Fe-57 Mossbauer spectroscopy, X-ray photoelectron spectroscopy, neutron activation analysis, and N-2 sorption measurements were used to characterize all catalysts. The results were correlated to the mass activity of these catalysts measured at 0.8 V in H-2/O-2 PEM-FC. It was found that all catalysts contain the same FeN4-like species already found in INRS Standard (Phys. Chem. Chem. Phys. 2012, 14, 11673). Among all FeN4-like species, only D1 sites, assigned to FeN4/C, and D3, assigned to N-FeN2+2/C sites, were active for the oxygen reduction reaction (ORR). The difference between INRS Standard and the new catalysts is simply that there are many more D1 and D3 sites available in the new catalysts. All (Ar + NH3)-type catalysts have a much larger porosity than Ar-type catalysts, while the maximum number of their active sites is only slightly larger after a second heat treatment in NH3. The large difference in activity between the Ar-type catalysts and the Ar + NH3 ones stems from the availability of the sites to perform ORR, as many sites of the Ar-type catalysts are secluded in the material, while they are available at the surface of the Ar + NH3-type catalysts.
引用
收藏
页码:978 / 985
页数:8
相关论文
共 47 条
  • [1] Oxygen electroreduction on FeII and FeIII coordinated to N4 chelates.: Reversible potentials for the intermediate steps from quantum theory
    Anderson, AB
    Sidik, RA
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (16) : 5031 - 5035
  • [2] PYROLYSIS BEHAVIOR OF METALLOPORPHYRINS .2. A MOSSBAUER STUDY OF PYROLYZED FE(III) TETRAPHENYLPORPHYRIN CHLORIDE
    BLOMQUIST, J
    LANG, H
    LARSSON, R
    WIDELOV, A
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (14): : 2007 - 2011
  • [3] Phase identification of iron nitrides and iron oxy-nitrides with Mossbauer spectroscopy
    Borsa, DM
    Boerma, DO
    [J]. HYPERFINE INTERACTIONS, 2003, 151 (01): : 31 - 48
  • [4] On active-site heterogeneity in pyrolyzed carbon-supported iron porphyrin catalysts for the electrochemical reduction of oxygen: An in situ Mossbauer study
    Bouwkamp-Wijnoltz, AL
    Visscher, W
    van Veen, JAR
    Boellaard, E
    van der Kraan, AM
    Tang, SC
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (50) : 12993 - 13001
  • [5] Fe/N/C non-precious catalysts for PEM fuel cells: Influence of the structural parameters of pristine commercial carbon blacks on their activity for oxygen reduction
    Charreteur, Fanny
    Jaouen, Frederic
    Ruggeri, Stephane
    Dodelet, Jean-Pol
    [J]. ELECTROCHIMICA ACTA, 2008, 53 (06) : 2925 - 2938
  • [6] de Frank Bruijn A., 2013, ENCY SUSTAINABLE SCI, P7694
  • [7] Debrunner P G., 1989, In, P139
  • [8] Dodelet J.P., 2006, N4-Macrocyclic Metal Complexes, P83, DOI DOI 10.1007/978-0-387-28430-9_3
  • [9] Dodelet J.-P., 2013, LECT NOTES ENERGY, V9, P271
  • [10] Elbaz L., 2013, LECT NOTES ENERGY EL, V9, P213