Low Effective Activation Energies for Oxygen Release from Metal Oxides: Evidence for Mass-Transfer Limits at High Heating Rates

被引：49

作者：

Jian, Guoqiang ^{[1
,2
]}

Zhou, Lei ^{[1
,2
]}

Piekiel, Nicholas W. ^{[1
,2
]}

Zachariah, Michael R. ^{[1
,2
]}

机构：

[1] Univ Maryland, Dept Chem & Biomol Engn, College Pk, MD 20742 USA

[2] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

来源：

CHEMPHYSCHEM | 2014年 / 15卷 / 08期

基金：

美国国家科学基金会;

关键词：

activation energy; high heating rates; isoconversion; metal oxides; nanoparticles; THERMAL-DECOMPOSITION; ENERGETIC MATERIALS; THIN-FILMS; REDUCTION; KINETICS; SPECTROMETRY; COPPER; OXIDATION; EQUILIBRIA; COMBUSTION;

D O I：

10.1002/cphc.201301148

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Oxygen release from metal oxides at high temperatures is relevant to many thermally activated chemical processes, including chemical-looping combustion, solar thermochemical cycles and energetic thermite reactions. In this study, we evaluated the thermal decomposition of nanosized metal oxides under rapid heating (similar to 10(5) Ks(-1)) with time-resolved mass spectrometry. We found that the effective activation-energy values that were obtained using the Flynn-Wall-Ozawa isoconversional method are much lower than the values found at low heating rates, indicating that oxygen transport might be rate-determining at a high heating rate.

引用

页码：1666 / 1672

页数：7

共 50 条

[1]

[Anonymous], J RES NATL BUR STA A

[2] Oxygen Release and Oxidation Rates of MgAl2O4-Supported CuO Oxygen Carrier for Chemical-Looping Combustion with Oxygen Uncoupling (CLOU) [J].

Arjmand, Mehdi ;

Keller, Martin ;

Leion, Henrik ;

Mattisson, Tobias ;

Lyngfelt, Anders .

ENERGY & FUELS, 2012, 26 (11) :6528-6539

[3] Ab initio thermodynamics of oxide surfaces:: O2 on Fe2O3(0001) -: art. no. 195409 [J].

Bergermayer, W ;

Schweiger, H ;

Wimmer, E .

PHYSICAL REVIEW B, 2004, 69 (19) :195409-1

[4] Species-specific isoconversion effective activation energies derived by thermogravimetry mass spectrometry [J].

Bonnet, E ;

White, RL .

THERMOCHIMICA ACTA, 1998, 311 (1-2) :81-86

[5] CHEMICAL ENERGY-STORAGE BY THE REACTION CYCLE CUO/CU2O [J].

CHADDA, D ;

FORD, JD ;

FAHIM, MA .

INTERNATIONAL JOURNAL OF ENERGY RESEARCH, 1989, 13 (01) :63-73

[6] EFFECT OF HEATING RATE ON ACTIVATION-ENERGIES DERIVED BY A DYNAMIC KINETIC METHOD [J].

CHEN, DTY .

JOURNAL OF THERMAL ANALYSIS, 1975, 7 (01) :61-64

[7]

Childs P. R. N., 2001, PRACTICAL TEMPERATUR, P146

[8] Comparison of iron-, nickel-, copper- and manganese-based oxygen carriers for chemical-looping combustion [J].

Cho, P ;

Mattisson, T ;

Lyngfelt, A .

FUEL, 2004, 83 (09) :1215-1225

[9] Effect of Heating Rate on the Activation Energy for Crystallization of Amorphous Ge2Sb2Te5 Thin Film [J].

Choi, Yunjung ;

Jung, Minsu ;

Lee, Young-Kook .

ELECTROCHEMICAL AND SOLID STATE LETTERS, 2009, 12 (07) :F17-F19

[10] Diffusive vs Explosive Reaction at the Nanoscale [J].

Chowdhury, Snehaunshu ;

Sullivan, Kyle ;

Piekiel, Nicholas ;

Zhou, Lei ;

Zachariah, Michael R. .

JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (20) :9191-9195

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