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ScienceDirect
Solar Energy 103 (2014) 425437
www.elsevier.com/locate/solener
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy,
Dalian 116023, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China
Received 13 December 2013; received in revised form 19 February 2014; accepted 21 February 2014
Available online 15 March 2014
Communicated by: Associate Editor Michael Epstein
Abstract
An ecient redox material for two-step thermochemical CO2 splitting reaction requires high chemical yield at relatively low reduction
temperature. Herein, the oxides with perovskite structure of formula LaxA1xFeyB1yO3 (A = Sr, Ce, B = Co, Mn; 0 6 x, y 6 1) start to
release O2 at 800 C and the largest O2 production is 11.8 ml/gperovskite at 1300 C. However, for these unsupported LaxA1xFeyB1yO3
materials, the CO production is low in spite of high reduction yield. ZrO2, Al2O3 and SiO2 are thus considered as supports to disperse
LaxA1xFeyB1yO3 materials and dierent supports induce great dierences in the reaction activity. By A-site or B-site substitution of
LaFeO3, the O2 releasing temperature has fallen from 1230 C to 800-950 C and the CO production is enhanced 23 times. LaFe0.7Co0.3O3 (25 wt%)/SiO2 shows the highest reaction activity among these investigated materials with the O2 production of 4.0 ml/gmaterial
(16.0 ml/gperovskite) and CO production of 7.6 ml/gmaterial (30.4 ml/gperovskite) when it is reduced at 1300 C and re-oxidized at 1100 C,
and the activity is relatively stable even after 10 cycles of the reaction. By contrast, the CO production is 4.5 ml/g for CeO2 when it
is reduced at 1400 C. The estimated activation energy for the reduction step of LaFe0.7Co0.3O3 (25 wt%)/SiO2 is around 89149 KJ/
mol according to dierent models. The CO generation step of LaFe0.7Co0.3O3 (25 wt%)/SiO2 is mainly controlled by bulk diusion
(D1) at 1000 C and then it turns to rst order surface reaction (F1) at 1100 C.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Ecient utilization of solar energy is an important subject. The conversion of concentrated solar energy into
chemical fuels via two-step thermochemical H2O and CO2
splitting reaction which uses the entire solar spectrum is
Corresponding author. Tel.: +86 411 84379070; fax: +86 411
84694447.
E-mail address: canli@dicp.ac.cn (C. Li).
http://dx.doi.org/10.1016/j.solener.2014.02.033
0038-092X/ 2014 Elsevier Ltd. All rights reserved.
1:1
1:2
Total reaction:
426
1:3
Fig. 1. (a) The O2 evolution rate-time proles from 800 C to 1300 C and (b) the CO generation rate-time proles at 1000 C of LaFexB1xO3 (B = Mn
and Co; x = 1.0, 0.7 and 0).
427
Fig. 2. SEM images of (a) LaFeO3, (b) LaFeO3 after high temperature treatment and (c) LaFe0.7Co0.3O3 (25 wt%)/SiO2 after 10 cycles.
428
Fig. 3. (a) The O2 evolution rate-time proles from 800 C to 1300 C and (b) the CO generation rate-time proles at 1000 C of LaFe0.7Co0.3O3 dispersed
on dierent supports for the rst cycle.
429
Fig. 4. XRD patterns of (a) LaFe0.7Co0.3O3, Al2O3 and LaFe0.7Co0.3O3 (25 wt%)/Al2O3 after reaction, (b) LaFe0.7Co0.3O3, ZrO2 and LaFe0.7Co0.3O3
(25 wt%)/ZrO2 after reaction, and (c) LaFe0.7Co0.3O3 (25 wt%)/SiO2 after 10 cycles of CO2 splitting reaction.
Fig. 5. The CO generation activity of (a) LaAl11xFexO19 (b) CoxFe3xO4 at 1000 C. The value of x is according to the content of iron in LaFe0.7Co0.3O3
(25 wt%)/Al2O3 and LaFe0.7Co0.3O3 (25 wt%)/ZrO2.
Co into LaFeO3 makes the thermal reduction step thermodynamically more favorable in comparison to pure LaFeO3.
The corresponding O2 production is increased from
1.3 ml/gperovskite up to 8.5 ml/gperovskite for LaFe0.7Mn0.3O3
and 6.4 ml/gperovskite for LaFe0.7Co0.3O3, respectively.
The generation of CO for these reduced LaFexB1xO3
materials shown in Fig. 1(b) demonstrates that CO2 splitting reaction activity is poor at 1000 C. These samples
present low CO generation rate and negligible CO production at 1000 C in spite of high reduction yield. SEM
images show that the samples are aggregated into large
particles after high temperature treatment and the poor
CO generation activity may be due to sintering (Fig. 2(a
and b)). Therefore, the perovskite oxides are dispersed
on supports to enhance the high temperature thermal
stability.
430
Fig. 6. XRD patterns of (a) SrFeO3, La0.7Sr0.3FeO3, La0.7Ce0.3FeO3 and LaFeO3 and (b) LaMnO3, LaCoO3, LaFe0.7Co0.3O3, LaFe0.7Mn0.3O3 and
LaFeO3.
Table 1
BET surface areas and crystallite sizes of these perovskite oxides.
Samples
Crystallite size
)
(A
Surface area
(m2 g1)
LaFeO3
La0.7Sr0.3FeO3
La0.7Ce0.3FeO3
LaFe0.7Co0.3O3
LaFe0.7Mn0.3O3
SiO2
LaFe0.7Co0.3O3/SiO2 after10 cycles
The crystallite size is calculated
from XRD
233
316
465
249
207
10.7
9.7
9.6
9.2
18.5
2.9
0.6
Fig. 7. (a) The O2 evolution rate-time proles, (b) CO generation rate-time proles at 1100 Cof LaxA1xFeO3 (A = Sr and Ce) (25 wt%)/SiO2 for the rst
cycle.
LaFe0.7Co0.3O3 (25 wt%)/SiO2 is 13 greater, for LaFe0.7Co0.3O3 (25 wt%)/Al2O3 is 5.6 greater, and for LaFe0.7Co0.3O3 (25 wt%)/ZrO2 is 2.9 greater, than that
produced by unsupported LaFe0.7Co0.3O3. LaFe0.7Co0.3O3
(25 wt%)/SiO2 is considered to be the best candidate which
could be reduced to a greater extent at same reduction temperature. The O2 evolution curves are quite dierent from
each other mainly due to dierent high temperature solid
state reactions occur between LaFe0.7Co0.3O3 and
supports.
As shown in Fig. 3(b), the CO generation activity
follows the order of intensities LaFe0.7Co0.3O3 (25 wt%)/
SiO2 > LaFe0.7Co0.3O3 (25 wt%)/ZrO2 > LaFe0.7Co0.3O3
(25 wt%)/Al2O3 > LaFe0.7Co0.3O3. The dierent productivities of LaFe0.7Co0.3O3 dispersed on dierent supports are
thus attributed to the dierent structural changes after high
temperature treatment.
The XRD patterns shown in Fig. 4(a) indicates that Fesubstituted hexaaluminate (LaAl11xFexO19) is formed for
LaFe0.7Co0.3O3 (25 wt%)/Al2O3 after high temperature
treatment. The CO production of LaAl11xFexO19 is negligible (Fig. 5(a)) and thus Al2O3 supported LaFe0.7Co0.3O3
exhibits low CO generation activity. For LaFe0.7Co0.3O3
(25 wt%)/ZrO2 after high temperature treatment, phases
of La2Zr2O7, CoxFe3xO4, and ZrO2 are observed. The
reaction activity of LaFe0.7Co0.3O3 (25 wt%)/ZrO2 is simi-
431
Fig. 8. (a) The O2 evolution rate-time proles and (b) the CO generation rate-time proles at 1100 C of LaFexCo1xO3 (x = 1, 0.9, 0.7, 0.5) (25 wt%)/
SiO2 for the rst cycle.
432
Fig. 9. The (a) O2 evolution rate-time proles and (b) CO generation rate-time proles at 1100 C of LaFexB1xO3 (B = Mn and Co) (25 wt%)/SiO2 for
the rst cycle.
Fig. 10. (a) O2 and (b) CO production of LaxA1xFeyB1yO3 (A = Sr, Ce; B = Co, Mn) (25 wt%)/SiO2 for the rst cycle.
433
Fig. 11. (a) The O2 rate-time proles at 1200 C, 1300 C, and 1400 C, (b) the corresponding CO generation activity at 1100 C of LaFe0.7Co0.3O3/SiO2.
434
(25 wt%)/SiO2. The initial CO generation rate of LaFe0.7Mn0.3O3 (25 wt%)/SiO2 is similar to that of LaFeO3
(25 wt%)/SiO2, and it is much lower than that of
LaFe0.7Co0.3O3 (25 wt%)/SiO2 (Fig. 9(b)), nevertheless, the
CO productivity is comparable to that of LaFe0.7Co0.3O3
(25 wt%)/SiO2, as shown in Fig. 10(b).
Fig. 11 exhibits the CO2 splitting activity for LaFe0.7Co0.3O3 (25 wt%)/SiO2 as the reduction temperature varies
from 1200 C to 1400 C. The O2 production is largely
increased as reduction temperature increases from
1200 C to 1400 C, from 1.6 ml/gmaterial up to 6.3 ml/gmaterial.
The corresponding CO production is only 0.4 ml/gmaterial
when the reduction temperature is 1200 C which indicates
Fig. 13. (a) O2 evolution rate of LaFe0.7Co0.3O3 (25 wt%)/SiO2 under heating rate of 10 C/min, (be) Arrhenius plot for the non-isothermal reduction of
LaFe0.7Co0.3O3 (25 wt%)/SiO2 according to dierent models. F1 means rst order reaction; F2 means second order reaction; R2 and R3 means
geometrical-contracting models.
3:2
435
Total O2 t
Total O2
The curve of ln
3:3
h
da=dT b
f a
Fig. 14. (a) the CO generation rate-time proles for LaFe0.7Co0.3O3 (25 wt%)/SiO2 from 900 C to 1100 C (b and c) normalized rate data compared to
solid state reaction model of the CO generation reaction for LaFe0.7Co0.3O3 (25 wt%)/SiO2 at 1000 C and 1100 C. F1 means rst order reaction; D1
means rst order diusion reaction model.
436
is 108 KJ/mol for F1, 149 KJ/mol for F2, 89 KJ/mol for
R2, and 97 KJ/mol for R3, respectively.
The CO generation rate can be expressed as follows:
da
kf a
dt
Acknowledgements
3:4
da=dta0:5 f aa0:5
3:5
437
Royer, S., Alamdari, H., Duprez, D., Kaliaguine, S., 2005. Oxygen storage
capacity of La1xAxBO3 perovskites (with A = Sr, Ce; B = Co, Mn)
relation with catalytic activity in the CH4 oxidation reaction. Appl.
Catal. B: Environ. 58, 273288.
Schee, J.R., Steinfeld, A., 2012. Thermodynamic analysis of ceriumbased oxides for solar thermochemical fuel production. Energy Fuels
26, 19281936.
Schunk, L.O., Steinfeld, A., 2009. Kinetics of the thermal dissociation of
ZnO exposed to concentrated solar irradiation using a solar-driven
thermogravimeter in the 18002100 K range. AIChE J. 55, 14971503.
Steinfeld, A., 2005. Solar thermochemical production of hydrogena
review. Solar Energy 78, 603615.
Tanaka, H., Misono, M., 2001. Advances in designing perovskite
catalysts. Curr. Opin. Solid State Mater. Sci. 5, 381387.
Wang, C.H., Chen, C.L., Weng, H.S., 2004. Surface properties and
catalytic performance of La1xSrxFeO3 perovskite-type oxides for
methane combustion. Chemosphere 57, 11311138.
Yang, Tan, Liang, Gu, X.H., Jin, W.Q., Zhang, L.X., Xu, N.P., 2003.
New series of Sr(Co, Fe, Zr)O3-dperovskite-type membrane materials
for oxygen permeation. Ind. Eng. Chem. Res. 42, 22992305.
Yang, H.C., Eun, H.C., Cho, Y.Z., Lee, H.S., Kim, I.T., 2009. Kinetic
analysis of dechlorination and oxidation of PrOCl by using a nonisothermal TG method. Thermochim. Acta 484, 7781.