Materials Chemistry and Physics 62 (2000) 4451

Studies on the decomposition of carbon dioxide into carbon with oxygen-decient magnetite I. Preparation, characterization of magnetite, and its activity of decomposing carbon dioxide
a

Chun-lei Zhanga,b,*, Shuang Lib, Li-jun Wangb, Tong-hao Wub, Shao-yi Pengc

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China b Department of Chemistry, Jilin University, Changchun 130023, China c Shanxi Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, China Received 15 January 1999; received in revised form 24 June 1999; accepted 2 July 1999

Abstract The magnetite Fe3 O4 (0  < 0.5) of different particle sizes were prepared using wet-heating oxidation method, supercritical uid dry method and ferrous oxalate and ferric oxalate high-temperature decomposition method, and their structure were characterized by XRD, ssbauer spectra, IR spectra and STEM. The oxygen-decient magnetite of Fe3 O4 (0 <  < 1) was prepared using H2 reduction of Mo Fe3 O4 (0  < 0.5) at 573 K and its properties (lattice constant, magnetism, stability, and reduction ability) were studied in detail. The activity of decomposing CO2 with oxygen-decient magnetite of different sizes were compared and the effects of degree of oxygendeciency, reaction time, and temperature on the activity of the decomposing CO2 into carbon with oxygen-decient magnetite were investigated. It is found that oxygen in the CO2 was incorporated in the form of O2 into oxygen-decient magnetite and CO2 was reduced to carbon, at the same time Fe3O4 converted into stoichiometric Fe3O4. The smaller the particle size of magnetite is, the larger the oxygen-decient degree is, the higher the reaction temperature is, and the higher the activity of decomposing CO2 is. # 2000 Elsevier Science S.A. All rights reserved.
ssbauer spectra; Stability; Reduction Keywords: Decomposition of carbon dioxide; Magnetite; Oxygen-deciency; Carbon; Mo

1. Introduction The system of guarantee life is an important part of space shuttle spaceport and a major content of Life-sustaining system is how to condense and decompose carbon dioxide. It is important to clear away carbon dioxide and supply oxygen as soon as possible for living condition in space capsule and other sealed and discirculation air environmental system. Carbon dioxide of living discharge waste gas not only affects the quality of atmosphere, but also leads to `green house effect' which is warming the globe and affects natural environment of man-living with high developing modern industrialization. Now some developed countries have put giant fund into studies on the xation of carbon dioxide [1] to solve the problem of spaceship, charge of warming the globe, and crisis of energy source.
Corresponding author. Tel.: 86-411-469-4447; fax: 86-411-4691570 E-mail address: xucui@ms.dicp.ac.cn (C.-l. Zhang)
*

The xation of carbon dioxide has been extensively studied [210], but there are only a few reports concerning the complete decomposition of carbon dioxide into carbon by ferrites [510]. Recently, we reported the results which indicate that decomposing efciently carbon dioxide into carbon (nearly 100%) could be done with magnetite reduced by H2 which was prepared by wet-heating oxidation method [11] and ferrous oxalate decomposition method [12], the spinel structure of magnetite is kept before and after reaction so that it could easily be regenerated. Reid et al. [12] studied the Bosch reaction with metal iron in which the conversion of CO2 is below 30% at above 800 K and a lot of CO and CH4 of by products were formed, after reaction the iron changed to be oxides and carbides and couldn't be regenerated. Therefore, decomposing CO2 with oxygendecient magnetite is better than Bosch method [5,11]. The magnetite of different particle sizes were prepared by four methods in this paper. Based on the reduction activation and structural characterization of these magnetites, the activity of decomposing CO2 over oxygen-decient magne-

0254-0584/00/$ see front matter # 2000 Elsevier Science S.A. All rights reserved. PII: S 0 2 5 4 - 0 5 8 4 ( 9 9 ) 0 0 1 6 9 - 8

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tite was studied and correlated with the degree of oxygendeciency and the size of magnetite. 2. Experimental 2.1. Preparation of magnetite According to the wet-heating oxidation method [13,14] the suspensions of Fe(OH)2 with 2NaOH/FeSO4 1.0 (mol rate) was oxidized by air ow of 200 ml/min for 20 h at 358 K to obtain Fe3O4-II sample. Aquogel of Fe(OH)3 was prepared with Fe(NO3)3 solution by adding excess aqueous ammonia at room-temperature. After ltration, Fe(OH)3 was washed by anhydrous ethanol several times which become ethanol-gel, which was put into a high pressure chamber by adding anhydrous-ethanol in the chamber. The chamber was heated at the rate of 80 K/h until the temperature is above supercritical temperature (tc 516 K), and was kept at 533 K for 30 min. The ethanol was slowly released and then blown in N2 atmosphere until roomtemperature. Finally, Fe3O4-III was obtained by the supercritical uid dry method [1517]. Ferrous oxalate and ferric oxalate were put into quartz tube, respectively, after the samples were dried in the He gas stream at 473 K, they were heated rapidly to 923 K and kept at 923 K for 10 h. Products were cooled to the room-temperature in the He gas to obtain Fe3O4-IV and Fe3O4-V, respectively. Twenty grams of above-mentioned magnetite samples were reduced by H2 at a rate of 40 ml/min at 573 K for different time, so the magnetites with different oxygendecient degree were prepared. 2.2. Characterization of magnetite and determination of oxygen-deficient degree The analysis of X-ray diffraction (XRD) was determined by Rigaku P/MAX-IIIA type rotary X-ray diffractometry with Cu K radiation, whose scanning speed of phase analyzed is 48/min; lattice constant was determined by using 0.1258/min scanning speed, collecting all X-ray diffraction peaks within 20708 according to internal standard of Si, and calculated with least square method. The average particle size was measured by small-angle X-ray scattering method. The shape and particle size of the crystal were ssbauer specrecorded by STEM (Hitachi H-8100). The Mo bssbauer tra were recorded by Oxford type accelerating Mo
Table 1 Particle size, lattice constant, and chemical composition of magnetite samples Samples Average particle size (nm) Distribution of particle size (nm) Lattice constant (nm) Chemical composition Fe3O4-II 108.8 50.0140.8 0.8389 Fe3O4.1086

spectrometer with a 57Co source at room temperature. The spectra were calibrated by -Fe and calculated by a computer curve tting method to pure Lorentzian spapes. The IR-spectra was determined by Nicolet 5PC-IR optical spectrometer. Self-supporting wafers were pressed using a mixture of samples and CsI. The amount of Fe2 and total Fe of magnetite which was dissolved with a concentrated hydrochloric acid were measured by redox titration with solution of K2Cr2O7 and SnCl2K2Cr2O7, respectively, using diphenylamine-4-sulfonic acid sodium salt as the indicator. The chemical composition and the oxygen-decient degree of magnetite were obtained according to the ratio of Fe2/Fetot [11]. When magnetite samples contained Fe1x O and/or -Fe, the amount of Fe2 which is equal to the amount of Fe1x O ssbauer spectra, and/or -Fe in sample measuring with Mo were deducted from the amount of Fe2 and total Fe obtaining by chemical analysis, respectively. 2.3. Decomposition reaction of carbon dioxide and analysis of the products A closed reaction cell of 0.5 l without temperature and concentration gradient with 20 g of oxygen-decient magnetite was blown by an extremely pure He gas for 10 min and then was treated in vacuo for 20 min, nally CO2 was introduced into the reaction cell and the decomposition reaction was carried out at different temperatures (CO2 was rst introduced into a vessel with the same volume as the reactor to reach the pressure of 1.013 105 Pa at room temperature, then press CO2 from the vessel into the reactor at reaction temperatures). The inner pressure of the reaction cell was measured with the pressure gauge and the inner gas species were analyzed by SP-2305 type gas chromatography. The carbon deposited on the magnetite was analyzed by PerkinElmer 2400 CHN elementary analysis instrument. 3. Results and discussion 3.1. Structure characterization of magnetite The XRD of series of magnetite samples were given in Fig. 1, their lattice constants and average particle size were listed in Table 1, it is obvious that characteristic XRD peaks of the spinel-type compound appeared in the XRD spectra of

Fe3O4-III 28.5 16.735.4 0.8385 Fe3O4.1512

Fe3O4-IV 135.0 88.2180.5 0.8396 Fe3O4.0014

Fe3O4-V 8.5 5.012.6 0.8393 Fe3O4.0302

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Fig. 1. X-ray diffraction patterns of magnetite samples.

all these magnetite samples, but the weak peaks corresponding to -Fe and Fe1x O only appeared in Fe3O4-IV. It indicated that there were pure phases of spinel type compounds of those magnetite samples prepared by these three methods, except Fe3O4-IV containing a little amount of -Fe and Fe1x O which was prepared by high temperature decomposing ferrous oxalate. From Fig. 1, it was seen that the particle size of samples declined in order of Fe3O4IV > Fe3O4-II > Fe3O4-III > Fe3O4-V, which are 135.0, 108.8, 28.5, and 8.5 nm, respectively. It is quite evident that Fe3O4-V are superne particles. Their lattice constants are 0.8396, 0.8389, 0.8385, and 0.8393 nm, respectively, which are smaller than the lattice constant of the stoichiometric Fe3O4 (0.8397 nm), and it indicated that all of the samples whose chemical composition is Fe3O4d ( > 0) are oxygen-excess, this may be caused by the oxidation of parts of small particles of Fe3O4 into g-Fe2O3 in the process of preparation, and, therefore, became the solid solution of Fe3O4 (0 <  < 0.5) i.e., the oxygen-excess magnetite [13]. ssbauer spectra of magnetite samples and correThe Mo sponding parameters are given in Fig. 2 and Table 2. It can be seen that with the decrease of the average particle size of ssbauer spectra broadened and HA and HB magnetite, the Mo of internal magnetic eld decreased (except of Fe3O4-IV), isomeric shift (IS) decreased and quadruple splitting moment (QS ) increased because super exchangeable effect of A-site and B-site in spinel structure decreased [18]. From Table 2 it was known, the ratio (S SB/SA) of the peak area corresponding to B-site and A-site is below 2.0 (stoichio-

ssbauer spectre of magnetite samples. Fig. 2. Room-temperature Mo

metric Fe3O4, S 2.0), it was also further proven that the samples of original magnetite are oxygen-excess [13]. According to equation of (2 S)/(5S 6) of the cationdecient concentration given by Topsoe [19], the cationdecient concentration of Fe3O4-i (i IV, II, III, V) are 0.104, 7.87, 11.03 and 2.21%, respectively (the calculated chemical composition for Fe3O4-II: ion-distribution of the sample is Fe3[Fe31.1575Fe20.7639&0.0787]O4, corresponding oxygen-excess type is Fe3O4.1077), corresponding chemical composition are Fe3O4.0014, Fe3O4.1077, Fe3O4.1527 and Fe3O4.0297, which is very approachable to the results of chemical analysis in Table 1. The IR-spectrum of magnetites were shown in Fig. 3, two strong absorbed peaks appeared in these four samples. The peak near 600 cm1 belonged to tetrahedral elastic vibration, and the peak around 400 cm1 was ascribed to octahedral elastic and wresting vibration for these four samples [20]. Moreover, these absorption bands were signicantly broadened with the decrease of particle size of samples in order of Fe3O4-i (i IV, II, III, V).

C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 4451 Table 2 ssbauer parameter of magnetites at room temperature Mo Samples Fe3O4-IV Crystal phase Fe3O4 Fe1x O -Fe Fe3O4 Fe3O4 Fe3O4 Fe3O4 Fe3O4-II (3 h)a Fe3O4-II (5 h)a Fe3O4-II (10 h)a Fe3O4-II (20 h)a Fe3O4 Fe3O4 Fe3O4 -Fe Fe3O4 -Fe
a

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Coordination centre A B A B A B A B A B A B A B A B A B

IS (mm/s) 0.42 0.85 1.31 0.07 0.38 0.74 0.29 0.68 0.28 0.67 0.18 0.66 0.36 0.62 0.35 0.61 0.32 0.60 0.04 0.28 0.59 0.01

QS (mm/s) 0.01 0.04 0.20 0.25 0.02 0.02 0.08 0.01 0.27 0.0 0.48 0.38 0.02 0.0 0.0 0.0 0.0 0.01 0.01 0.01 0.0 0.0

H (kOe) 485.7 455.5 0.0 332.6 492.2 459.2 486.8 454.0 459.4 414.8 0.0 0.0 485.6 455.4 481.2 452.3 478.4 450.5 331.0 477.8 451.0 332.4

Fe% 27.21 53.97 17.01 1.81 47.70 52.30 53.71 46.29 15.04 21.38 22.30 41.29 31.82 68.18 28.94 71.26 25.18 66.12 8.80 21.31 55.89 22.80

SB/SA 1.9835

Fe3O4-II Fe3O4-III Fe3O4-V

1.0964 0.8619 1.4267 1.8520 2. 1447 2.4671 2.6230 2.6244

Reduction time.

Fig. 3. IR spectra of magnetite samples. ssbauer spectra for samples reduced Fe3O4Fig. 4. Room-temperature Mo II for 5 h (a) and 20 h (b) by H2 at 573 K.

3.2. The effect of reduction time on oxygen-deficiency of magnetite and its resulting properties It is known from Fig. 4 and Table 2 that the Fe3O4-II reduced by H2 gas for 5 h at 573 K maintained the spinel-structure, and no other phases appeared, there wasn't a little amount of -Fe formed until reached 10 h of reduction time. The longer the reduction time is, the more

amount of -Fe produced, and the amount of produced -Fe is about 22.8% when reduction time reached 20 h. Similar changes occurred on other samples with the increase of reduction time just that on the Fe3O4-II sample discussed above.

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Table 3 Lattice constant and chemical composition of Fe3O4-II under different reduction time at 573 K Reduction time (h) Lattice constant (nm) Chemical composition -value of oxygen deficiency 0 0.8389 Fe3O4.1086 0.1086 3 0.8403 Fe3O3.9545 0.0455 5 0.8410 Fe3O3.8676 0.1324 10 0.8418 Fe3O3.8281 0.1719 20 0.8419 Fe3O3.8277 0.1723

Table 4 Stability of oxygen-deficient magnetite of Fe3O4 ( 0.1324) Time In the air (298 K) 1 min 5 min 10 min 48 h In the He gas (623 K) 60 min Chemical composition of magnetites Fe3O3.9825 ( 0.0175) Fe3O4.0978( 0.0978) Fe3O4.1565 ( 0.1565) Ee3O4.1676 ( 0.1676) Fe3O3.8678 ( 0.1322) Time in the He gas (298 K) 10 min 100 min 300 min 48 h in the He gas (!673 K) 60 min Chemical composition of magnetites Fe3O3.8676 ( 0.1324) Fe3O3.8676 ( 0.1324) Fe3O3.8677( 0.1323) Fe3O3.8680 ( 0.1320) Fe3O4 -Fe

As shown in Tables 2 and 3 that within 5 h of reduction time (i.e., before a part of Fe3O4 reduced into -Fe), the lattice constant and -value of oxygen decient degree ssbauer increased and the internal magnetic eld of Mo spectra declined with increasing reduction time. When reduction time was over 10 h, the spinel structure initially disintegrated and a part of it decomposed into -Fe. At this moment the lattice constant, oxygen-decient degree and internal magnetic eld of Fe3O4 was still kept basically. Therefore, the change of lattice constant and internal magnetic eld of the samples accompany with the change of chemical composition, i.e., the larger the oxygen-decient degree is, the bigger the lattice constant is and smaller is the inner-magnetic-eld. It is known from Table 4 that the oxygen-decient magnetite Fe3O4 ( > 0) is stable in the He gas below 623 K, but it is unstable in the He gas at above 673 K and decomposed to -Fe and Fe3O4. This agrees with the result of Darken [21]. The oxygen-decient magnetite is unstable in air at room temperature and it is rapidly oxidized and converted into the Fe3O4 ( > 0) of oxygen-excess magnetite. By comparison of the oxygen-decient magnetite Fe3O4 ( > 0) with oxygen-excess and stoichiometric magnetite Fe3O4 ( ! 0), it can be seen that the oxygen-decient magnetite has relatively larger lattice constant, ssbauer spectrum and smaller internal magnetic eld of Mo higher chemical-potential energy, thus it is active and unstable and is easily to decompose into Fe3O4 and -Fe. At room-temperature, Fe3O4 is able to convert O2 gas into O2 of crystal grating rapidly, which lled in oxygendeciency, and appears stronger reducing ability. Similarly, it is probable that Fe3O4 converts oxygen in gaseous oxides, such as CO2, into O2 in the crystal grating of magnetite and reduces non-oxygen element.

3.3. Reactivity of decomposition of CO2 with the oxygen deficient magnetite 3.3.1. Decomposing activity of CO2 and its relation of particle size of sample and reduction time Table 5 gives the activity of CO2 decomposition over series of oxygen-decient magnetites with different particle size. With the same reduction time, it is evident that the conversion of CO2 and the amount of carbon deposited on the magnetite increased in order of Fe3O4-II < Fe3O4-III < Fe3O4-V < Fe3O4-IV, i.e., according to the decrease order of the particle size of magnetites (expect that of Fe3O4-IV), but the changes of the partial pressure of CO2 and CO are on the opposite. Though particle size of the magnetite of Fe3O4-IV is larger, the conversion of CO2 and the amount of carbon deposited on the magnetite are the largest in all of the samples at the same reduction time. From Table 5, it was also found that the conversion of CO2 and the amount of deposited carbon increased with the increase of reduction time, no matter which kind of particle size of the magnetite is. The sample of magnetite reduced for 5.0 h was nearly able to decompose completely 0.5 l of CO2 for 3 h. 3.3.2. Relation between reactivity of CO2 decomposition and reaction time From Fig. 5 it can be seen that the partial pressure of CO2 gas declined sharply from 1.013 l05 Pa to 0.36 105 Pa within the initial 45 min, then the decrease of CO2 gas slowed down. The carbon dioxide was nearly completely converted after 180 min (about 97%). The carbon monoxide reached a maximum value of 30% (about 0.30 105 Pa) at 45 min, then it declined and disappeared after 180 min. In the process of the reaction, the inner pressure gradually declined, nally the system became a vacuum and the total inner pressure (curve c) was nearly equal to the sum of the

C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 4451 Table 5 Data of activity of decomposition of CO2 with magnetite with different particle size and reduction time with reaction time 3 ha Sample Fe3O4-II Fe3O4-III Fe3O4-IV Fe3O4-V Average particle size (nm) 108.8 28.5 135.0 8.5 Reduction time (h) 0 3 5 0 3 5 0 3 5 0 3 5 Conversion of CO2 (%) 0 64 97 0 70 100 75 100 100 0 85 100 Deposited carbon a(mg) 0 131.3 259.8 0 155.3 267.8 176.8 267.8 267.8 0 208.9 267.8 Pressure of CO2 (105 Pa) 1.01 0.36 0.03 1.01 0.30 0 0.25 0 0 1.01 0.15 0

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Pressure of CO ( 105 Pa) 0 0.15 0 0 0.12 0 0.09 0 0 0 0.07 0

The amount of carbon deposited on 20 g magnetite by elemental analysis, for Fe3O4-IV including the carbon in Fe3C.

Fig. 5. The decrease in PCO2 (a), PCO (b) and inner pressure (c) as function of time for the reaction between CO2 and magnetite Fe3O3.8676 at 573 K.

Fig. 6. The relationship between the partial pressure of CO2 and the reaction time on the magnetite Fe3O3.8676 at various temperatures.

partial pressure of CO2 (curve a ) and the partial pressure of CO (curve b), it suggested that the inner gas species are composed of gaseous CO2 and CO and this was also proved by gas chromatography. The above discussion indicated that when the oxygen-decient magnetite decomposed CO2, a part of CO2 rstly converted into the CO intermediate and then CO converted into carbon with a speed faster than that of CO2 decomposed directly to carbon. The XRD patterns of the reacted samples revealed that it maintained the spinel structure and the calculated lattice constant was 0.8396 nm which was nearly equal to the lattice constant 0.8397 nm of stoichiometric Fe3O4. These results indicated that the spinel structure of oxygen-decient magnetite did not change after reaction and it converted into the stoichiometric Fe3O4. Simultaneously, it also indicated that Fe3O4 was able to seize oxygen in the CO2, and incorporate the oxygen in the form of O2 into oxygen-deciency of crystal grating. Finally, CO2 was reduced to carbon. From the tangent of the curve of the variation of partial pressure of CO2 with the time, the decomposition speed of CO2 on Fe3O3.8676 at 573 K (tangent slope) is evaluated to be 2.9 $ 3.5

106 mol min1 g1. The results of carbon elemental analysis show that the amount of carbon deposited on the magnetite (Table 5) after reaction 180 min was nearly equal to the amount of carbon in the initial CO2, in the reaction system, which strongly supported the conclusion that carbon dioxide completely decomposed into C and the oxygen in the CO2 transferred was incorporate into the crystal lattice of oxygen-decient magnetite. 3.3.3. Relation between reactivity of CO2 decomposition and reaction temperature Figs. 6 and 7 showed the changes of the partial pressure of CO2 and CO, respectively, on Fe3O3.8676 at different temperature with reaction time. It is evident that the partial pressure of CO2 rapidly declined, while the partial pressure of CO was rapidly risen in the initial period of the reaction. When the partial pressure of CO reached a maximum, the decrease of the partial pressure of CO2 slowed down, and after the maximum the partial pressure of CO decreased slowly, nally disappeared. At last the system become a vacuum, CO2 and CO were completely converted into

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Fig. 7. The relationship between the partial pressure of CO and the reaction time on the magnetite Fe3O3.8676 at various temperature.

Fig. 8. The relative curves between the partial pressure of CO2 for reaction time 180 min and -value of Fe3 O4 at 573 K.

carbon and O2 in lattice of magnetite. From Fig. 6 it also can be seen that the decrease speed of the partial pressure of CO2 was fast, i.e., the decomposed speed of CO2 increased with increasing temperature, it needed 180 min to completely convert CO2 (97%) at 573 K. While at 623 and 673 K it only needed about 100 and 30 min to completely decompose CO2, respectively. The initially rising speed (produced speed) of partial pressure of CO and its lately declining speed (decomposed speed) both increased with rising temperature. In the process of the reaction, the speed of decomposition of carbon monoxide is faster than the speed of decomposition of carbon dioxide. It takes only 25 min to completely decompose CO at 673 K, and 70 min, 180 min are needed at 623 and 573 K, respectively. When the reaction temperature was above 523 K, the time before reaching maximum value of partial pressure of CO was shorter and the maximum value of partial pressure of CO was smaller with rising temperature, while the maximum values increased with increasing temperature when the reaction temperature is below 523 K. 3.3.4. Correlation of reactivity of CO2 decomposition to -value of oxygen deficient degree of Fe3O4 Fig. 8 indicated that with the same reaction time, the larger oxygen-decient degree of Fe3O4 is, the lower is the partial pressure of CO2. After reacting for 180 min, the conversion of carbon dioxide into carbon were 97, 78, and 60%, with the -value of Fe3O4 of 0.1324, 0.0832 and 0.0315, respectively. When -value of Fe3O4 of magnetite is 0.1719, 100% of carbon dioxide was decomposed to carbon only for 75 min. Fig. 9 shows the variation of the partial pressure of CO with the reaction time. It is obvious that larger the -value of Fe3O4 is, the less amount of the produced CO is, and faster is the CO further converted to carbon. When the -value of magnetite was equal to 0.1719 and 0.1324, the partial pressure of CO achieved a maximum value of 0.l6 105 Pa for 20 min and 0.3 105 Pa for 37 min, which were completely converted to carbon for 57 and 180 min, respectively. When the -value of Fe3O4

Fig. 9. The relative curves between the partial pressure of CO for reaction time 180 min and -value of Fe3 O4 at 573 K.

was 0.0832, the partial pressure of CO achieved a maximum value of 0.34 105 Pa for 55 min, and the partial pressure of CO reached 0.10 l05 Pa for 180 min. But when the -value of sample was 0.0315, the partial pressure of CO achieved a maximum value of 0.37 105 Pa for 68 min and at that moment the partial pressure of CO2 were 0.61 105 Pa, from which it was seen that the converted CO2 (about 95%) nearly completely decomposed to CO. It was seen that the larger -value of Fe3O4 is, and the shorter time needed for achieving the maximum value of the partial pressure of CO is, the less amount of CO is, the faster the CO2 and CO further converted into carbon is. The above analysis indicated that the decomposition of CO2 over magnetite relates directly to the degree of oxygendeciency of magnetite. When -value of magnetite is larger, main products of CO2 decomposition is carbon and a little intermediate CO was formed but it abruptly converted into carbon. When -value of magnetite is relatively smaller, major decomposition product is intermediate CO and then CO converted into carbon. If -value was near 0, the nally product would be CO and the conversion of CO2 is very low.

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4. Conclusions 1. The particle size of magnetite Fe3O4-i (i II $ V) declined in order of i IV, II, III, V and all of them are the oxygen-excess of Fe3O4 ( > 0) prepared by wetheating oxidation, supercritical uid dry, ferrous and ferric oxalate high-temperature decomposing methods, respectively. With particle size decreasing, internal ssbauer spectra of magnetite magnetic-eld of Mo ssbauer spectra and IR spectrum declined, peaks of Mo were signicantly broadened. 2. The -value of oxygen-deficient magnetite Fe3O4 ( > 0) increased with increasing time of H2 reducing Fe3O4 ( > 0) at 573 K. Fe3O4 is stable in the He gas below 673 K. But it is unstable in the He gas at above 673 K or in the air at room-temperature. The larger the oxygen-deficient degree is, and the larger the lattice constant of Fe3O4 is, the smaller the internal ssbauer spectra is, the higher magnetic field of Mo chemical potential energy of Fe3O4 is, and the more unstable it is, the stronger the ability of its reduction is. 3. The oxygen-deficient magnetite of Fe3O4 ( > 0) is able to efficiently seize oxygen in the CO2 so that CO2 decomposed to carbon and the Fe3O4 ( > 0) changed to be stoichiometric Fe3O4. The smaller the particle size of magnetite is, the higher reaction temperature is, and the higher decomposing activity of CO2 is. The larger the oxygen-deficient degree is, the less amount of intermediate CO is, the faster the speed of CO2 and CO conversion into carbon are.

Acknowledgements Financial support from the National Natural Science Foundation of China (NNSFC 29703002) are gratefully acknowledged. References
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