氫氣的來源相當多元化且使用後主要產物為水，具有低污染的優點。而現今之製氫技術朝向水分解產氫之脈絡發展，因此使用化學迴圈程序分解水產氫技術值得研究探討。化學迴圈產氫程序利用載氧體在三個反應器之間與燃料、水氣、與空氣間交互氧化還原反應並連續迴圈循環，分別於燃料反應器獲得高純度二氧化碳、水蒸氣反應器進行水分解產氫與空氣反應器將載氧體反應回至原始狀態，此被視為一項具有不需CO2分離程序、低環境衝擊、高能源效率之能源技術。此技術提供氧化所需氧原子來源為金屬氧化物載氧體，而三氧化二鐵(Fe2O3)具有高度機械強度、高載氧率、低成本等，因此被廣泛應用於此製程技術，但其多種的氧化相態，與燃料氣體進行還原反應時將有顯著的遲緩現象，且經多數迴圈後材料會有嚴重的顆粒團聚，限制了產氫的反應效能。
本研究將以不同金屬離子摻雜Fe2O3以SEM、XRD和ICP分析觀察其表面、組成結構之變化以及不同金屬離子摻雜之含量，再於熱重分析儀模擬其還原活性，以期了解還原反應動力。實驗結果顯示添加微量金屬離子可改善其氧化鐵在不同氣氛下於600˚C-900˚C間之還原性能，反應速率將會隨著溫度的提升而增加，且在高溫下可判斷出屬於三個階段之還原反應。此外載氧體的還原反應可視為一個相態轉換過程，改質過之氧化鐵與純氧化鐵在不同氣氛下所得到之反應型態屬於一階反應。
由於三氧化二鋁具有耐高溫、價格低廉及產量豐富之特性，因此本研究使用三氧化二鋁做為惰性擔體應用於化學迴圈程序中，並使用固定床反應器搭配氫氣感測器分析在不同改質之氧化鐵搭配三氧化二鋁複合載氧體系統之水分解產氫效能與氧化反應動力，其材料分析方面以XRD、SEM以及孔隙率觀察其經化學迴圈程序反應前後之表面結構組成與剖面結構變化，進而評估不同金屬離子摻雜氧化鐵載氧體於化學迴圈水分解產氫技術之可行性。結果顯示，摻雜不同金屬離子可有效增強其氧化反應時與水蒸氣之反應進而提升其反應速率，同時提高氧化鐵之氫氣產生量。其中以FA、Ca-FA和Co-FA載氧體之氧化轉化率曲線獲得之斜率介於1-2之間，推測其氧化階段反應屬於一階反應(First-order reaction)；而Mg-FA和Cu-FA其氧化轉化率之斜率接近於1.0，可視為相界控制 (Phase-boundary controlled)機制。

Hydorgen is the most abundant chemical element in the universe. On the ground surface, hydorgen primarily exists in compounds, in particular, mostly in the form of water molecule. As a quiet and clean energy, hydorgen energy plays an important role in future energy development. Hydorgen production by water splitting with photocatalyst is still under development with the efforts on improving it lower efficiency. At present, renewable energies, such as hydraulic power, wind power, solar power and solar thermal power, are consumed to produce Hydorgen by electrolysis of water, which result in high cost issue. A new process for producing hydorgen from fuel gases (syngas or natural gas), based on chemical looping (CL) are declared elsewhere. The core of the process is composed of three-reactors system, in which iron oxide are transferred to: (i) oxidize fuel gases, (ii) water-splitting for producing hydorgen, (iii) react with air stream to the original. Iron Oxide (Fe2O3) is a potential substitute for other materials of hydorgen production. However, the performance of Fe2O3 oxygen carriers was dramatically reduced due to the agglomeration of particles. Thus, the ability of water-splitting for H2 production decreased at higher temperatures.
This study is to investigate the effects of various metal additives in the modified iron oxide on the redox performance of CL process by TGA system. Integrating with the materials characterizations by SEM, XRD and ICP analyses, the mechanism of reduction behavior will be addressed accordingly. The results showed that the doped metals promoted the reduction of Fe2O3 at 600-900˚C under different fuel gases. The pure and modified Fe2O3 samples prepared at higher temperature showed three reduction steps due to the change of oxidation states of iron. Also, it is noticed that the reduction model of the modified Fe2O3 can be assumed as the first order reaction.
Aluminium oxide (Al2O3) is a stable and inexpensive material which can be used in chemical looping hydrogen generation as an inner support. The modified iron oxide with Al2O3 composite system under H2/N2 as fuel gas in a fixed bed reactor with the hydorgen detector was investigated by its kinetics study of oxidation, the conversion efficiency and the ability of water-splitting for H2 production. The characterisitics of the prepared and reacted oxygen carriers were studied using XRD, SEM, and porosity analysis. Then, the feasibility of Metal-modified Fe2O3/Al2O3 composite system in CL process for hydorgen production would be expected to transfer for the real commercialization. The experimental results indicate that the doped metals in iron oxide effectiveky enhanced the oxidation with water of the iron oxide and increased the reaction rate. It was also concluded that the oxidation reaction of FA, Ca-FA and Co-FA were controlled by first-order reaction. The oxidation process of Mg-FA and Cu-FA could be interpreted as a phase-boundary-controlled reaction.

1.http://topics.nytimes.com/topics/news/science/topics/globalwarming/index.html.
2.吳龍暉，「用之不竭的乾淨氫氣能源」，太陽能學刊，第4卷，第1期，(1999)。
3.曲新生、陳發林、呂錫民，「產氫與儲氫技術」，五南圖書出版股份有限公司， (2007)。
4.A. Fujishima, K. Honda, “Electrochemical Photolysis of Water at a Semiconductor Electrode” Nature, Vol. 238, pp. 37-38, (1972).
5.E. Chao Raul, “Thermochemical Hydorgen Production. An Assessment of Nonideal Cycles” Industrial and Engineering Chemistry Process Design and Development, Vol. 14, pp. 276-279, (1975).
6.L. Stuart, “Thermochemical Solar Hydorgen Generation” Chemical Communications, pp. 4635-4646, (2005).
7.P. Christopher, W. Weimer Alan, “Likely Near-term Solar-thermal Water Splitting Technologies” International Journal of Hydorgen Energy, Vol. 29, pp. 1587-1599, (2004).
8.K. Akihiko, “Photocatalyst Materials for Water Splitting” Catalysis Surveys from Asia, Vol. 7, pp. 31-38, (2003) .
9.經濟部能源局，「我國燃料燃燒二氧化碳排放統計與分析」(2012)。
10.National energy technology laboratory “DOE/NETL Carbon Dioxide Capture and Storage RDandD Roadmap” pp. 31, (2010).
11.H.J. Richter, K.F Knoche, “Reversibility of Combustion Processes, in Efficiency and Costing - Second Law Analysis of Processes” ACS Symposium Series, pp. 71-85, (1983).
12.E. Jerndal, H. Leion, L. Axelsson, T. Ekvall, M. Hedberg, K. Johansson, M. Ka ̈lle ́n, R. Svensson, T. Mattisson, A. Lyngfelt, “Using Low-Coat Iron-Based Materials as Oxygen Carriers for Chemical Looping Combustion” Oil and Gas Science and Technology-Revue d’IFP Energies nouvelles, Vol. 66, pp. 235-248, (2011).
13.P. Gupta, L.G. Velazquez-Vargas, L.S. Fan, “Syngas Redox (SGR) Process to Produce Hydorgen from Coal Derived Syngas” Energy and Fuels, Vol. 21, pp. 2900-2908, (2007).
14.S.Y. Chen, Q. Shi, Z.P. Xue, X.Y. Sun, W.G. Xiang, “Experimental Investigation of Chemical-Looping Hydorgen Generation using Al2O3 or TiO2-supported Iron Oxides in a Batch Fluidized Bed” International Journal of Hydorgen Energy, Vol. 36, pp. 8915-8926, (2011).
15.T. Mattisson1, Q. Zafar, M. Johansson, A. Lyngfelt, “Chemical-Looping Combustion as a New CO2 Management Technology” First Regional Symposium on Carbon Management, (2006).
16.T. Mattisson, A. Lyngfelt, “A. Capture of CO2 using Chemical-Looping Combustion” First Biennial Meeting of the Scandinavian-Nordic Section of the Combustion Institute, (2001)
17.E. Jerndal, T. Mattisson, A. Lyngfelt, “A. Thermal Analysis of Chemical-Looping Combustion” Chemical Engineering Research and Design, Vol. 84, pp. 795-806.
18.J.S. Dennis, “Chemical Looping Combustion: One Answer to Sequestering Carbon Dioxide” Proceedings of the European Combustion Meeting, (2009).
19.H. Fang, L. Haibin, Z. Zengli, “Advancements in Development of Chemical-Looping Combustion: A Review” International Journal of Chemical Engineering, Vol. 2009, pp. 1-16, (2009).
20.P. Gayan, L.F. de Diego, F. Garćıa-Labiano, J. Adanez, A. Abad, C. Dueso, “Effect of Support on Reactivity and Selectivity of Ni-based Oxygen Carriers for Chemical-Looping Combustion” Fuel, Vol. 87, pp. 2641-2650, (2008).
21.Z. Gao, L. Shen, J. Xiao, C. Qing, Q. Song, “Use of Coal as Fuel for Chemical-Looping Combustion with Ni-Based Oxygen Carrier” Industrial and Engineering Chemistry Research, Vol. 47, pp. 9279-9287, (2008).
22.M. Ishida, H. Jin, “A Novel Chemical-Looping Combustor without NOx Formation” Industrial and Engineering Chemistry Research, Vol. 35, pp. 2469-2472, (1996).
23.H. Jin, M. Ishida, “Reactivity Study on Nnatural-gas-fueled Chemical-Looping Combustion by a Fixed-bed Reactor” Industrial and Engineering Chemistry Research, Vol. 41, pp. 4004-4007, (2002).
24.M. Ishida, H. Jin, T. Okamoto, “Kinetic Behavior of Solid Particle in Chemical-Looping Combustion: suppressing carbon deposition in reduction” Energy and Fuels, Vol. 12, pp. 223-229, (1998).
25.M. Ishida, H. Jin, T. Okamoto, “A fundamental study of a new kind of medium material for Chemical-Looping Combustion” Energy and Fuels, Vol. 10, pp. 958-963, (1996).
26.H. Jin, T. Okamoto, M. Ishida, “Development of a Novel Chemical-Looping Combustion: Synthesis of a Solid Looping Material of NiO/NiAl2O4” Industrial and Engineering Chemistry Research, Vol. 38, pp. 126-132, (1999).
27.P. Cho, T. Mattisson, A. Lyngfelt, “Defluidization Conditions for a Fluidized Bed of Iron Oxide-, Nickel Oxide-, and Manganese Oxide-containing Oxygen Carriers for Chemical-Looping Combustion” Industrial and Engineering Chemistry Research, Vol. 45, pp. 968-977, ( 2006).
28.P. Cho, T. Mattisson, A. Lyngfelt, “Carbon formation on nickel and Iron Oxide-containing Oxygen Carriers for Chemical-Looping Combustion” Industrial and Engineering Chemistry Research, Vol. 44, pp. 668-676, (2005).
29.M. Johansson, T. Mattisson, A. Lyngfelt, “Using of NiO/NiAl2O4 particles in a 10kW Chemical-Looping Combustor” Industrial and Engineering Chemistry Research, Vol. 45, pp. 5911-5919, (2006).
30.R. Villa, C. Cristiani, G. Groppi, L. Lietti, P. Forzatti, U. Cornaro, S. Rossini, “Ni Based Mixed Oxide Materials for CH4 Oxidation under Redox Cycle Conditions” Journal of Molecular Catalysis A, Vol. 204-205, pp. 637-646, (2003).
31.Q. Zafar, T. Mattisson, B. Gevert, “Redox Investigation of Some Oxides of Transition-state Metals Ni, Cu, Fe, and Supported on SiO2 and MgAl2O4” Energy and Fuels, Vol. 20, pp. 34-44, (2006).
32.E. Johansson, T. Mattisson, A. Lyngfelt, H. Thunman, “A 300W Laboratory Reactor System for Chemical-Looping Combustion with Particle Circulation” Fuel, Vol. 85, p. 1428-1438, (2006).
33.F. Garćıa-Labiano, L.F. de Diego, J. Adanez, A. Abad, P. Gayan, “Reduction and Oxidation Kinetics of a Copper-based Oxygen Carrier Prepared by Impregnation for Chemical-Looping Combustion” Industrial and Engineering Chemistry Research, Vol. 43, pp. 8168-8177, (2004).
34.A. Abad, J. Adanez, F. Garćıa-Labiano, L.F. de Diego, P. Gayan, J. Celaya, “Mapping of the Range of Operational Conditions for Cu-, Fe-, and Ni-based Oxygen Carriers in Chemical-Looping Combustion” Chemical Engineering Science, Vol. 62, pp. 533-549, (2007).
35.L.F. de Diego, F. Garćıa-Labiano, P. Gayan, J. Celaya, J.M. Palacios, J. Adanez, “Operation of a 10kWth Chemical-Looping Combustor during 200h with a CuO-Al2O3 Oxygen Carrier” Fuel, Vol. 86, pp. 1036-1045, (2007).
36.L.F. de Diego, F. Garćıa-Labiano, J. Adanez, et al., “Development of Cu-based Oxygen Carriers for Chemical-Looping Combustion” Fuel, Vol. 83, pp. 1749-1757, (2004).
37.T. Mattisson, A. Jardnas, A. Lyngfelt, “Reactivity of Some Metal Oxides Supported on Alumina with Alternating Methane and Oxygen-application for Chemical-Looping Combustion” Energy and Fuels, Vol. 17, pp. 643-651, (2003).
38.L.F. de Diego, P. Gayan, F. Garćıa-Labiano, J. Celaya, A. Abad, J. Adanez, “Impregnated CuO/Al2O3 Oxygen Carriers for Chemical-Looping Combustion: Avoiding Fluidized Bed Agglomeration” Energy and Fuels, Vol. 19, pp. 1850-1856, (2005).
39.S.Y. Chuang, J.S. Dennis, A.N. Hayhurst, S.A. Scott,“Development and performance of Cu-based Oxygen Carriers for Chemical-Looping Combustion” Combustion and Flame, Vol. 154, pp. 109-121, (2008).
40.P. Cho, T. Mattisson, A. Lyngfelt, “Comparison of Iron-, Nickel-, Copper-, and Manganese-based Oxygen Carriers for Chemical-Looping Combustion” Fuel, Vol. 83, pp. 1225-1245, (2004).
41.B.M. Corbella, L.F. de Diego, F. Garćıa-Labiano, J. Adanez, J.M. Palacios, “Characterization and Performance in a Multicycle Test in a Fixed-bed Reactor of Silica-supported Copper Oxide as Oxygen Carrier for Chemical-Looping Combustion of Methane” Energy and Fuels, Vol. 20, pp. 148-154, (2006).
42.T. Mattisson, H. Leion, and A. Lyngfelt, “Chemical-Looping with Oxygen Uncoupling using CuO/ZrO2 with Petroleum Coke,” Fuel, Vol. 88, pp. 683-690, (2009).
43.B.M. Corbella, L.F. de Diego, F. Garćıa-Labiano, J. Adanez, J.M. Palacios, “The Performance in a Fixed Bed Reactor of Copper-based Oxides on Titania as Oxygen Carriers for Chemical Looping Combustion of Methane” Energy and Fuels, Vol. 19, p. 433-441, (2005).
44.H. Tian, K. Chaudhari, T. Simonyi, J. Poston, T. Liu, T. Sanders, G. Veser, R. Siriwardane, “Chemical-Looping Combustion of Coal-derived Synthesis Gas over Copper Oxide Oxygen Carriers” Energy and Fuels, Vol. 22, pp. 3744-3755, (2008).
45.J.A. Pena, E. Lorente, E. Romero, J. Herguido, “Kinetic Study of the Redox Process for Storing Hydorgen Reduction Stage” Catalysis Today, Vol. 116, pp. 439-444, (2006).
46.A. Pineau, N. Kanari, I. Gaballah, “Kinetics of Reduction of Iron Oxides by H2 Part I: Low Temperature Reduction of Hematite” Thermochimica Acta, Vol. 447, pp. 89-100, (2006).
47.A. Pineau, N. Kanari, I. Gaballah, “Kinetics of Reduction of Iron Oxides by H2 Part II. Low Temperature Reduction of Magnetite” Thermochimica Acta, Vol. 456, pp. 75-88, (2007).
48.E. Romero, R. Soto, P. Duran, J. Herguido, J.A. Pena, “Molybdenum Addition to Modified Iron Oxides for Improving Hydorgen Separation in Fixed Bed by Redox Processes” International Journal of Hydorgen Energy, Vol. 37, pp. 6978-6984, (2012).
49.S. Chen, W.G. Xiang, Z.P. Xue, X.Y Sun, “Experimental Investigation of Chemical Looping Hydorgen Generation using Iron Oxides in a Batch Fluidized Bed” Proceedings of the Combustion Institute, Vol. 33, pp. 2691-2699, (2011).
50.M. Shimokawabe, R. Furuichi, T. Ishii, “Influence of the Preparation History of α-Fe2O3 on its Reactivity for Hydorgen Reduction” Thermachimica Acta, Vol. 28, pp. 287-305, (1979).
51.D. Wagner, O. Devisme, F. Patisson, D. Ablitzer, “A Laboratory Study of the Reduction of Iron Oxides by Hydorgen” Sohn International Symposium, Proceedings, Vol. 2, pp. 111-120, (2006).
52.M. Et-Tabirou, B. Duprie, C. Gleitzer, “Hematite Single Crystal Reduction into Magnetite with CO-CO2” Metallurgical Transactions B, Vol. 19B, pp. 311-317, (1988).
53.C.D. Bohn, J.P. Cleeton, C.R. Muller, J.F. Davidson and A. N. Hayhurst, S.A. Scott, J.S. Dennis, “The Kinetics of the Reduction of Iron Oxide by Carbon Monoxide Mixed with Carbon Dioxide” AIChE Journal, Vol. 56, pp. 1016-1029, (2009).
54.J.P.E. Cleeton, C.D. Bohn, C.R. Muller, J.S. Dennis, S.A. Scott, “Clean Hydorgen Production and Electricity from Coal via Chemical Looping：Identifying a Suitable Operating Regime” International Journal of Hydorgen Energy, Vol. 34, pp. 1-12, (2009).
55.K.S. Go, S.R. Son, S.D. Kim, “Reaction Kinetics of Reduction and Oxidation of Metal Oxides for Hydorgen Production” International Journal of Hydorgen Energy, 33, pp. 5986-5995, (2008).
56.K.S. Go, S.R. Son, S.D. Kim, K.S. Kang, C.S. Park, “Hydorgen Production from Two-step Steam Methane Reforming in a Fluidized Bed Reactor” International Journal of Hydorgen Energy, Vol. 34, pp. 1301-1309, (2009).
57.V. Galvita, T. Hempel, H. Lorenz, L.K. Rihko-Struckmann, K. Sundmacher, “Deactivation of Modified Iron Oxide Materials in the Cyclic Water Gas Shift Process for CO-Free Hydorgen Production” Industrial and Engineering Chemistry Research, Vol. 47, pp. 303-310, (2008).
58.M. Ishida, K. Takeshita, K. Suzuki, T. Ohba, “Application of Fe2O3-Al2O3 Composite Particles as Solid Looping Material of the Chemical-Loop Combustor” Energy and Fuels, Vol. 19, pp. 2514-2518, (2005).
59.A.M. Kierzkowska, C.D. Bohn, S.A. Scott, J.P. Cleeton, J.S. Dennis, C.R. Muller, “Development of Iron Oxide Carriers for Chemical Looping Combustion Using Sol-Gel” Industrial and Engineering Chemistry Research, Vol 49, pp. 5383–5391, (2010).
60.A. Abad, T. Mattisson, A. Lyngfelt, M. Johansson, “The Use of Iron Oxide as Oxygen Carrier in a Chemical-Looping Reactor” Fuel, Vol. 86, pp. 1021-1035, (2007).
61.P.H. Bolt, F.H.P.M. Habraken, J.W. Geus, “Formation of Nickel, Cobalt, Copper, and Iron Aluminates from α- and γ-Alumina-Supported Oxides: A Comparative Study” Journal of Solid State Chemistry, Vol. 135, pp. 59-69, (1998).
62.M. Johansson, T. Mattisson, and A. Lyngfelt, “Investigation of Fe2O3 with MgAl2O4 for Chemical-Looping Combustion” Industrial and Engineering Chemistry Research, Vol. 43, pp. 6978-6987, (2004).
63.H. Leion, T. Mattisson, and A. Lyngfelt, “The Use of Petroleum Coke as Fuel in Chemical-Looping Combustion” Fuel, Vol. 86, pp. 1947-1958, (2007).
64.B.M. Corbella, J.M. Palacios, “Titania-supported Iron Oxide as Oxygen Carrier for Chemical-Looping Combustion of Methane” Fuel, Vol. 86, pp. 113-122, (2007).
65.劉祐誠，「以合成器為燃料評估Fe2TiO5載氧體在化學迴圈程序的應用」，碩士論文，國立台灣科技大學(2011)。
66.Q. Zafar, T. Mattisson, B. Gevert, “Integrated Hydorgen and Power Production with CO2 Capture using Chemical-Looping Reforming-Redox Reactivity of Particles of CuO, Mn2O3, NiO, and Fe2O3 using SiO2 as a Support,” Industrial and Engineering Chemistry Research, Vol. 44, pp. 3485-3496, (2005).
67.P.R. Westmoreland, D.P. Harrison, “Evaluation of Candidate Solids for High-Temperature Desulfurization of Low-Btu Gases” Environmental Science Technology, Vol. 10, pp. 659-661, (1976).
68.K. Otsuka, T. Kaburagi, C. Yamada, S. Takenaka, “Chemical Storage of Hydorgen by Modified Iron Oxides” Journal of Power Sources, Vol. 122, pp. 111-121, (2003).
69.W. de Bruijn, A. van Sandwijk, J. Trouw, R.H. Heerema, Miner. Metall. Process, pp. 43-49, Feb. (1989).
70.R. Chaigneau, R.H. Heerema, “The Influence of Specific Impurities on the Nucleation and Growth of Magnetite during Reduction of Artificially Prepared Hematite” Metallurgical Transactions B, Vol. 22B, pp.503-511, (1991).
71.A.A. El-Geassy, “Stepwise Reduction of CaO and/or to Magnetite Then Subsequently to MgO Doped-Fe2O3 Compacts Iron at 1173-1473K” ISIJ International, Vol. 37, pp. 844-853, (1997).
72.U.F. Chinje, J.H.E. Jeffes, “Effects of Chemical Composition of Iron Oxides on Their Rates of Reduction: Part 1 Effect of Trivalent Metal Oxides on Reduction of Hematite to Lower Iron Oxides” Ironmaking and Steelmaking, Vol. 16, pp. 90-98, (1989).
73.M.H. Khedr, “Isothermal Reduction Kinetics of Fe2O3 Mixed with 1–10% Cr2O3 at 1173-1473K” ISIJ International, Vol. 40, pp. 309-314, (2000).
74.K. Otsuka, C. Yamada, T. Kaburagi, S. Takenaka, “Hydorgen Storage and Production by Redox of Iron Oxide for Polymer Electrolyte Fuel Cell Vehicles” International Journal of Hydorgen Energy, Vol. 28, pp. 335-342, (2003).
75.J.C. Ryu, D.H. Lee, K.S. Kang, C.S. Park, J.W. Kim, Y.H. Kim, “Effect of Additives on Redox Behavior of Iron Oxide for Chemical Hydorgen Storage” Journal of Industrial and Engineering Chemistry, Vol. 14, pp. 252-260, (2008).
76.F. Wen, H. Wang, Z. Tang, “Kinetic Study of the Redox Process of Iron Oxide for Hydorgen Production at Oxidation Step” Thermochimica Acta, Vol. 520, pp. 55-60, (2011).
77.H.M. Gu, L.H. Shen, J. Xiao, S.W. Zhang, T. Song, D.Q. Chen, “Iron Ore as Oxygen Carrier Improved with Potassium for Chemical Looping Combustion of Anthracite Coal” Combustion and Flame, Vol. 159, pp.2480-2490, (2012).
78.K. Otsuka, S. Takenaka, “Storage and Supply of Pure Hydorgen Mediated by the Redox of Iron Oxides” Journal of the Japan Petroleum Institute, Vol. 47, pp. 377-386, (2004).
79.S. Takenaka, T. Kaburagi, C. Yamada, K. Nomura, K. Otsuka, “Storage and Supply of Hydorgen by means of the Redox of the Iron Oxides Modified with Mo and Rh Species” Journal of Catalysis, Vol. 228, pp. 66-74, (2004).
80.K. Urasaki, N. Tanimoto, T. Hayashi, Y. Sekine, E. Kikuchi, M. Matsukata, “Hydorgen Production via Steam–Iron Reaction using Iron Oxide Modified with very small amounts of Palladium and Zirconia” Applied Catalysis A：General, Vol. 288, pp.143-148, (2005).
81.D.H. Lee, K.S. Cha, Y.S. Lee, K.S. Kang, C.S. Park, Y.H. Kim, “Effects of CeO2 Additive on Redox Characteristics of Fe-based Mixed Oxide Mediums for Storage and Production of Hydorgen” International Journal of Hydorgen Energy, Vol. 34, pp. 1417-1422, (2009).
82.S. Takenak, K. Nomura, N. Hanaizumi, K. Otsuka, “Storage and Formation of Pure Hydorgen Mediated by the Redox of Modified Iron Oxides” Applied Catalysis A： General, Vol. 282, pp. 333-341, (2005).
83.S. Takenak, N. Hanaizumi, V.T.D. Son, K. Otsuka, “Production of Pure Hydorgen from Methane Mediated by the Redox of Ni- and Cr-added Iron Oxides” Journal of Catalysis, Vol. 228, pp. 405-416, (2004).
84.H. Wang, X.Q. Feng, X.F. Wang, S.P. Cheng, S.L. Gao, “Hydorgen Production by Redox of Bimetal Cation-modified Iron Oxide” International Journal of Hydorgen Energy, Vol.33, pp. 7122-7128, (2008).
85.X.J. Liu, H. Wang, “Hydorgen Production from Water Decomposition by Redox of Fe2O3 Modified with Single-or Double-metal Additives” Journal of Solid State Chemistry, Vol. 183, pp. 1075-1082, (2010).
86.S. Hu, G. Liu, D. Zhu, C. Chen, S. Liao, “Synthesis, Characterization, and Evaluation of Boron-Doped Iron Oxides for the Photocatalytic Degradation of Atrazine under Visible Light” International Journal of Photoenergy, Vol. 2012, pp. 1-4, (2011).
87.M.H. Khedr, “Isothermal Reduction Kinetics at 900-1100˚C of NiFe2O4 Sintered at 1000-1200˚C” Journal of Analytical and Applied Pyrolysis, Vol. 73, pp. 123-129, (2005).
88.莊家哲，向性一，「Ce0.6Zr0.4O2奈米粉末之相分離行為與氧化還原特性」，中華民國陶業研究學會 會刊，國立成功大學資源工程研究所(2012)。
89.Z. Sun, Q. Zhou, L.S. Fan, “Reactive Solid Surface Morphology Variation via Ionic Diffusion” Langmuir, Vol. 28, pp. 11827-11833, (2012).
90.林保賢，「製備錠狀氧化鐵載氧體擔載Al2O3及TiO2惰性載體，並應用於化學迴圈燃燒與產氫之探討」，碩士論文，國立台灣科技大學(2013)。
91.K. Piotrowski, K. Mondal, H. Lorethova, L. Stonawski, T. Szymański, T. Wiltowski, “Effect of Gas Composition on the Kinetics of Iron Oxide Reduction in a Hydorgen Production Process” International Journal of Hydorgen Energy, Vol. 30, pp. 1543-1554, (2005).