Selective Reduction of Carbon Dioxide into Amorphous Carbon over Activated Natural Magnetite

Zhong-qing Liu; Jian Zheng; Yi Wang; Xu Liu

doi:10.1007/s12613-020-2034-z

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Selective Reduction of Carbon Dioxide into Amorphous Carbon over Activated Natural Magnetite

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Available online: 10 March 2020

Abstract

Natural magnetite formed by isomorphism substitutions of Fe, Ti, Co, etc. was activated by mechanical grind followed by H₂ reduction. Temperature-programmed reduction of hydrogen (H₂-TPR) and temperature-programmed surface reaction of carbon dioxide (CO₂-TPSR) were carried out to investigate the processes of oxygen loss and CO₂ reduction. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and so on. It was found that the stability of spinel phases and oxygen-deficient degree were obviously increased after natural magnetite was mechanically milled and reduced in H₂ atmosphere. Meanwhile, the activity and selectivity of CO₂ reduction into carbon were enhanced. The deposited carbon on activated natural magnetite was confirmed as amorphous. The amounts of carbon after CO₂ reduction at 300℃ for 90 min over the activated natural magnetite attained to 2.87wt% relative to natural magnetite.
- CO₂ reduction;
- natural magnetite;
- isomorphism substitutions;
- grind activation;
- oxygen-deficient degree;
- amorphous carbon

Acknowledgements

This work was supported by National key research and development program of China (Grant No. 2016YFB0600904). The authors gratefully acknowledge the support of the Analytical and Test Center of Sichuan University.

References

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Selective Reduction of Carbon Dioxide into Amorphous Carbon over Activated Natural Magnetite

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Zhong-qing Liu E-mail: lzq_301@126.com, liuzq_hgxy@scu.edu.cn

School of Chemical Engineering, Sichuan University, Chengdu 610065, China

Available online: 10 March 2020

Abstract: Natural magnetite formed by isomorphism substitutions of Fe, Ti, Co, etc. was activated by mechanical grind followed by H₂ reduction. Temperature-programmed reduction of hydrogen (H₂-TPR) and temperature-programmed surface reaction of carbon dioxide (CO₂-TPSR) were carried out to investigate the processes of oxygen loss and CO₂ reduction. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and so on. It was found that the stability of spinel phases and oxygen-deficient degree were obviously increased after natural magnetite was mechanically milled and reduced in H₂ atmosphere. Meanwhile, the activity and selectivity of CO₂ reduction into carbon were enhanced. The deposited carbon on activated natural magnetite was confirmed as amorphous. The amounts of carbon after CO₂ reduction at 300℃ for 90 min over the activated natural magnetite attained to 2.87wt% relative to natural magnetite.

Acknowledgements This work was supported by National key research and development program of China (Grant No. 2016YFB0600904). The authors gratefully acknowledge the support of the Analytical and Test Center of Sichuan University.

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Reference (39)

[1]	A. Chen and B. Lin, A Simple Framework for Quantifying Electrochemical CO₂ Fixation, Joule, 2(2018), No. 4, p. 594.
[2]	A.S. Agarwal, D.Y. Zhai, D.D. Hill, and D.N. Sridhar, The Electrochemical Reduction of Carbon Dioxide to Formate/Formic Acid:Engineering and Economic Feasibility, ChemSusChem, 4(2011), No. 12, p. 1705.
[3]	D. Gao, R.M. Arán-Ais, H.S. Jeon, and B. Roldan Cuenya, Rational catalyst and electrolyte design for CO₂ electroreduction towards multicarbon products, Nat Catal, 2(2019), No. 3, p. 198.
[4]	X. Tan, H.A. Tahini, H. Arandiyan, and S.C. Smith, Electrocatalytic Reduction of Carbon Dioxide to Methane on Single Transition Metal Atoms Supported on a Defective Boron Nitride Monolayer:First Principle Study, Adv. Theory Simul., 2(2019), No. 3.
[5]	P. Chen, B. Cui, Y.M. Bu, Z.F. Yang, and Y.Y. Wang, Synthesis and characterization of mesoporous and hollow-mesoporous M_xFe_3-xO₄ (M=Mg, Mn, Fe, Co, Ni, Cu, Zn) microspheres for microwave-triggered controllable drug delivery, J. Nanopart. Res., 19(2017), No. 12, p. 398.
[6]	H.P. He, Y.H. Zhong, X.L. Liang, W. Tan, J.X. Zhu, and C.Y. Wang, Natural Magnetite:an efficient catalyst for the degradation of organic contaminant, Sci Rep-UK, 5(2015), No. 3, p. 10139.
[7]	M. Munoz, Z.M. de Pedro, J.A. Casas, and J.J. Rodriguez, Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation-A review, Appl. Catal. B-Environ., 176-177(2015), p. 249.
[8]	M.S. Fu, L.S. Chen, and S.Y. Chen, Preparation, structure of doped ferrite and its performance of decomposition of carbon dioxide to carbon, Chem. J. Chinese. U., 26(2005), No. 12, p. 2279.
[9]	L.J. Ma, L.S. Chen, and S.Y. Chen, Study of the CO₂decomposition over doped Ni-ferrites, J. Phys. Chem. Solids., 68(2007), No. 7, p. 1330.
[10]	L.J. Ma, L.S. Chen, and S.Y. Chen, Study on the cycle decomposition of CO₂ over NiCr_0.08Fe_1.92O₄ and the microstructure of products, Mater. Chem. Phys., 105(2007), No. 1, p. 122.
[11]	L.J. Ma, L.S. Chen, and S.Y. Chen, Studies on redox H₂-CO₂ cycle on CoCr_xFe_2-xO₄, Solid. State. Sci., 11(2009), No. 1, p. 176.
[12]	L.J. Ma, L.S. Chen, and S.Y. Chen, Study on the characteristics and activity of Ni-Cu-Zn ferrite for decomposition of CO₂, Mater. Chem. Phys., 114(2009), No. 2-3, p. 692.
[13]	Y. Tamaura and M. Tabata, Complete Reduction of Carbon-Dioxide to Carbon Using Cation-Excess Magnetite, Nature, 346(1990), No. 6281, p. 255.
[14]	C.L. Zhang, T.H. Wu, H.M. Yang, Y.Z. Jiang, and S.Y. Peng, Reduction of Carbon-Dioxide to Carbon with Active Cation Excess Magnetite, Chem. J. Chinese. U., 16(1995), No. 6, p. 955.
[15]	H.M. Yang, C.L. Zhang, T.H. Wu, Y.Z. Jiang, and S.Y. Peng, Preparation of Fe_3+δO₄ and their complete decomposition of CO₂ to carbon, Acta. Chim. Sinica., 53(1995), No. 11, p. 1101.
[16]	S. Álvarez-Torrellas, M. Munoz, V. Mondejar, Z.M. de Pedro, and J.A. Casas, Boosting the catalytic activity of natural magnetite for wet peroxide oxidation, Environ Sci Pollut Res, (2018), No. p. 1.
[17]	E. Yamasue, H. Yamaguchi, H. Nakaoku, H. Okumura, and K.N. Ishihara, Carbon dioxide reduction into carbon by mechanically milled wustite, J. Mater. Sci., 42(2007), No. 13, p. 5196.
[18]	E. Yamasue, H. Yamaguchi, H. Okumura, and K.N. Ishihara, Decomposition of carbon dioxide using mechanically-milled magnetite, J. Alloys. Compd., 434(2007), No. p. 803.
[19]	J.S. Kim and J.R. Ahn, Characterization of wet processed (Ni, Zn)-ferrites for CO₂ decomposition, J. Mater. Sci., 36(2001), No. 19, p. 4813.
[20]	J.S. Kim, J.R. Ahn, C.W. Lee, Y. Murakami, and D. Shindo, Morphological properties of ultra-fine (Ni, Zn)-ferrites and their ability to decompose CO₂, J. Mater. Sci., 11(2001), No. 12, p. 3373.
[21]	C. Nordhei, K. Mathisen, I. Bezverkhyy, and D. Nicholson, Decomposition of carbon dioxide over the putative cubic spinel nanophase cobalt, nickel, and zinc ferrites, J. Phys. Chem-C., 112(2008), No. 16, p. 6531.
[22]	C. Nordhei, K. Mathisen, O. Safonova, W. van Beek, and D.G. Nicholson, Decomposition of Carbon Dioxide at 500℃ over Reduced Iron, Cobalt, Nickel, and Zinc Ferrites:A Combined XANES-XRD Study, J. Phys. Chem-C., 113(2009), No. 45, p. 19568.
[23]	L.S. Chen, S.Y. Chen, and G.L. Lu, Study the structure stability of NiFe_2-xCr_xO₄ (x=0, 0.08) during H₂/CO₂ cycle reaction, J. Mater. Sci., 41(2006), No. 19, p. 6465.
[24]	M.H. Khedr and A.A. Farghali, Microstructure, kinetics and mechanisms of CO₂ catalytic decomposition over freshly reduced nano-crystallite CuFe₂O₄ at 400-600℃, Appl. Catal. B-Environ, 61(2005), No. 3-4, p. 219.
[25]	M.H. Khedr, A.A. Omar, and S.A. Abdel-Moaty, Reduction of carbon dioxide into carbon by freshly reduced CoFe₂O₄ nanoparticles, Mat. Sci. Eng. a-Struct., 432(2006), No. 1-2, p. 26.
[26]	T. Kodama, Y. Kitayama, M. Tsuji, and Y. Tamaura, Methanation of CO₂ using ultrafine Ni_xFe_3-xO₄, Energy, 22(1997), No. 2-3, p. 183.
[27]	D.G. Streets, K.J. Jiang, X.L. Hu, J.E. Sinton, X.Q. Zhang, D.Y. Xu, M.Z. Jacobson, and J. E. Hansen, Climate change-Recent reductions in China's greenhouse gas emissions, Science, 294(2001), No. 5548, p. 1835.
[28]	J. Tollefson, Panel negotiates climate ‘synthesis report’, Nature, 450(2007), No. 7168, p. 327.
[29]	M. Tsuji, T. Yamamoto, Y. Tamaura, T. Kodama, and Y. Kitayama, Catalytic acceleration for CO₂ decomposition into carbon by Rh, Pt or Ce impregnation onto Ni(II)-bearing ferrite, Appl. Catal. a-Gen., 142(1996), No. 1, p. 31.
[30]	G.C. Shin, S.C. Choi, K.D. Jung, and S.H. Han, Mechanism of M ferrites (M=Cu and Ni) in the CO₂ decomposition reaction, Chem. Mater., 13(2001), No. 4, p. 1238.
[31]	C.L. Zhang, S. Li, T.H. Wu, and S.Y. Peng, Reduction of carbon dioxide into carbon by the active wustite and the mechanism of the reaction, Mater. Chem. Phys., 58(1999), No. 2, p. 139.
[32]	C.L. Zhang, S. Li, L.J. Wang, T.H. Wu, and S.Y. Peng, Studies on the decomposition of carbon dioxide into carbon with oxygen-deficient magnetite I. Preparation, characterization of magnetite, and its activity of decomposing carbon dioxide, Mater. Chem. Phys., 62(2000), No. 1, p. 44.
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Selective Reduction of Carbon Dioxide into Amorphous Carbon over Activated Natural Magnetite

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