CeO2/RP-PSCFM@CoFe阳极材料用于质子导体乙烷燃料电池共生乙烯和电能

doi:10.3866/PKU.WHXB202009107

物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2009107.doi: 10.3866/PKU.WHXB202009107

所属专题：电催化

CeO₂/RP-PSCFM@CoFe阳极材料用于质子导体乙烷燃料电池共生乙烯和电能

樊赟¹, 陈国诞¹, 奚修安¹, 李俊¹, 王琦², 骆静利¹, 符显珠¹^,*()

¹ 深圳大学材料学院，广东深圳 518060
² 中国地质大学材料科学与技术学院，北京 100083

收稿日期:2020-09-30 录用日期:2020-10-30 发布日期:2020-11-05
通讯作者: 符显珠 E-mail:xz.fu@szu.edu.cn
作者简介:第一联系人：
^†These authors contributed equally to this work and should be considered co-first authors.
基金资助:
国家自然科学基金项目(21975163)

Co-Generation of Ethylene and Electricity from Ethane by CeO₂/RP-PSCFM@CoFe Anode Materials in Proton Conductive Fuel Cells

Yun Fan¹, Guodan Chen¹, Xiuan Xi¹, Jun Li¹, Qi Wang², Jingli Luo¹, Xianzhu Fu¹^,*()

¹ College of Material Science and Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, China
² School of Materials Science and Technology, China University of Geosciences, Beijing 100083, China

Received:2020-09-30 Accepted:2020-10-30 Published:2020-11-05
Contact: Xianzhu Fu E-mail:xz.fu@szu.edu.cn
About author:Xianzhu Fu, Email: xz.fu@szu.edu.cn; Tel.: +86-755-86392151
Supported by:
the National Natural Science Foundation of China(21975163)

摘要/Abstract

摘要：

固体氧化物燃料电池钙钛矿阳极材料可以通过改性获得优异的催化活性，低的极化阻抗和稳定的抗积炭能力。在此，以立方相钙钛矿Pr_0.4Sr_0.6Co_0.2Fe_0.7Mo_0.1O_3−δ作为阳极前驱体，然后将CeO₂成功地浸渍到阳极的多孔结构中。通过原位还原技术获得了纳米合金粒子负载钙钛矿基底的复合阳极用于质子导体乙烷固体氧化物燃料电池。在氢气和乙烷气氛中，750 ℃时，燃料电池峰值功率密度分别达到253和183 mW∙cm⁻²。而且，在十小时的测试中燃料电池性能没有衰减反而电流密度随着时间的延长而增加，表明CeO₂浸渍表现出优异的催化活性和抗积炭稳定性。同时，通过产物分析，乙烯的产率从650 ℃下的23.52%增加到750 ℃下的34.09%，并且乙烯选择性超过94%。因此改性的阳极通过析出的纳米颗粒与CeO₂的协同作用，促进了燃料电池电极的催化活性和稳定性，将其运用到质子导体固体氧化物乙烷燃料电池中成功实现了乙烯与电能的共生。

关键词: 复合阳极, 浸渍, 乙烷, 共生燃料电池, 抗积炭

Abstract:

The continuous consumption and excessive use of fossil fuels promote the exploration of new energy conversion technologies. Meanwhile, the increase in the supply of ethane encourages the development of industrial technology for the production of ethylene chemical raw materials. Compared with traditional fossil fuel energy conversion equipment, solid oxide ethane cogeneration fuel cells are an efficient energy processing device. Through selective oxidation of fuel gas on the anode, the endothermic process of ethane dehydrogenation is converted into an exothermic oxidation reaction, which has a greater driving force for reaction thermodynamics, and simultaneously produces clean electricity and value-added chemicals without CO₂ emissions. The anode material used for the proton conductor ethane fuel cells needs to operate stably and efficiently under hydrocarbon fuel. Consequently, excellent catalytic activity, low polarization resistance, and anti-coking stability are essential. In this work, CeO₂ was uniformly impregnated into the surface of the porous cubic perovskite Pr_0.4Sr_0.6Co_0.2Fe_0.7Mo_0.1O_3−δ anode by wet impregnation, and then calcined and reduced to obtain a CeO₂/RP-PSCFM@CoFe composite anode embedded with nanoparticles, which was successfully used in electrolyte-supported proton conductor fuel cells. CeO₂ has a high ionic conductivity and transport capacity, which accelerates the transfer rate of protons on the anode and improves the catalytic reaction and transport process. Moreover, uniformly dispersed CeO₂ can effectively increase the three-phase interface of the anode reaction and increase the range of reaction activity. The peak power densities before and after wet impregnation reached 172 and 253 mW·cm⁻², respectively, at 750 ℃. When switching to ethane as the fuel, the peak power densities reached 136 and 183 mW·cm⁻², respectively. The polarization resistance of the impregnated single cell was significantly reduced, and the catalytic activity improved. Moreover, there was no attenuation for 10 h in the long-term test. Inversely, the current density increased with the continuous reduction of the composite anode. Product analysis revealed that the yield of ethylene increased from 23.52% at 650 ℃ to 34.09% at 750 ℃, and the ethylene selectivity exceeded 94%. These results clearly show that the impregnated anode exhibited excellent catalytic activity and anti-coking ability in hydrocarbon fuels at high temperatures. Combining CoFe nanoparticles with CeO₂ enhanced the electronic conductance and ionic conductance of the electrode, improved the transmission of electric energy and the efficient conversion of chemicals, thus successfully producing the cogeneration of electric energy and ethylene.

Key words: Composite anode, Impregnation, Ethane, Cogeneration fuel cells, Anti-coking

樊赟, 陈国诞, 奚修安, 李俊, 王琦, 骆静利, 符显珠. CeO₂/RP-PSCFM@CoFe阳极材料用于质子导体乙烷燃料电池共生乙烯和电能[J]. 物理化学学报, 2021, 37(7), 2009107. doi: 10.3866/PKU.WHXB202009107

Yun Fan, Guodan Chen, Xiuan Xi, Jun Li, Qi Wang, Jingli Luo, Xianzhu Fu. Co-Generation of Ethylene and Electricity from Ethane by CeO₂/RP-PSCFM@CoFe Anode Materials in Proton Conductive Fuel Cells[J]. Acta Phys. -Chim. Sin. 2021, 37(7), 2009107. doi: 10.3866/PKU.WHXB202009107

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202009107

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I7/2009107

图/表 10

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Fig 10

参考文献 39

1	Atkinson A. ; Barnett S. ; Gorte R. J. ; Irvine J. T. ; McEvoy A. J. ; Mogensen M. ; Singhal S. C. ; Vohs J. Nat. Mater. 2004, 3, 17. doi: 10.1038/nmat1040
2	Sun W. ; Shi Z. ; Liu M. ; Bi L. ; Liu W. Adv. Funct. Mater. 2014, 24, 5695. doi: 10.1002/adfm.201401478
3	Sengodan S. ; Choi S. ; Jun A. ; Shin T. H. ; Ju Y. W. ; Jeong H. Y. ; Shin J. ; Irvine J. T. ; Kim G. Nat. Mater. 2015, 14, 205. doi: 10.1038/nmat4166
4	Fu X. Z. ; Luo J. L. ; Sanger A. R. ; Luo N. ; Chuang K. T. J. Power Sources 2010, 195, 2659. doi: 10.1016/j.jpowsour.2009.10.069
5	Wang S. Y. ; Luo J. L. ; Sanger A. R. ; Chuang K. T. J. Phys. Chem. C 2007, 111, 5069. doi: 10.1021/jp066690w
6	Fan Y. ; Wang Q. ; Li J. ; Luo J. L. ; Fu X. Z. J. Electrochem 2020, 26, 243.
	樊赟; 王琦; 李俊; 骆静利; 符显珠. 电化学, 2020, 26, 243. doi: 10.13208/j.electrochem.191145
7	Wang W. ; Xu M. G. ; Xu X. M. ; Zhou W. ; Shao Z. P. Angew. Chem. Int. Ed. 2020, 59, 136. doi: 10.1002/anie.201900292
8	Li Y. F. ; Zhang W. Q. ; Zheng Y. ; Chen J. ; Yu B. ; Chen Y. ; Liu M. L. Chem. Soc. Rev. 2017, 46, 6345. doi: 10.1039/c7cs00120g
9	Xie C. ; Yan D. F. ; Chen W. ; Zou Y. Q. ; Chen R. ; Zang S. Q. ; Wang Y. Y. ; Yao X. D. ; Wang S. Y. Mater. Today 2019, 31, 47. doi: 10.1016/j.mattod.2019.05.021
10	Jarrige I. ; Ishii K. ; Matsumura D. ; Nishihata Y. ; Yoshida M. ; Kishi H. ; Taniguchi M. ; Uenishi M. ; Tanaka H. ; Kasai H. ; et al ACS Catal. 2015, 5, 1112. doi: 10.1021/cs501608k
11	Zhang J. ; Gao M. R. ; Luo J. L. Chem. Mater. 2020, 32, 5424. doi: 10.1021/acs.chemmater.0c00721
12	Zhang X. R. ; Ye L. T. ; Li H. ; Chen F. L. ; Xie K. ACS Catal. 2020, 10, 3505. doi: 10.1021/acscaatal.9b05409
13	Sun Y. F. ; Zhang Y. Q. ; Chen J. ; Li J. H. ; Zhu Y. T. ; Zeng Y. M. ; Amirkhiz B. S. ; Li J. ; Hua B. ; Luo J. L. Nano Lett 2016, 16, 5303. doi: 10.1021/acs.nanolett.6b02757
14	Neagu, D.; Tsekouras, G.; Miller, D. N.; Menard, H.; Irvine, J. T. Nat. Chem. 2013, 5. doi: 10.1038/nchem.1773
15	Liu S. ; Liu Q. ; Fu X. Z. ; Luo J. L. Appl. Catal. B: Environ. 2018, 220, 283. doi: 10.1016/j.apcatb.2017.08.051
16	Lv H. F. ; Lin L. ; Zhang X. M. ; Song Y. F. ; Matsumoto H. ; Zeng C. B. ; Ta N. ; Liu W. ; Gao D. F. ; Wang G. X. ; et al Adv. Mater. 2019, 32, 2063. doi: 10.1002/adma.201906193
17	Shi N. ; Xue S. ; Xie Y. ; Yang Y. ; Huan D. ; Pan Y. ; Peng R. ; Xia C. ; Zhan Z. ; Lu Y. Appl. Catal. B: Environ 2020, 272, 118973. doi: 10.1016/j.apcatb.2020.118973
18	Hua B. ; Yan N. ; Li M. ; Sun Y. F. ; Zhang Y. Q. ; Li J. ; Etsell T. ; Sarkar P. ; Luo J. L. Adv. Mater 2016, 28, 8922. doi: 10.1002/adma.201602103
19	Xi X. ; Cao Z. -S. ; Shen X. Q. ; Lu Y. ; Li J. ; Luo J. L. ; Fu X. Z. J. Power Sources 2020, 459, 228071. doi: 10.1016/j.jpowsour.2020.228071
20	Liu S. ; Chuang K. T. ; Luo J. L. ACS Catal. 2015, 6, 760. doi: 10.1021/acscatal.5b02296
21	Lv X. ; Chen H. ; Zhou W. ; Cheng F. ; Li S. D. ; Shao Z. Renewable Energy 2020, 150, 334. doi: 10.1016/j.renene.2019.12.126
22	Ding S. ; Li M. ; Pang W. ; Hua B. ; Duan N. ; Zhang Y. -Q. ; Zhang S. -N. ; Jin Z. ; Luo J. L. Electrochim. Acta 2020, 335, 135683. doi: 10.1016/j.electacta.2020.135683
23	Bian L. ; Duan C. ; Wang L. ; O'Hayre R. ; Cheng J. ; Chou K. C. J. Mater. Chem. A. 2017, 5, 15253. doi: 10.1039/c7ta03001k
24	Fu X. Z. ; Luo X. X. ; Luo J. L. ; Chuang K. T. ; Sanger A. R. ; Krzywicki A. J. Power Sources 2011, 196, 1036. doi: 10.1016/j.jpowsour.2010.08.043
25	McIntosh S. ; Gorte R. J. Chem. Rev. 2004, 104, 4845. doi: 10.1021/cr020725g
26	Silva A. A. A. ; Bion N. ; Epron F. ; Baraka S. ; Fonseca F. C. ; Rabelo N. R. C. ; Mattos L. V. ; Noronha F. B. Appl. Catal. B: Environ 2017, 206, 626. doi: 10.1016/j.apcatb.2017.01.069
27	Liu Z. ; Liu B. ; Ding D. ; Liu M. ; Chen F. ; Xia C. J. Power Sources 2013, 237, 243. doi: 10.1016/j.jpowsour.2013.03.025
28	Lei Z. ; Zhu Q. S. ; Han M. F. Acta Phys. -Chim. Sin 2010, 26, 583.
	雷泽; 朱庆山; 韩敏芳. 物理化学学报, 2010, 26, 583. doi: 10.3866/PKU.WHXB20100323
29	Mackenzie J. D. ; Bescher E. P. Acc. Chem. Res 2007, 40, 810. doi: 10.1021/ar7000149
30	Zuo C. ; Zha S. ; Liu M. ; Hatano M. ; Uchiyama M. Adv. Mater. 2006, 18, 3318. doi: 10.1002/adma.200601366
31	Zhang L. ; Yang C. ; Frenkel A. I. ; Wang S. ; Xiao G. ; Brinkman K. ; Chen F. J. Power Sources. 2014, 262, 421. doi: 10.1016/j.jpowsour.2014.04.009
32	Yang C. ; Li J. ; Lin Y. ; Liu J. ; Chen F. ; Liu M. Nano Energy 2015, 11, 704. doi: 10.1016/j.nanoen.2014.12.001
33	Wang Z. ; Tian Y. ; Li Y. J. Power Sources 2011, 196, 6104. doi: 10.1016/j.jpowsour.2011.03.053
34	Song Y. ; Zhong Q. ; Tan W. ; Pan C. Electrochim. Acta 2014, 139, 13. doi: 10.1016/j.electacta.2014.07.022
35	Chen D. ; Chen C. ; Dong F. ; Shao Z. ; Ciucci F. J. Power Sources 2014, 250, 188. doi: 10.1016/j.jpowsour.2013.11.010
36	Pan X. ; Wang Z. ; He B. ; Wang S. ; Wu X. ; Xia C. Int. J. Hydrog. Energy 2013, 38, 4108. doi: 10.1016/j.ijhydene.2013.01.121
37	Osinkin D. A. ; Bogdanovich N. M. ; Gavrilyuk A. L. Electrochim. Acta 2016, 199, 108. doi: 10.1016/j.electacta.2016.03.133
38	Liu S. ; Behnamian Y. ; Chuang K. T. ; Liu Q. ; Luo J. L. J. Power Sources 2015, 298, 23. doi: 10.1016/j.jpowsour.2015.08.032
39	Fu X. Z. ; Lin J. Y. ; Xu S. ; Luo J. L. ; Chuang K. T. ; Sanger A. R. ; Krzywicki A. Phys. Chem. Chem. Phys. 2011, 13, 19615. doi: 10.1039/c1cp22837d

[1]	徐新宇, 陆迦勒, 苏波, 陈佳义, 陈雄, 汪思波. 调控电荷动力学与表面反应性用于Au/Ti-CeO₂光催化甲烷选择性氧化制乙烷[J]. 物理化学学报, 2025, 41(11): 100153 - .
[2]	丁心湄, 梁艳丽, 张海龙, 赵明, 王健礼, 陈耀强. 高分散还原态Pt基催化剂的制备及其NO氧化的催化性能[J]. 物理化学学报, 2022, 38(4): 2005009 - .
[3]	王粉粉, 王芃, 牛洪瑶, 余莹凤, 孙平川. 固体NMR研究PAA/PEO共混物中氢键相互作用与结构演化[J]. 物理化学学报, 2020, 36(4): 1912016 - .
[4]	胡益浩,宋通洋,王月娟,胡庚申,谢冠群,罗孟飞. Zn/SiO₂气相催化裂解1，1，2-三氯乙烷脱HCl：酸性与失活[J]. 物理化学学报, 2017, 33(5): 1017 -1026 .
[5]	谢永敏,王晓强,刘江,余长林. 管式电解质支撑型直接碳固体氧化物燃料电池的浸渍法制备及电性能[J]. 物理化学学报, 2017, 33(2): 386 -392 .
[6]	仇松柏,翁育靖,刘琪英,马隆龙,张琦,王铁军. 乙二醇促进制备高分散的Co/SiO₂催化剂及其催化乳酸乙酯转化为1,2-丙二醇的气相加氢活性[J]. 物理化学学报, 2016, 32(6): 1511 -1518 .
[7]	靳燕霞,汤岑,孟秀清,王小霞,谢冠群,罗孟飞,李小年. 气相法合成偏二氯乙烯的高稳定CsNO₃/SiO₂催化剂[J]. 物理化学学报, 2016, 32(2): 510 -518 .
[8]	刘治华, 余长春, 杨盼, 李然家, 周红军, 徐春明. 钍对浸渍型和蛋壳型钴基催化剂Co/SiO₂费托合成性能的影响[J]. 物理化学学报, 2015, 31(Suppl): 90 -94 .
[9]	夏龙飞, 江治, 上官文峰, 顾顺超, 平野真一. 二氧化钛负载的镍氧化态对乙腈气相加氢的影响[J]. 物理化学学报, 2015, 31(5): 941 -947 .
[10]	张远航, 王志远, 师春生, 刘恩佐, 何春年, 赵乃勤. 均匀负载氧化镍纳米颗粒多孔硬碳球的制备及其高性能锂离子电池负极材料应用[J]. 物理化学学报, 2015, 31(2): 268 -276 .
[11]	马娟,宋凤丹,周泽齐,齐随涛,伊春海,杨伯伦. 一维有序ZnO纳米棒阵列的制备和优化[J]. 物理化学学报, 2015, 31(11): 2213 -2219 .
[12]	李建梅, 刘坚, 任立伟, 刘清龙, 赵震, 韦岳长, 段爱军, 姜桂元. 钾调变Mo/SBA-15催化剂用于乙烷选择氧化制乙醛[J]. 物理化学学报, 2014, 30(9): 1736 -1744 .
[13]	任成军, 周丽娜, 尚鸿燕, 陈耀强. 浸渍法制备的Pd-MnO_x/γ-Al₂O₃催化剂及不同载体对地表O₃降解的影响[J]. 物理化学学报, 2014, 30(5): 957 -964 .
[14]	孙敬方, 葛成艳, 姚小江, 曹原, 张雷, 汤常金, 董林. 固相浸渍法制备NiO/CeO₂催化剂及其在CO氧化反应中的应用[J]. 物理化学学报, 2013, 29(11): 2451 -2458 .
[15]	孟秀霞, 宫勋, 杨乃涛, 谭小耀, 马紫峰. 梯度Cu-CeO₂-Ni-YSZ复合阳极直接甲烷SOFC的制备与性能[J]. 物理化学学报, 2013, 29(08): 1719 -1726 .

CeO₂/RP-PSCFM@CoFe阳极材料用于质子导体乙烷燃料电池共生乙烯和电能

Co-Generation of Ethylene and Electricity from Ethane by CeO₂/RP-PSCFM@CoFe Anode Materials in Proton Conductive Fuel Cells

RichHTML

PDF

赞