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First principles study on methane reforming over Ni/TiO2(110) surface in solid oxide fuel cells under dry and wet atmospheres

Ni/TiO2(110) 表面甲烷重整反应生成CO和H2反应机理的第一性原理研究

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Abstract

Understanding the carbon-tolerant mechanisms from a microscopic view is of special importance to develop proper anodes for solid oxide fuel cells. In this work, we employed density-functional theory calculations to study the CH4 reaction mechanism over a Ni/TiO2 nanostructure, which experimentally demonstrated good carbon tolerance. Six potential pathways for methane reforming reactions were studied over the Ni/TiO2(110) surface under both dry and wet atmospheres, and the main concerns were focused on the impact of TiO2 and Ni/TiO2 interface on CO/H2 formation. Our calculations suggest that the reaction between carbon and the interfacial lattice oxygen to form CO* is the dominant pathway for CH4 reforming under both dry and wet atmospheres, and intervention of steam directly to oxidize C* with its dissociated OH* group is less favorable in energy than that to wipe off oxygen vacancy to get ready for next C* oxidation. In all investigated paths, desorption of CO* is one of the most difficult steps. Fortunately, CO* desorption can be greatly promoted by the large heat released from the previous CO* formation process under wet atmosphere. H2O adsorption and dissociation over the TiO2 surface are found to be much easier than those over Ni, yttria stabilized zirconia (YSZ) and CeO2, which should be the key reason for the greatly depressed carbon deposition over Ni-TiO2 particles than traditional YSZ-Ni and CeO2-Ni anode. Our study presents the detailed CO* formation mechanism in CH4 reforming process over the Ni/TiO2 surface, which will benefit future research for exploring new carbon-tolerant solid oxide fuel cell anodes.

摘要

基于密度泛函理论(DFT)计算, 本文研究了Ni/TiO2(110)表面甲烷重整反应的机理, 揭示了固体氧化物燃料电池中TiO2基阳极较传统ZrO2或者CeO2基阳极材料具有良好抗积碳性能的重要原因. 本文对六种不同的甲烷重整反应路径(干燥和湿润的气氛环境)进行了详细研究, 阐明了TiO2, Ni/TiO2界面和水分子在甲烷重整反应中的作用以及Ni/TiO2基阳极抗积碳性能的来源. 经过计算发现, 在干燥和湿润的环境下, 碳原子和界面的TiO2晶格氧反应生成CO以及后续水分子吸附和解离在界面的氧空位上并提供反应所需O原子是甲烷重整反应的主要路径(C-O路径), 而水分子直接参与C原子或者CH基团的氧化反应则要困难很多. 值得注意的是, 在研究的六种反应路径中, CO从反应表面的脱附都非常困难, 需要约2.3 eV的能量才能使得其脱附. 因而造成大量表面反应活性位点被占据, 这是目前很多阳极材料不具备抗积碳性能的一个重要原因. 然而, 在湿润环境中, 水分子的吸附放热大大降低了整个反应体系所需能量, 尤其是本文中水分子在TiO2表面的快速解离吸附更是大大降低了整个反应体系的能量. 进一步研究发现, 水分子在Ni, YSZ和CeO2表面的吸附解离要比在TiO2表面困难很多. 这也是TiO2 基阳极材料具有较好抗积碳性能的一个重要原因. 本研究对于指导合成碳氢燃料气氛下具有优异抗积碳性能的固体氧化物燃料电池阳极材料具有重要的意义.

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Acknowledgements

This work was financially supported by the National Basic Research Program of China (2017YFA0402800 and 2016YFA0200602), the National Natural Science Foundation of China (51472228 and 21573204), the Fundamental Research Funds for the Central Universities (WK3430000004), and the One Hundred Person Project of CAS. The authors acknowledge the Supercomputing Center of the University of Science and Technology of China and the National Supercomputing Center in Tianjin for providing computational resources. Figures with geometry are based on the Jmol package (Jmol: an opensource Java viewer for chemical structures in 3D. http://www.jmol.org/).

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Authors and Affiliations

  1. CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Wenqiang Yang  (杨文强), Zhenbin Wang  (王振斌), Wenzhou Tan  (谭文周), Ranran Peng  (彭冉冉), Xiaojun Wu  (武晓君) & Yalin Lu  (陆亚林)

  2. Hefei National Laboratory of Physical Science at the Microscale, University of Science and Technology of China, Hefei, 230026, China

    Xiaojun Wu  (武晓君) & Yalin Lu  (陆亚林)

  3. Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, 230026, China

    Xiaojun Wu  (武晓君) & Yalin Lu  (陆亚林)

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  1. Wenqiang Yang  (杨文强)
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  2. Zhenbin Wang  (王振斌)
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  3. Wenzhou Tan  (谭文周)
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  6. Yalin Lu  (陆亚林)
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Contributions

Author contributions Yang W designed and performed the calculations, analyzed the data, and wrote the paper; Wang Z helped build the computational models; Tan W made contributions to Fig. 9 in the manuscript; Peng R, Wu X and Lu Y conceived the framework of this paper and revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Ranran Peng  (彭冉冉), Xiaojun Wu  (武晓君) or Yalin Lu  (陆亚林).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Wenqiang Yang was born in Sichuan, China. He received his bachelor’s (2012) and master’s (2015) degrees in materials science from Nanjing University of Science and Technology and the University of Science and technology of China (USTC), respectively. He is now a PhD student at Andreas Heyden’s group at University of South Carolina. His current research focuses on computational heterogeneous catalysis and machine learning application on catalysis.

Ranran Peng received her PhD degree in materials science from the USTC in 2003. She currently is an associate professor in USTC. Her scientific interests include exploring novel electrode materials and revealing electrode reaction mechanisms for solid oxide fuel cells, and developing fantastic spintronic and multiferroic materials.

Yalin Lu was born in Jiangsu, China. He received his PhD from Nanjing University in 1991, and is now a full professor in USTC. Before joining USTC, he was a professor in AFA, Tufts University and Lawrence Berkeley National Laboratory. He currently serves as the Director of National Synchrotron Radiation Laboratory of China. His research focuses on quantum functional materials, nanophotonics, new energy materials and THz technologies.

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First principles study on methane reforming over Ni/TiO2(110) surface in solid oxide fuel cells under dry and wet atmospheres

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Yang, W., Wang, Z., Tan, W. et al. First principles study on methane reforming over Ni/TiO2(110) surface in solid oxide fuel cells under dry and wet atmospheres. Sci. China Mater. 63, 364–374 (2020). https://doi.org/10.1007/s40843-019-1218-1

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