The formation of O vacancy on ZrO2/Pd and its effect on methane dry reforming: Insights from DFT and microkinetic modeling

被引:16
作者
Shi, Xue-Rong [1 ]
Wang, Peijie [1 ]
Jing, Caihong [2 ]
Wu, Kaiwei [1 ]
Xu, Shusheng [1 ]
Klotzer, Bernhard [3 ]
机构
[1] Shanghai Univ Engn Sci, Sch Mat Sci & Engn, 333 Longteng Rd, Shanghai, Peoples R China
[2] Tongji Univ, Sch Mat Sci & Engn, Shanghai, Peoples R China
[3] Univ Innsbruck, Inst Phys Chem, Innrain 80-82, Innsbruck, Austria
基金
中国国家自然科学基金;
关键词
Dry reforming of methane; Density-functional theory; Microkinetic modeling; Oxide; metal catalyst; Oxygen defects; ZrO2; Pd phase boundary; WATER-GAS SHIFT; CATALYSTS; DISSOCIATION; SURFACE;
D O I
10.1016/j.apsusc.2023.156679
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The dry (CO2) reforming of CH4 (DRM) for syngas production is presently one of the most promising processes for CO2 utilization. Revealing the role of oxygen defects at ZrO2/Pd catalyst in DRM is crucial for the rational design and regulation of highly efficient and stable catalyst. This work employed first-principle calculations and microkinetic modeling to explore the DRM reaction mechanism on ZrO2/Pd at the atomic level. It is found that the reduction of perfect ZrO2 into Zr is impossible but the full reduction of hydroxylated zirconia ZrOxHy into Zr is feasible thermodynamically under the ultrahigh vacuum condition. The formation of O vacancy at the hy-droxylated phase boundary of ZrO2/Pd is feasible kinetically and thermodynamically as well. The yielded coordinatively unsaturated metal active center at the phase boundary of ZrO2/Pd can efficiently activate CO2 and promote the rate-limiting step of DRM. Both density-functional theory calculations and microkinetic modeling revealed a low surface carbon coverage at the phase boundary of ZrO2/Pd. This work proves the vital role of O vacancy and metal-oxide phase boundary in improving the DRM activity.
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页数:10
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  • [1] Structural and kinetic aspects of CO oxidation on ZnOx-modified Cu surfaces
    Bikaljevic, Djuro
    Rameshan, Raffael
    Koepfle, Norbert
    Goetsch, Thomas
    Muehlegger, Eva
    Schloegl, Robert
    Penner, Simon
    Memmel, Norbert
    Kloetzer, Bernhard
    [J]. APPLIED CATALYSIS A-GENERAL, 2019, 572 : 151 - 157
  • [2] CHD3 Dissociation on the Kinked Pt(210) Surface: A Comparison of Experiment and Theory
    Chadwick, Helen
    Gutierrez-Gonzalez, Ana
    Beck, Rainer D.
    Kroes, Geert-Jan
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2019, 123 (23) : 14530 - 14539
  • [3] Dry (CO2) reforming of methane over zirconium promoted Ni-MgO mixed oxide catalyst: Effect of Zr addition
    Chatla, Anjaneyulu
    Almanassra, Ismail W.
    Kallem, Parashuram
    Atieh, Muataz Ali
    Alawadhi, Hussain
    Akula, Venugopal
    Banat, Fawzi
    [J]. JOURNAL OF CO2 UTILIZATION, 2022, 62
  • [4] Dry reforming of methane over the cobalt catalyst: Theoretical insights into the reaction kinetics and mechanism for catalyst deactivation
    Chen, Shuyue
    Zaffran, Jeremie
    Yang, Bo
    [J]. APPLIED CATALYSIS B-ENVIRONMENTAL, 2020, 270
  • [5] Descriptor Design in the Computational Screening of Ni-Based Catalysts with Balanced Activity and Stability for Dry Reforming of Methane Reaction
    Chen, Shuyue
    Zaffran, Jeremie
    Yang, Bo
    [J]. ACS CATALYSIS, 2020, 10 (05): : 3074 - 3083
  • [6] The growth of ultra-thin zirconia films on Pd3Zr(0001)
    Choi, J. I. J.
    Mayr-Schmoelzer, W.
    Mittendorfer, F.
    Redinger, J.
    Diebold, U.
    Schmid, M.
    [J]. JOURNAL OF PHYSICS-CONDENSED MATTER, 2014, 26 (22)
  • [7] Plasma-assisted dry reforming of methane over Mo2C-Ni/Al2O3 catalysts: Effects of β-Mo2C promoter
    Diao, Yanan
    Zhang, Xiao
    Liu, Yang
    Chen, Bingbing
    Wu, Guohao
    Shi, Chuan
    [J]. APPLIED CATALYSIS B-ENVIRONMENTAL, 2022, 301
  • [8] A first-principles study on Pd modified ZSM-12 zeolites
    Feng, Gang
    Yang, Jinmei
    Wang, Changqing
    Lu, Kun
    Zhou, Jian
    Liu, Jianwen
    Wang, Xuewen
    Zhang, Rongbin
    Zhang, Ning
    [J]. MICROPOROUS AND MESOPOROUS MATERIALS, 2018, 260 : 227 - 234
  • [9] Contrasting the Role of Ni/Al2O3 Interfaces in Water-Gas Shift and Dry Reforming of Methane
    Foppa, Lucas
    Margossian, Tigran
    Kim, Sung Min
    Mueller, Christoph
    Coperet, Christophe
    Larmier, Kim
    Comas-Vives, Aleix
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (47) : 17128 - 17139
  • [10] Intrinsic reactivity of Ni, Pd and Pt surfaces in dry reforming and competitive reactions: Insights from first principles calculations and microkinetic modeling simulations
    Foppa, Lucas
    Silaghi, Marius-Christian
    Larmier, Kim
    Comas-Vives, Aleix
    [J]. JOURNAL OF CATALYSIS, 2016, 343 : 196 - 207