Nickel Speciation and Methane Dry Reforming Performance of Ni/CexZr1–xO2 Prepared by Different Synthesis Methods

  • Yimeng Lyu
    Yimeng Lyu
    School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
    More by Yimeng Lyu
  • Jennifer Jocz
    Jennifer Jocz
    School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
  • Rui Xu
    Rui Xu
    School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
    More by Rui Xu
  • Eli Stavitski
    Eli Stavitski
    National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, United States
  • , and 
  • Carsten Sievers*
    Carsten Sievers
    School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
    *Email: [email protected]
Cite this: ACS Catal. 2020, 10, 19, 11235–11252
Publication Date (Web):September 3, 2020
Copyright © 2020 American Chemical Society
Article Views
Read OnlinePDF (5 MB)
Supporting Info (1)»


Ceria–zirconia-supported Ni catalysts (Ni/Ce0.83Zr0.17O2 or Ni/CZ) are prepared by dry impregnation, strong electrostatic adsorption, coprecipitation (CP), and combustion synthesis (CS). The nature and abundance of Ni species in these samples are characterized by X-ray adsorption spectroscopy, temperature-programmed reduction, and CO chemisorption. The bulk synthesis methods (i.e., CP and CS) produce Ni cations that are incorporated into the CZ lattice forming mixed-metal oxides with Ni3+ species at low Ni content. The formation of mixed-metal oxides increases the reducibility of CZ and increases the abundance of active surface oxygen. All NiO/CZ catalysts are active for methane dry reforming and retain some of their activity at a steady state. The initial methane conversion correlates linearly with the fraction of accessible Ni after reduction. The predominant path of catalyst deactivation strongly depends on the structure of the catalyst and, thus, on the synthesis method used. All catalysts experience agglomeration of Ni particles under reaction conditions. Improving the Ni dispersion to isolated species embedded in a support does not improve resistance to Ni particle growth. Coke formation is inversely related to the concentration of active surface oxygen. The dominant deactivation mechanism for catalysts made by CS is the encapsulation of Ni particles by the support.

Supporting Information

Jump To

The Supporting Information is available free of charge at

  • Adsorption/desorption isotherms and pore size distribution for unreduced samples; linear combination fitting of XANES spectra for unreduced catalysts; standards used for LCF XANES fittings; EXAFS fits and fitted parameters for unreduced samples; XPS survey scans and XPS Ni 2p spectra for unreduced samples; XPS fits and fitted parameters for unreduced samples; deconvoluted TPR patterns; reactivity performance for all samples; adsorption/desorption isotherms and pore size distribution for spent samples; TGA of spent samples; SEM images of spent samples; and relationship between the initial CO2 conversion and the surface Ni concentration (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 13 publications.

  1. Zhourong Xiao, Fang Hou, Junjie Zhang, Qiancheng Zheng, Jisheng Xu, Lun Pan, Li Wang, Jijun Zou, Xiangwen Zhang, Guozhu Li. Methane Dry Reforming by Ni–Cu Nanoalloys Anchored on Periclase-Phase MgAlOx Nanosheets for Enhanced Syngas Production. ACS Applied Materials & Interfaces 2021, 13 (41) , 48838-48854.
  2. Xiaoyu Zhang, Jiang Deng, Max Pupucevski, Sarawoot Impeng, Bo Yang, Guorong Chen, Sanchai Kuboon, Qingdong Zhong, Kajornsak Faungnawakij, Lirong Zheng, Gang Wu, Dengsong Zhang. High-Performance Binary Mo–Ni Catalysts for Efficient Carbon Removal during Carbon Dioxide Reforming of Methane. ACS Catalysis 2021, 11 (19) , 12087-12095.
  3. Yongdi Zhang, Shaowen Wu, Yuanzhi Li, An Zhang, Qianqian Hu, Jichun Wu, Xin Tan. Quasi-Monolayer Rh Nanoclusters Stabilized on Spinel MgAl2O4 Nanosheets for Catalytic CO2 Reforming of Methane. ACS Applied Nano Materials 2021, 4 (9) , 9866-9875.
  4. Yimeng Lyu, Rui Xu, Olivia Williams, Ziyuan Wang, Carsten Sievers. Reaction paths of methane activation and oxidation of surface intermediates over NiO on Ceria-Zirconia catalysts studied by In-situ FTIR spectroscopy. Journal of Catalysis 2021, 404 , 334-347.
  5. Jiawei Hu, Plaifa Hongmanorom, Prae Chirawatkul, Sibudjing Kawi. Efficient integration of CO2 capture and conversion over a Ni supported CeO2-modified CaO microsphere at moderate temperature. Chemical Engineering Journal 2021, 426 , 130864.
  6. Shuangshuang Zhang, Tao Yang, Jun Yu, Wangcheng Zhan, Li Wang, Yun Guo, Yanglong Guo. Robust nanosheet-assembled Al 2 O 3 -supported Ni catalysts for the dry reforming of methane: the effect of nickel content on the catalytic performance and carbon formation. New Journal of Chemistry 2021, 45 (46) , 21750-21762.
  7. Plaifa Hongmanorom, Jangam Ashok, Prae Chirawatkul, Sibudjing Kawi. Interfacial synergistic catalysis over Ni nanoparticles encapsulated in mesoporous ceria for CO2 methanation. Applied Catalysis B: Environmental 2021, 297 , 120454.
  8. Sixue Lin, Jing Wang, Yangyang Mi, Senyou Yang, Zheng Wang, Wenming Liu, Daishe Wu, Honggen Peng. Trifunctional strategy for the design and synthesis of a [email protected] catalyst with remarkable low-temperature sintering and coking resistance for methane dry reforming. Chinese Journal of Catalysis 2021, 42 (10) , 1808-1820.
  9. Zhenxin Lin, Kai Zhao, Gang Cheng, Shuozhen Hu, Min Chen, Jun Li, Dongchu Chen, Qing Xu, Menglei Chang, Ogenko Volodymyr. Catalyst layer supported solid oxide fuel cells running on methane. Journal of Power Sources 2021, 507 , 230317.
  10. Qiangqiang Xue, Zhengwen Li, Meng Chen, Yujun Wang, Binhang Yan, Guangsheng Luo. Co-precipitation continuous synthesis of the Ni-Rh-Ce0.75Zr0.25O2-δ catalyst in the membrane dispersion microreactor system for n-dodecane steam reforming to hydrogen. Fuel 2021, 297 , 120785.
  11. Yimeng Lyu, Jennifer N. Jocz, Rui Xu, Olivia C. Williams, Carsten Sievers. Selective Oxidation of Methane to Methanol over Ceria‐Zirconia Supported Mono and Bimetallic Transition Metal Oxide Catalysts. ChemCatChem 2021, 13 (12) , 2832-2842.
  12. Shuang Yang, Dedong He, Liming Zhang, Yaliu Zhang, Jichang Lu, Yongming Luo. Toxic chromium treatment induce amino-assisted electrostatic adsorption for the synthesis of highly dispersed chromium catalyst. Journal of Hazardous Materials 2021, 354 , 126155.
  13. Dmitriy M. Zakharov, Nikolay A. Zhuravlev, Tatiana A. Denisova, Alexander S. Belozerov, Anna Yu. Stroeva, Emma G. Vovkotrub, Andrei S. Farlenkov, Maxim V. Ananyev. Catalytic methane activation over La1−xSrxScO3−α proton-conducting oxide surface: A comprehensive study. Journal of Catalysis 2021, 394 , 67-82.