High-Performance PdNi Nanoalloy Catalyst in Situ Structured on Ni Foam for Catalytic Deoxygenation of Coalbed Methane: Experimental and DFT Studies

Qiaofei Zhang, Xin Ping Wu, Yakun Li, Ruijuan Chai, Guofeng Zhao, Chunzheng Wang, Xue Qing Gong, Ye Liu, Yong Lu

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

A Ni-foam-structured PdNi nanoalloy catalyst engineered from nano- to macro-scales has been successfully fabricated for the catalytic deoxygenation of coalbed methane (CBM). The catalyst was obtainable by embedment of Pd nanoparticles onto Ni-foam substrate via a galvanic exchange reaction method and subsequent in situ activation in the reaction, which was active at low temperature, selective (no CO formation), and oscillation free in this CH4-rich catalytic combustion process. Special Pd@NiO (Pd nanoparticles partially wrapped by tiny NiO fragments) ensembles were formed in the galvanic deposition stage and could merely be transformed into PdNi nanoalloys in the real reaction stream at elevated temperatures (e.g., 450 °C or higher). Density functional theory (DFT) calculations were carried out to reveal the role of Ni decoration at Pd in PdNi nanoalloy catalyst for the CBM deoxygenation. By nature, the Pd-Ni alloying modified the electronic structure of surface Pd and led to a decrease in the O adsorption energy, which can be taken as the activity descriptor for the CBM deoxygenation. A reaction kinetic study indicated that the Ni decoration at Pd by Pd-Ni alloying lowered the apparent activation energy in comparison to the pristine Pd catalyst, while leading to an increase of the reaction order of O2 from -0.6 at Pd catalyst to -0.3. The foam-structured PdNi nanoalloy catalyst thus offered enhanced low-temperature activity and the elimination of oscillating phenomena as the result of a transient balance obtained between the cycles of O2 adsorption/activation and CH4 oxidation.

Original languageEnglish (US)
Pages (from-to)6236-6245
Number of pages10
JournalACS Catalysis
Volume6
Issue number9
DOIs
StatePublished - Sep 2 2016

Fingerprint

Density functional theory
Foams
Catalysts
Alloying
Chemical activation
Nanoparticles
Adsorption
Carbon Monoxide
Reaction kinetics
Temperature
Electronic structure
Macros
Coal bed methane
Ion exchange
Activation energy
Oxidation
Substrates

Keywords

  • DFT calculations
  • catalytic combustion
  • coalbed methane
  • foam
  • nanoalloy catalysis
  • reaction kinetics
  • structured catalyst

Cite this

High-Performance PdNi Nanoalloy Catalyst in Situ Structured on Ni Foam for Catalytic Deoxygenation of Coalbed Methane : Experimental and DFT Studies. / Zhang, Qiaofei; Wu, Xin Ping; Li, Yakun; Chai, Ruijuan; Zhao, Guofeng; Wang, Chunzheng; Gong, Xue Qing; Liu, Ye; Lu, Yong.

In: ACS Catalysis, Vol. 6, No. 9, 02.09.2016, p. 6236-6245.

Research output: Contribution to journalArticle

Zhang, Qiaofei ; Wu, Xin Ping ; Li, Yakun ; Chai, Ruijuan ; Zhao, Guofeng ; Wang, Chunzheng ; Gong, Xue Qing ; Liu, Ye ; Lu, Yong. / High-Performance PdNi Nanoalloy Catalyst in Situ Structured on Ni Foam for Catalytic Deoxygenation of Coalbed Methane : Experimental and DFT Studies. In: ACS Catalysis. 2016 ; Vol. 6, No. 9. pp. 6236-6245.
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abstract = "A Ni-foam-structured PdNi nanoalloy catalyst engineered from nano- to macro-scales has been successfully fabricated for the catalytic deoxygenation of coalbed methane (CBM). The catalyst was obtainable by embedment of Pd nanoparticles onto Ni-foam substrate via a galvanic exchange reaction method and subsequent in situ activation in the reaction, which was active at low temperature, selective (no CO formation), and oscillation free in this CH4-rich catalytic combustion process. Special Pd@NiO (Pd nanoparticles partially wrapped by tiny NiO fragments) ensembles were formed in the galvanic deposition stage and could merely be transformed into PdNi nanoalloys in the real reaction stream at elevated temperatures (e.g., 450 °C or higher). Density functional theory (DFT) calculations were carried out to reveal the role of Ni decoration at Pd in PdNi nanoalloy catalyst for the CBM deoxygenation. By nature, the Pd-Ni alloying modified the electronic structure of surface Pd and led to a decrease in the O adsorption energy, which can be taken as the activity descriptor for the CBM deoxygenation. A reaction kinetic study indicated that the Ni decoration at Pd by Pd-Ni alloying lowered the apparent activation energy in comparison to the pristine Pd catalyst, while leading to an increase of the reaction order of O2 from -0.6 at Pd catalyst to -0.3. The foam-structured PdNi nanoalloy catalyst thus offered enhanced low-temperature activity and the elimination of oscillating phenomena as the result of a transient balance obtained between the cycles of O2 adsorption/activation and CH4 oxidation.",
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AU - Zhang, Qiaofei

AU - Wu, Xin Ping

AU - Li, Yakun

AU - Chai, Ruijuan

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AU - Wang, Chunzheng

AU - Gong, Xue Qing

AU - Liu, Ye

AU - Lu, Yong

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N2 - A Ni-foam-structured PdNi nanoalloy catalyst engineered from nano- to macro-scales has been successfully fabricated for the catalytic deoxygenation of coalbed methane (CBM). The catalyst was obtainable by embedment of Pd nanoparticles onto Ni-foam substrate via a galvanic exchange reaction method and subsequent in situ activation in the reaction, which was active at low temperature, selective (no CO formation), and oscillation free in this CH4-rich catalytic combustion process. Special Pd@NiO (Pd nanoparticles partially wrapped by tiny NiO fragments) ensembles were formed in the galvanic deposition stage and could merely be transformed into PdNi nanoalloys in the real reaction stream at elevated temperatures (e.g., 450 °C or higher). Density functional theory (DFT) calculations were carried out to reveal the role of Ni decoration at Pd in PdNi nanoalloy catalyst for the CBM deoxygenation. By nature, the Pd-Ni alloying modified the electronic structure of surface Pd and led to a decrease in the O adsorption energy, which can be taken as the activity descriptor for the CBM deoxygenation. A reaction kinetic study indicated that the Ni decoration at Pd by Pd-Ni alloying lowered the apparent activation energy in comparison to the pristine Pd catalyst, while leading to an increase of the reaction order of O2 from -0.6 at Pd catalyst to -0.3. The foam-structured PdNi nanoalloy catalyst thus offered enhanced low-temperature activity and the elimination of oscillating phenomena as the result of a transient balance obtained between the cycles of O2 adsorption/activation and CH4 oxidation.

AB - A Ni-foam-structured PdNi nanoalloy catalyst engineered from nano- to macro-scales has been successfully fabricated for the catalytic deoxygenation of coalbed methane (CBM). The catalyst was obtainable by embedment of Pd nanoparticles onto Ni-foam substrate via a galvanic exchange reaction method and subsequent in situ activation in the reaction, which was active at low temperature, selective (no CO formation), and oscillation free in this CH4-rich catalytic combustion process. Special Pd@NiO (Pd nanoparticles partially wrapped by tiny NiO fragments) ensembles were formed in the galvanic deposition stage and could merely be transformed into PdNi nanoalloys in the real reaction stream at elevated temperatures (e.g., 450 °C or higher). Density functional theory (DFT) calculations were carried out to reveal the role of Ni decoration at Pd in PdNi nanoalloy catalyst for the CBM deoxygenation. By nature, the Pd-Ni alloying modified the electronic structure of surface Pd and led to a decrease in the O adsorption energy, which can be taken as the activity descriptor for the CBM deoxygenation. A reaction kinetic study indicated that the Ni decoration at Pd by Pd-Ni alloying lowered the apparent activation energy in comparison to the pristine Pd catalyst, while leading to an increase of the reaction order of O2 from -0.6 at Pd catalyst to -0.3. The foam-structured PdNi nanoalloy catalyst thus offered enhanced low-temperature activity and the elimination of oscillating phenomena as the result of a transient balance obtained between the cycles of O2 adsorption/activation and CH4 oxidation.

KW - DFT calculations

KW - catalytic combustion

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KW - nanoalloy catalysis

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