Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Yanan Liu, Alan J. McCue, Junting Feng, Shaoliang Guan, Dianqing Li, James A. Anderson

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Unsupported, bulk phase palladium sulfide has been studied for the selective hydrogenation of acetylene. The sample underwent significant change during thermal pretreatments, the extent of which depends on temperature. Exposure to hydrogen at temperatures of 150°C or above results in the loss of sulfur from the sample, primarily as hydrogen sulfide. As sulfur is lost, the sample is progressively transformed from a sulfur rich phase (PdS) to a sulfur lean phase (Pd4S) via an intermediate phase (Pd16S7). Reduction at 250°C produces a material, which contains Pd4S as the surface phase, whereas reduction at 350°C results in a largely pure Pd4S phase. Thermal treatments which produce a Pd4S surface display excellent catalytic properties. At complete acetylene conversion at 250°C, ethylene selectivites of 82.8% and 90.0% were obtained under non-competitive and competitive conditions, respectively. Beneficial catalytic properties arise from the uniformity of Pd sites due to the crystal structure of Pd4S along with electronic influences on the adsorption/desorption processes arising from sulfur neighbours. No indications of deactivation or significant deposition of carbon were observed over Pd4S sample after 50 h on stream.
Original languageEnglish
Pages (from-to)204-215
Number of pages12
JournalJournal of Catalysis
Volume364
Early online date14 Jun 2018
DOIs
Publication statusPublished - Aug 2018

Fingerprint

Acetylene
Palladium
Sulfides
Sulfur
acetylene
Hydrogenation
hydrogenation
sulfides
palladium
sulfur
Heat treatment
Hydrogen Sulfide
hydrogen sulfide
Hydrogen sulfide
pretreatment
deactivation
Hydrogen
Desorption
Ethylene
indication

Keywords

  • Acetylene
  • ethylene
  • selective hydrogenation
  • palladium sulphide

Cite this

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation. / Liu, Yanan; McCue, Alan J.; Feng, Junting; Guan, Shaoliang; Li, Dianqing; Anderson, James A.

In: Journal of Catalysis, Vol. 364, 08.2018, p. 204-215.

Research output: Contribution to journalArticle

Liu, Yanan ; McCue, Alan J. ; Feng, Junting ; Guan, Shaoliang ; Li, Dianqing ; Anderson, James A. / Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation. In: Journal of Catalysis. 2018 ; Vol. 364. pp. 204-215.
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abstract = "Unsupported, bulk phase palladium sulfide has been studied for the selective hydrogenation of acetylene. The sample underwent significant change during thermal pretreatments, the extent of which depends on temperature. Exposure to hydrogen at temperatures of 150°C or above results in the loss of sulfur from the sample, primarily as hydrogen sulfide. As sulfur is lost, the sample is progressively transformed from a sulfur rich phase (PdS) to a sulfur lean phase (Pd4S) via an intermediate phase (Pd16S7). Reduction at 250°C produces a material, which contains Pd4S as the surface phase, whereas reduction at 350°C results in a largely pure Pd4S phase. Thermal treatments which produce a Pd4S surface display excellent catalytic properties. At complete acetylene conversion at 250°C, ethylene selectivites of 82.8{\%} and 90.0{\%} were obtained under non-competitive and competitive conditions, respectively. Beneficial catalytic properties arise from the uniformity of Pd sites due to the crystal structure of Pd4S along with electronic influences on the adsorption/desorption processes arising from sulfur neighbours. No indications of deactivation or significant deposition of carbon were observed over Pd4S sample after 50 h on stream.",
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author = "Yanan Liu and McCue, {Alan J.} and Junting Feng and Shaoliang Guan and Dianqing Li and Anderson, {James A.}",
note = "We thank Diamond Light Source for beamline access B18 (SP15151-5) and are grateful to the expertise and help provided by Dr Emma Gibson (UK Catalysis Hub, Harwell) and Diego Gianolio (Beamline Scientist on B18) whilst data collecting. XPS data collection was performed at the EPSRC National Facility for XPS (‘HarwellXPS’), operated by Cardiff University and UCL, under contract No. PR16195. We would also like to thank Prof. Philip R. Davies for helpful discussions on XPS data analysis. This work was partly supported by the National Key Research and Development Program of China (2016YFB0301601), National Natural Science Foundation of China.",
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AU - Anderson, James A.

N1 - We thank Diamond Light Source for beamline access B18 (SP15151-5) and are grateful to the expertise and help provided by Dr Emma Gibson (UK Catalysis Hub, Harwell) and Diego Gianolio (Beamline Scientist on B18) whilst data collecting. XPS data collection was performed at the EPSRC National Facility for XPS (‘HarwellXPS’), operated by Cardiff University and UCL, under contract No. PR16195. We would also like to thank Prof. Philip R. Davies for helpful discussions on XPS data analysis. This work was partly supported by the National Key Research and Development Program of China (2016YFB0301601), National Natural Science Foundation of China.

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N2 - Unsupported, bulk phase palladium sulfide has been studied for the selective hydrogenation of acetylene. The sample underwent significant change during thermal pretreatments, the extent of which depends on temperature. Exposure to hydrogen at temperatures of 150°C or above results in the loss of sulfur from the sample, primarily as hydrogen sulfide. As sulfur is lost, the sample is progressively transformed from a sulfur rich phase (PdS) to a sulfur lean phase (Pd4S) via an intermediate phase (Pd16S7). Reduction at 250°C produces a material, which contains Pd4S as the surface phase, whereas reduction at 350°C results in a largely pure Pd4S phase. Thermal treatments which produce a Pd4S surface display excellent catalytic properties. At complete acetylene conversion at 250°C, ethylene selectivites of 82.8% and 90.0% were obtained under non-competitive and competitive conditions, respectively. Beneficial catalytic properties arise from the uniformity of Pd sites due to the crystal structure of Pd4S along with electronic influences on the adsorption/desorption processes arising from sulfur neighbours. No indications of deactivation or significant deposition of carbon were observed over Pd4S sample after 50 h on stream.

AB - Unsupported, bulk phase palladium sulfide has been studied for the selective hydrogenation of acetylene. The sample underwent significant change during thermal pretreatments, the extent of which depends on temperature. Exposure to hydrogen at temperatures of 150°C or above results in the loss of sulfur from the sample, primarily as hydrogen sulfide. As sulfur is lost, the sample is progressively transformed from a sulfur rich phase (PdS) to a sulfur lean phase (Pd4S) via an intermediate phase (Pd16S7). Reduction at 250°C produces a material, which contains Pd4S as the surface phase, whereas reduction at 350°C results in a largely pure Pd4S phase. Thermal treatments which produce a Pd4S surface display excellent catalytic properties. At complete acetylene conversion at 250°C, ethylene selectivites of 82.8% and 90.0% were obtained under non-competitive and competitive conditions, respectively. Beneficial catalytic properties arise from the uniformity of Pd sites due to the crystal structure of Pd4S along with electronic influences on the adsorption/desorption processes arising from sulfur neighbours. No indications of deactivation or significant deposition of carbon were observed over Pd4S sample after 50 h on stream.

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