Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation

Adam F. Lee, Karen Wilson, Christopher M.A. Parlett, Christine V. Gaskell, Mark A. Newton, Zhi Liu

Research output: Contribution to conferenceAbstract

Abstract

The aerobic selective oxidation (selox) of alcohols represents an environmentally benign and atom efficient chemical valorisation route to commercially important allylic aldehydes, such as crotonaldehyde and cinnamaldehyde, which find application in pesticides, fragrances and food additives. Palladium nanoparticles are highly active and selective heterogeneous catalysts for such oxidative dehydrogenations, permitting the use of air (or dioxygen) as a green oxidant in place of stoichiometric chromate permanganate saltsor H2O2.
Here we discuss how time-resolved, in-situ X-ray spectroscopies (XAS and XPS) reveal dynamic restructuring of dispersed Pd nanoparticles and Pd single-crystals in response to changing reaction environments, and thereby identify surface PdO as the active species responsible for palladium catalysed crotyl alcohol selox (Figure 1); on-stream reduction to palladium metal under oxygen-poor regimes thus appears the primary cause of catalyst deactivation. This insight has guided the subsequent application of surfactant-templating and inorganic nanocrystal methodologies to optimize the density of desired active PdO sites for the selective oxidation of natural products such as sesquiterpenoids.

Original languageEnglish
Publication statusPublished - 10 Sep 2013
Event246th ACS national meeting and exposition - Indiana, Indianapolis, United States
Duration: 8 Sep 201312 Sep 2013

Meeting

Meeting246th ACS national meeting and exposition
CountryUnited States
CityIndianapolis
Period8/09/1312/09/13

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Palladium
2-butenal
Alcohols
Single crystals
Nanoparticles
Oxidation
Food additives
Oxygen
Chromates
Fragrances
Catalyst deactivation
Dehydrogenation
X ray spectroscopy
Biological Products
Pesticides
Oxidants
Aldehydes
Surface-Active Agents
Nanocrystals
X ray photoelectron spectroscopy

Cite this

Lee, A. F., Wilson, K., Parlett, C. M. A., Gaskell, C. V., Newton, M. A., & Liu, Z. (2013). Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation. Abstract from 246th ACS national meeting and exposition, Indianapolis, United States.
Lee, Adam F. ; Wilson, Karen ; Parlett, Christopher M.A. ; Gaskell, Christine V. ; Newton, Mark A. ; Liu, Zhi. / Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation. Abstract from 246th ACS national meeting and exposition, Indianapolis, United States.
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title = "Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation",
abstract = "The aerobic selective oxidation (selox) of alcohols represents an environmentally benign and atom efficient chemical valorisation route to commercially important allylic aldehydes, such as crotonaldehyde and cinnamaldehyde, which find application in pesticides, fragrances and food additives. Palladium nanoparticles are highly active and selective heterogeneous catalysts for such oxidative dehydrogenations, permitting the use of air (or dioxygen) as a green oxidant in place of stoichiometric chromate permanganate saltsor H2O2. Here we discuss how time-resolved, in-situ X-ray spectroscopies (XAS and XPS) reveal dynamic restructuring of dispersed Pd nanoparticles and Pd single-crystals in response to changing reaction environments, and thereby identify surface PdO as the active species responsible for palladium catalysed crotyl alcohol selox (Figure 1); on-stream reduction to palladium metal under oxygen-poor regimes thus appears the primary cause of catalyst deactivation. This insight has guided the subsequent application of surfactant-templating and inorganic nanocrystal methodologies to optimize the density of desired active PdO sites for the selective oxidation of natural products such as sesquiterpenoids.",
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Lee, AF, Wilson, K, Parlett, CMA, Gaskell, CV, Newton, MA & Liu, Z 2013, 'Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation' 246th ACS national meeting and exposition, Indianapolis, United States, 8/09/13 - 12/09/13, .

Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation. / Lee, Adam F.; Wilson, Karen; Parlett, Christopher M.A.; Gaskell, Christine V.; Newton, Mark A.; Liu, Zhi.

2013. Abstract from 246th ACS national meeting and exposition, Indianapolis, United States.

Research output: Contribution to conferenceAbstract

TY - CONF

T1 - Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation

AU - Lee, Adam F.

AU - Wilson, Karen

AU - Parlett, Christopher M.A.

AU - Gaskell, Christine V.

AU - Newton, Mark A.

AU - Liu, Zhi

PY - 2013/9/10

Y1 - 2013/9/10

N2 - The aerobic selective oxidation (selox) of alcohols represents an environmentally benign and atom efficient chemical valorisation route to commercially important allylic aldehydes, such as crotonaldehyde and cinnamaldehyde, which find application in pesticides, fragrances and food additives. Palladium nanoparticles are highly active and selective heterogeneous catalysts for such oxidative dehydrogenations, permitting the use of air (or dioxygen) as a green oxidant in place of stoichiometric chromate permanganate saltsor H2O2. Here we discuss how time-resolved, in-situ X-ray spectroscopies (XAS and XPS) reveal dynamic restructuring of dispersed Pd nanoparticles and Pd single-crystals in response to changing reaction environments, and thereby identify surface PdO as the active species responsible for palladium catalysed crotyl alcohol selox (Figure 1); on-stream reduction to palladium metal under oxygen-poor regimes thus appears the primary cause of catalyst deactivation. This insight has guided the subsequent application of surfactant-templating and inorganic nanocrystal methodologies to optimize the density of desired active PdO sites for the selective oxidation of natural products such as sesquiterpenoids.

AB - The aerobic selective oxidation (selox) of alcohols represents an environmentally benign and atom efficient chemical valorisation route to commercially important allylic aldehydes, such as crotonaldehyde and cinnamaldehyde, which find application in pesticides, fragrances and food additives. Palladium nanoparticles are highly active and selective heterogeneous catalysts for such oxidative dehydrogenations, permitting the use of air (or dioxygen) as a green oxidant in place of stoichiometric chromate permanganate saltsor H2O2. Here we discuss how time-resolved, in-situ X-ray spectroscopies (XAS and XPS) reveal dynamic restructuring of dispersed Pd nanoparticles and Pd single-crystals in response to changing reaction environments, and thereby identify surface PdO as the active species responsible for palladium catalysed crotyl alcohol selox (Figure 1); on-stream reduction to palladium metal under oxygen-poor regimes thus appears the primary cause of catalyst deactivation. This insight has guided the subsequent application of surfactant-templating and inorganic nanocrystal methodologies to optimize the density of desired active PdO sites for the selective oxidation of natural products such as sesquiterpenoids.

UR - http://abstracts.acs.org/chem/246nm/program/view.php?obj_id=206013&terms=

M3 - Abstract

ER -

Lee AF, Wilson K, Parlett CMA, Gaskell CV, Newton MA, Liu Z. Dynamic restructuring of Pd nanoparticles and single crystals during catalytic selective alcohol oxidation. 2013. Abstract from 246th ACS national meeting and exposition, Indianapolis, United States.