On the Role of Oxygen in the Liquid-Phase Aerobic Oxidation of Alcohols on Palladium

Keresszegi, Csilla; Bürgi, Thomas; Mallát, Tamás; Baiker, Alfons

doi:10.1006/jcat.2002.3723

Cited by 80 publications

(127 citation statements)

References 41 publications

Supporting

Mentioning

121

Contrasting

Order By: Relevance

“…The preceding observation that surface oxygen is not only critical for the removal of hydrogen adatoms but also to suppress decarbonylation of selox products over metallic palladium is in excellent agreement with an in situ ATR-IR study of cinnamyl alcohol selox over Pd/Al 2 O 3 [148]. In related earlier investigations employing aqueous electrochemical protocols, the same researchers postulated that oxidative dehydrogenation of alcohols requires PGM catalysts in a reduced state, hypothesising that 'over-oxidation' was responsible for deactivation of palladium selox catalysts [69].…”

Section: Nature Of the Active Sitesupporting

confidence: 81%

“…12 Impact of oxygen on the selective oxidation of (top left) cinnamyl alcohol; (bottom left) 1-phenylethanol; and (right) 2-octanol. Adapted from references [148,151,154] with permission from Elsevier temperatures, palladium nanoparticles were partially oxidised, and unperturbed by exposure to sequential alcohol or oxygen pulses (Fig. 14).…”

Section: Nature Of the Active Sitementioning

confidence: 99%

See 1 more Smart Citation

Catalysing Sustainable Fuel and Chemical Synthesis

Lee¹

2015

Advanced Biofuels

View full text Add to dashboard Cite

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO 2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century's grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands.

show abstract

Section: Nature Of the Active Sitesupporting

confidence: 81%

Section: Nature Of the Active Sitementioning

confidence: 99%

Catalysing Sustainable Fuel and Chemical Synthesis

Lee¹

2015

Advanced Biofuels

View full text Add to dashboard Cite

show abstract

“…However, the cinnamaldehyde product is unstable with respect to decarbonylation (to styrene) and hydrogenation (to 3-phenylpropionaldehyde), leaving only 22 % of reactively formed cinnamaldehyde intact. [3][4][5][6][7][8][9][10][11][12][13][14][15] phenylpropionaldehyde intermediate is itself extremely unstable with respect to subsequent oxidation to the corresponding 3-phenylpropanoic acid. Interestingly, reactively-formed cinnamaldehyde does not undergo over-oxidation to cinnamic acid under our conditions, presumably because surface hydrogen 20 co-liberated during its formation from cinnamyl alcohol promotes competing hydrogenolysis/hydrogenation pathways.…”

Section: Cinnamyl Alcohol Selective Oxidationmentioning

confidence: 99%

“…[7][8][9] Palladium has been extensively studied for the selective oxidation of allylic alcohols, 4,[10][11][12] wherein sophisticated in-situ/operando spectroscopic and kinetic measurements have identified surface PdO as the active site responsible for crotyl and cinnamyl alcohol. 13 22 is also effective towards allylic alcohol selox.…”

Section: Introductionmentioning

confidence: 99%

Tunable Pt nanocatalysts for the aerobic selox of cinnamyl alcohol

et al. 2013

View full text Add to dashboard Cite

The selective aerobic oxidation of cinnamyl alcohol over Pt nanoparticles has been tuning via the use of 5 mesoporous silica supports to control their dispersion and oxidation state. High area two-dimensional SBA-15, and three-dimensional, interconnected KIT-6 silica significantly enhance Pt dispersion, and thus surface PtO 2 concentration, over that achievable via commercial low surface area silica. Selective oxidation activity scales with Pt dispersion in the order KIT-6 ≥ SBA-15 > SiO 2 , evidencing surface PtO 2 as the active site for cinnamyl alcohol selox to cinnamaldehyde. Kinetic mapping has quantified key 10 reaction pathways, and the importance of high O 2 partial pressures for cinnamaldehyde production.

show abstract

“…In a more general perspective, poisoning impurities in the feed can be eliminated by dedicated treatments. In selective oxidation over noble metal catalysts, deactivation can also occur due to the over-oxidation of Pt [14] and Pd [14,17] catalysts when an excess of (molecular) oxygen is present. This over-oxidation means that too much atomic oxygen (a reaction intermediate) is present on the catalytic sites, thereby blocking their accessibility for hydrocarbon adsorption.…”

Section: Introductionmentioning

confidence: 99%

Inhibition of a Gold-Based Catalyst in Benzyl Alcohol Oxidation: Understanding and Remediation

et al. 2014

View full text Add to dashboard Cite

Benzyl alcohol oxidation was carried out in toluene as solvent, in the presence of the potentially inhibiting oxidation products benzaldehyde and benzoic acid. Benzoic acid, or a product of benzoic acid, is identified to be the inhibiting species. The presence of a basic potassium salt (K 2 CO 3 or KF) suppresses this inhibition, but promotes the formation of benzyl benzoate from the alcohol and aldehyde. When a small amount of water is added together with the potassium salt, an even greater beneficial effect is observed, due to a synergistic effect with the base. A kinetic model, based on the three main reactions and four major reaction components, is presented to describe the concentration-time profiles and inhibition. The inhibition, as well as the effect of the base, was captured in the kinetic model, by combining strong benzoic acid adsorption and competitive adsorption with benzyl alcohol. The effect of the potassium salt is accounted for in terms of neutralization of benzoic acid. OPEN ACCESSCatalysts 2014, 4 90

show abstract

On the Role of Oxygen in the Liquid-Phase Aerobic Oxidation of Alcohols on Palladium

Cited by 80 publications

References 41 publications

Catalysing Sustainable Fuel and Chemical Synthesis

Catalysing Sustainable Fuel and Chemical Synthesis

Tunable Pt nanocatalysts for the aerobic selox of cinnamyl alcohol

Inhibition of a Gold-Based Catalyst in Benzyl Alcohol Oxidation: Understanding and Remediation

Contact Info

Product

Resources

About